US20090071067A1 - Environmentally-Friendly Additives And Additive Compositions For Solid Fuels - Google Patents
Environmentally-Friendly Additives And Additive Compositions For Solid Fuels Download PDFInfo
- Publication number
- US20090071067A1 US20090071067A1 US11/856,205 US85620507A US2009071067A1 US 20090071067 A1 US20090071067 A1 US 20090071067A1 US 85620507 A US85620507 A US 85620507A US 2009071067 A1 US2009071067 A1 US 2009071067A1
- Authority
- US
- United States
- Prior art keywords
- compounds
- organometallic
- test
- inorganic
- additive composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 117
- 239000000654 additive Substances 0.000 title claims abstract description 59
- 230000000996 additive effect Effects 0.000 title claims abstract description 51
- 239000004449 solid propellant Substances 0.000 title claims abstract description 32
- 239000000446 fuel Substances 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 46
- 239000002816 fuel additive Substances 0.000 claims abstract description 32
- 231100000693 bioaccumulation Toxicity 0.000 claims abstract description 31
- 230000002085 persistent effect Effects 0.000 claims abstract description 22
- 231100000252 nontoxic Toxicity 0.000 claims abstract description 13
- 230000003000 nontoxic effect Effects 0.000 claims abstract description 12
- 238000012360 testing method Methods 0.000 claims description 193
- -1 alkyl nitrates Chemical class 0.000 claims description 82
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 52
- 150000001875 compounds Chemical class 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- 239000003607 modifier Substances 0.000 claims description 27
- 239000010802 sludge Substances 0.000 claims description 25
- 238000006065 biodegradation reaction Methods 0.000 claims description 24
- 238000002485 combustion reaction Methods 0.000 claims description 24
- 241000251468 Actinopterygii Species 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 23
- 231100000704 bioconcentration Toxicity 0.000 claims description 21
- 239000003245 coal Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 229910052748 manganese Inorganic materials 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 20
- 239000002893 slag Substances 0.000 claims description 19
- 229910052749 magnesium Inorganic materials 0.000 claims description 18
- 239000011777 magnesium Substances 0.000 claims description 18
- 150000002736 metal compounds Chemical class 0.000 claims description 18
- 230000002588 toxic effect Effects 0.000 claims description 18
- 150000002902 organometallic compounds Chemical class 0.000 claims description 17
- 231100000331 toxic Toxicity 0.000 claims description 17
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 239000002023 wood Substances 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- 230000007797 corrosion Effects 0.000 claims description 13
- 238000005260 corrosion Methods 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 13
- 241000238578 Daphnia Species 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- 239000013049 sediment Substances 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- 230000007059 acute toxicity Effects 0.000 claims description 11
- 231100000403 acute toxicity Toxicity 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 150000001298 alcohols Chemical class 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000003085 diluting agent Substances 0.000 claims description 10
- 150000002170 ethers Chemical class 0.000 claims description 10
- 230000005764 inhibitory process Effects 0.000 claims description 10
- 239000002006 petroleum coke Substances 0.000 claims description 10
- 230000029058 respiratory gaseous exchange Effects 0.000 claims description 10
- 240000008042 Zea mays Species 0.000 claims description 9
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 9
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 9
- 150000007942 carboxylates Chemical class 0.000 claims description 9
- 235000005822 corn Nutrition 0.000 claims description 9
- 239000012530 fluid Substances 0.000 claims description 9
- 125000002524 organometallic group Chemical group 0.000 claims description 9
- 239000010451 perlite Substances 0.000 claims description 9
- 235000019362 perlite Nutrition 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000010455 vermiculite Substances 0.000 claims description 9
- 229910052902 vermiculite Inorganic materials 0.000 claims description 9
- 235000019354 vermiculite Nutrition 0.000 claims description 9
- 239000002028 Biomass Substances 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 150000001805 chlorine compounds Chemical class 0.000 claims description 8
- 239000000571 coke Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 150000004694 iodide salts Chemical class 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 150000002823 nitrates Chemical class 0.000 claims description 8
- 239000013110 organic ligand Substances 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 239000003473 refuse derived fuel Substances 0.000 claims description 8
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 8
- 231100000820 toxicity test Toxicity 0.000 claims description 8
- 239000012717 electrostatic precipitator Substances 0.000 claims description 7
- 239000003230 hygroscopic agent Substances 0.000 claims description 7
- 235000012245 magnesium oxide Nutrition 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000002689 soil Substances 0.000 claims description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- ANHQLUBMNSSPBV-UHFFFAOYSA-N 4h-pyrido[3,2-b][1,4]oxazin-3-one Chemical group C1=CN=C2NC(=O)COC2=C1 ANHQLUBMNSSPBV-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000005749 Copper compound Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 150000001880 copper compounds Chemical class 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 150000002697 manganese compounds Chemical class 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 235000010755 mineral Nutrition 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- DEIHRWXJCZMTHF-UHFFFAOYSA-N [Mn].[CH]1C=CC=C1 Chemical compound [Mn].[CH]1C=CC=C1 DEIHRWXJCZMTHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- SHFGJEQAOUMGJM-UHFFFAOYSA-N dialuminum dipotassium disodium dioxosilane iron(3+) oxocalcium oxomagnesium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Na+].[Na+].[Al+3].[Al+3].[K+].[K+].[Fe+3].[Fe+3].O=[Mg].O=[Ca].O=[Si]=O SHFGJEQAOUMGJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052753 mercury Inorganic materials 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- 241000609240 Ambelania acida Species 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 4
- 241000209140 Triticum Species 0.000 claims description 4
- 235000021307 Triticum Nutrition 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000010905 bagasse Substances 0.000 claims description 4
- 239000003139 biocide Substances 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 235000013339 cereals Nutrition 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 4
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 4
- 150000002506 iron compounds Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000010813 municipal solid waste Substances 0.000 claims description 4
- 239000003415 peat Substances 0.000 claims description 4
- 239000008188 pellet Substances 0.000 claims description 4
- 239000011301 petroleum pitch Substances 0.000 claims description 4
- 229940100890 silver compound Drugs 0.000 claims description 4
- 150000003379 silver compounds Chemical class 0.000 claims description 4
- 238000004088 simulation Methods 0.000 claims description 4
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010920 waste tyre Substances 0.000 claims description 4
- 239000002916 wood waste Substances 0.000 claims description 4
- 239000005752 Copper oxychloride Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- HKMOPYJWSFRURD-UHFFFAOYSA-N chloro hypochlorite;copper Chemical compound [Cu].ClOCl HKMOPYJWSFRURD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003623 enhancer Substances 0.000 claims description 3
- NKRVGWFEFKCZAP-UHFFFAOYSA-N 2-ethylhexyl nitrate Chemical compound CCCCC(CC)CO[N+]([O-])=O NKRVGWFEFKCZAP-UHFFFAOYSA-N 0.000 claims description 2
- 206010011703 Cyanosis Diseases 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 claims description 2
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 125000003282 alkyl amino group Chemical group 0.000 claims description 2
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 claims description 2
- 235000010210 aluminium Nutrition 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012241 calcium silicate Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 239000000391 magnesium silicate Substances 0.000 claims description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 2
- 235000019792 magnesium silicate Nutrition 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 150000003873 salicylate salts Chemical class 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003784 tall oil Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 150000001649 bromium compounds Chemical class 0.000 claims 4
- 229940043430 calcium compound Drugs 0.000 claims 4
- 150000001674 calcium compounds Chemical class 0.000 claims 4
- 239000013522 chelant Substances 0.000 claims 4
- 150000002222 fluorine compounds Chemical class 0.000 claims 4
- 229910001503 inorganic bromide Inorganic materials 0.000 claims 4
- 229910052806 inorganic carbonate Inorganic materials 0.000 claims 4
- 229910001504 inorganic chloride Inorganic materials 0.000 claims 4
- 229910001506 inorganic fluoride Inorganic materials 0.000 claims 4
- 229910010276 inorganic hydride Inorganic materials 0.000 claims 4
- 229910001505 inorganic iodide Inorganic materials 0.000 claims 4
- 229910001959 inorganic nitrate Inorganic materials 0.000 claims 4
- 229910052809 inorganic oxide Inorganic materials 0.000 claims 4
- 229910052816 inorganic phosphate Inorganic materials 0.000 claims 4
- 229910052920 inorganic sulfate Inorganic materials 0.000 claims 4
- 150000002681 magnesium compounds Chemical class 0.000 claims 4
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 claims 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 3
- 150000003438 strontium compounds Chemical class 0.000 claims 3
- 150000003609 titanium compounds Chemical class 0.000 claims 3
- 241000208125 Nicotiana Species 0.000 claims 2
- 229940045985 antineoplastic platinum compound Drugs 0.000 claims 2
- 150000001553 barium compounds Chemical class 0.000 claims 2
- 150000001785 cerium compounds Chemical class 0.000 claims 2
- 150000001845 chromium compounds Chemical class 0.000 claims 2
- 150000001869 cobalt compounds Chemical class 0.000 claims 2
- 239000005078 molybdenum compound Substances 0.000 claims 2
- 150000002752 molybdenum compounds Chemical class 0.000 claims 2
- 150000002816 nickel compounds Chemical class 0.000 claims 2
- 150000002941 palladium compounds Chemical class 0.000 claims 2
- 150000003058 platinum compounds Chemical class 0.000 claims 2
- 150000003112 potassium compounds Chemical class 0.000 claims 2
- 150000003284 rhodium compounds Chemical class 0.000 claims 2
- 150000003298 rubidium compounds Chemical class 0.000 claims 2
- 150000003377 silicon compounds Chemical class 0.000 claims 2
- 150000003388 sodium compounds Chemical class 0.000 claims 2
- 150000001639 boron compounds Chemical class 0.000 claims 1
- FSBVERYRVPGNGG-UHFFFAOYSA-N dimagnesium dioxido-bis[[oxido(oxo)silyl]oxy]silane hydrate Chemical compound O.[Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O FSBVERYRVPGNGG-UHFFFAOYSA-N 0.000 claims 1
- 150000002504 iridium compounds Chemical class 0.000 claims 1
- 150000002604 lanthanum compounds Chemical class 0.000 claims 1
- 235000001055 magnesium Nutrition 0.000 claims 1
- 150000002908 osmium compounds Chemical class 0.000 claims 1
- 150000003282 rhenium compounds Chemical class 0.000 claims 1
- 150000003304 ruthenium compounds Chemical class 0.000 claims 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 claims 1
- 150000003606 tin compounds Chemical class 0.000 claims 1
- 150000003658 tungsten compounds Chemical class 0.000 claims 1
- 150000003748 yttrium compounds Chemical class 0.000 claims 1
- 150000003752 zinc compounds Chemical class 0.000 claims 1
- 150000003755 zirconium compounds Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 description 126
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
- 239000001301 oxygen Substances 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 20
- 238000004458 analytical method Methods 0.000 description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 13
- 239000012085 test solution Substances 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 12
- 239000010865 sewage Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 9
- 239000011575 calcium Substances 0.000 description 9
- 239000012141 concentrate Substances 0.000 description 9
- 239000002054 inoculum Substances 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 230000001988 toxicity Effects 0.000 description 8
- 231100000419 toxicity Toxicity 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 239000002199 base oil Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 244000005700 microbiome Species 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- 239000007003 mineral medium Substances 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 230000002688 persistence Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 5
- 241001465754 Metazoa Species 0.000 description 5
- 238000005273 aeration Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 229910052712 strontium Inorganic materials 0.000 description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 5
- 150000003871 sulfonates Chemical class 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 239000002956 ash Substances 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 150000003842 bromide salts Chemical class 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 150000003983 crown ethers Chemical class 0.000 description 4
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 4
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 description 4
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 150000004673 fluoride salts Chemical class 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 4
- 238000011534 incubation Methods 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002068 microbial inoculum Substances 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000013558 reference substance Substances 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 230000000153 supplemental effect Effects 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 210000001519 tissue Anatomy 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 150000002632 lipids Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052762 osmium Inorganic materials 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 229920000098 polyolefin Chemical class 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 230000009182 swimming Effects 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- OZIKUNPJXSWSMD-UHFFFAOYSA-L 2-carboxyphenolate;manganese(2+) Chemical compound [Mn+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O OZIKUNPJXSWSMD-UHFFFAOYSA-L 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 244000061176 Nicotiana tabacum Species 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000001154 acute effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 2
- 239000003830 anthracite Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 231100000636 lethal dose Toxicity 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 231100000706 no observed effect level Toxicity 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 229920005862 polyol Chemical class 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VPOMSPZBQMDLTM-UHFFFAOYSA-N 3,5-dichlorophenol Chemical compound OC1=CC(Cl)=CC(Cl)=C1 VPOMSPZBQMDLTM-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- JFMPNUSMYQTWLE-UHFFFAOYSA-N C(C)(C)(C)[Mn]C1C=CC=C1 Chemical compound C(C)(C)(C)[Mn]C1C=CC=C1 JFMPNUSMYQTWLE-UHFFFAOYSA-N 0.000 description 1
- DVOPUUNOXTXSGY-UHFFFAOYSA-N C(C)(C)[Mn]C1C=CC=C1 Chemical compound C(C)(C)[Mn]C1C=CC=C1 DVOPUUNOXTXSGY-UHFFFAOYSA-N 0.000 description 1
- CBFDCGBUJOPQRM-UHFFFAOYSA-N C(C)[Mn](C1C=CC=C1)C Chemical compound C(C)[Mn](C1C=CC=C1)C CBFDCGBUJOPQRM-UHFFFAOYSA-N 0.000 description 1
- LAWBUPNHLNLGIU-UHFFFAOYSA-N C(C)[Mn](C1C=CC=C1)CC Chemical compound C(C)[Mn](C1C=CC=C1)CC LAWBUPNHLNLGIU-UHFFFAOYSA-N 0.000 description 1
- UEGKGEVCXOBKSV-UHFFFAOYSA-N C(C)[Mn]C1C=CC=C1 Chemical compound C(C)[Mn]C1C=CC=C1 UEGKGEVCXOBKSV-UHFFFAOYSA-N 0.000 description 1
- BMLOSAYGXCELMP-UHFFFAOYSA-N C(CC)[Mn]C1C=CC=C1 Chemical compound C(CC)[Mn]C1C=CC=C1 BMLOSAYGXCELMP-UHFFFAOYSA-N 0.000 description 1
- YWMXGTUCTQNTTR-UHFFFAOYSA-N C(CCCCCCCCCCC)[Mn]C1C=CC=C1 Chemical compound C(CCCCCCCCCCC)[Mn]C1C=CC=C1 YWMXGTUCTQNTTR-UHFFFAOYSA-N 0.000 description 1
- GAHCCFASRFYYAQ-UHFFFAOYSA-N C1(C=CC2=CC=CC=C12)[Mn] Chemical compound C1(C=CC2=CC=CC=C12)[Mn] GAHCCFASRFYYAQ-UHFFFAOYSA-N 0.000 description 1
- JIALZGWIWNOXBE-UHFFFAOYSA-N C[Mn](C1C=CC=C1)(C)(C)(C)C Chemical compound C[Mn](C1C=CC=C1)(C)(C)(C)C JIALZGWIWNOXBE-UHFFFAOYSA-N 0.000 description 1
- AJSMUOQIBPTBGU-UHFFFAOYSA-N C[Mn](C1C=CC=C1)(C)(C)C Chemical compound C[Mn](C1C=CC=C1)(C)(C)C AJSMUOQIBPTBGU-UHFFFAOYSA-N 0.000 description 1
- FBPICIDSBHWIAN-UHFFFAOYSA-N C[Mn](C1C=CC=C1)(C)C Chemical compound C[Mn](C1C=CC=C1)(C)C FBPICIDSBHWIAN-UHFFFAOYSA-N 0.000 description 1
- PKLHPMBYWRLVGW-UHFFFAOYSA-N C[Mn](C1C=CC=C1)C Chemical compound C[Mn](C1C=CC=C1)C PKLHPMBYWRLVGW-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000195628 Chlorophyta Species 0.000 description 1
- 241001494246 Daphnia magna Species 0.000 description 1
- 241000238576 Daphnia pulex Species 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 231100000111 LD50 Toxicity 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 240000003433 Miscanthus floridulus Species 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 241001520808 Panicum virgatum Species 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 239000004614 Process Aid Substances 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 125000004946 alkenylalkyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 231100000209 biodegradability test Toxicity 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 231100000132 chronic toxicity testing Toxicity 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- LCGVCXIFXLGLHG-UHFFFAOYSA-N cyclopenta-1,3-diene;manganese(2+) Chemical compound [Mn+2].C1C=CC=[C-]1.C1C=CC=[C-]1 LCGVCXIFXLGLHG-UHFFFAOYSA-N 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002405 diagnostic procedure Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- NGHTXZCKLWZPGK-UHFFFAOYSA-N nefiracetam Chemical compound CC1=CC=CC(C)=C1NC(=O)CN1C(=O)CCC1 NGHTXZCKLWZPGK-UHFFFAOYSA-N 0.000 description 1
- 230000017066 negative regulation of growth Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229960001730 nitrous oxide Drugs 0.000 description 1
- 235000013842 nitrous oxide Nutrition 0.000 description 1
- HGASFNYMVGEKTF-UHFFFAOYSA-N octan-1-ol;hydrate Chemical compound O.CCCCCCCCO HGASFNYMVGEKTF-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000010627 oxidative phosphorylation Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000004202 respiratory function Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000563 toxic property Toxicity 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
- C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
- C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Definitions
- the present disclosure relates to the field of fuel additives, fuels, and fuel compositions, specifically environmentally-friendly fuel additives and fuel additive compositions suitable for use with solid fuels.
- an environmentally compatible fuel additive composition suitable for use with a solid fuel may comprise at least one functional component, wherein the component is selected from the group consisting of a non-persistent material, a non-bioaccumulative material, and a non-toxic material.
- the additive composition may be substantially devoid of any component that is persistent, bioaccumulative, and toxic.
- an environmentally compatible solid fuel composition may comprise a) a major amount of a solid fuel; and b) a minor amount of an additive composition.
- the additive composition may comprise at least one of a functional component, wherein the component comprises at least one of: i) an acceptable level biodegradation of at least one of: 1) a half-life in marine water of less than 60 days; 2) a half-life in fresh or estuarine water of less than 40 days; 3) a half-life in marine sediment of less than 180 days; 4) a half-life in fresh or estuarine water sediment less than 120 days; or 5) a half-life in soil less than 120 days, as determined by a biodegradation test; ii) a bioconcentration factor below 2000 in a bioconcentration factor test; or iii) is devoid of a toxic effect at an aqueous concentration below 0.01 mg/L on a toxicity test.
- a method of making an environmentally compatible solid fuel composition may comprise combining a major amount of a solid fuel and a minor amount of an additive composition.
- the additive composition may comprise at least one functional component wherein the component is selected from: i) a material having an acceptable level biodegradation of at least one of: 1) a half-life in marine water of less than 60 days; 2) a half-life in fresh or estuarine water of less than 40 days; 3) a half-life in marine sediment of less than 180 days; 4) a half-life in fresh or estuarine water sediment less than 120 days; or 5) a half-life in soil less than 120 days, as determined by a biodegradation test; ii) a material having a bioconcentration factor below 2000 in a bioconcentration factor test; or iii) a material that is devoid of a toxic effect at an aqueous concentration below 0.01 mg/L on a toxicity test.
- the solid fuel composition may comply with European Council Directive 67/548/EEC
- an environmentally compatible solid fuel composition may comprise a major amount of a solid fuel and a minor amount of an additive composition.
- the additive composition may comprise at least one functional component, wherein the component is at least selected from the group consisting of non-persistent materials, non-bioaccumulative materials, and non-toxic materials, and the additive composition is substantially devoid of any component that is persistent, bioaccumulative, and toxic.
- An advantage of embodiments of the disclosure is that an impact on the environment by the use of materials disclosed herein may be lessened.
- a further advantage is that accidental or inadvertent spills of the additive compositions and/or fuel compositions may not pose long term threats to humans and wildlife.
- Still further advantages of the compositions and methods described herein may be acceptable to national and state regulatory agencies.
- Solid fuel herein can in one embodiment be selected from the group consisting of coal, coke, coke breeze, carbonaceous char, petroleum pitch, petroleum coke, refuse derived fuel (RDF), municipal solid waste (MSW), biomass, bagasse, wood, wood pellets, wood bark, wood by-products, wood wastes, sawdust, hog fuel, black liquor solids, waste tires, charcoal, peat, corn, corn cobs, wheat, rye, and other grains, coffee grounds, and tobacco wastes.
- RDF refuse derived fuel
- MSW municipal solid waste
- biomass bagasse, wood, wood pellets, wood bark, wood by-products, wood wastes, sawdust, hog fuel, black liquor solids, waste tires, charcoal, peat, corn, corn cobs, wheat, rye, and other grains, coffee grounds, and tobacco wastes.
- additive package As used herein, the terms “additive package,” “additive concentrate,” and “additive composition” are considered synonymous, fully interchangeable terminology referring to the portion of the fuel composition excluding the solid fuel.
- a “functional” component means a component that is used in a fuel formulation to provide a measurable change in a characteristic or property of a fuel containing the component or in a property of the system delivering the fuel, or the system combusting the fuel, or the system exhausting the products from the combustion of the fuel.
- agent and “additive” are considered synonymous, fully interchangeable terminology referring to any single component of a fuel composition excluding the major amount of solid fuel in the mixture.
- substantially devoid means containing no more than, for example, a trace amount, an innocuous amount, or a contaminant amount.
- NO x refers to, for example, the chemical species nitric oxide (NO) and/or nitrogen dioxide (NO 2 ) which may be emitted from combustion sources.
- NO x may define dinitrogen monoxide (N 2 O), dinitrogen trioxide (N 2 O 3 ), dinitrogen tetroxide (N 2 O 4 ), and/or dinitrogen pentoxide N 2 O 5 ).
- European Council Directive 76/548/EEC incorporated herein by reference, provides regulatory guidance for the registration and evaluation of chemical substances that may be exposed to the environment during the normal course of use. Guidelines and testing procedures are enumerated therein, so that the potential environmental impact of any substance may be quantified.
- a number of diagnostic tests have been developed to measure the effects of certain chemical substances upon various aspects of the environment.
- three main parameters are used to classify such substances: namely, persistence, bioaccumulation, and toxicity.
- the persistence of a substance in the environment may be inversely related to the biodegradability of the substance.
- Biodegradability is the ability of microbes occurring in an environment to break down a substance into simpler substances.
- the persistence, or biodegradability, criterion is defined in European Council Directive 76/548/EEC Annex XIII section 1.1, which is herein incorporated by reference, as a substance fulfilling one of the following criteria: having a half-life in marine water longer than 60 days, having a half-life in fresh or estuarine water longer than 40 days, having a half-life in marine sediment longer than 180 days, having a half-life in fresh or estuarine water sediment longer than 120 days, or having a half-life in soil longer than 120 days.
- a material's persistence in the environment may be determined by a number of different test procedures, including the following tests: a dissolved organic carbon (DOC) die-away test, a modified OECD screening dissolved organic carbon die-away test, a carbon dioxide evolution test, a manometric respirometry test, a closed bottle test, a MITI test, a Zahn-Wellens test, an activated sludge simulation test, an activated sludge respiration inhibition test, and a modified SCAS test.
- DOC dissolved organic carbon
- a solution, or suspension, of the test substance in a mineral medium is introduced into an inoculum and incubated under aerobic conditions in the dark or in diffuse light.
- the amount of dissolved organic carbon (DOC) in the test solution due to microbial inoculum should be kept as low as possible compared to the amount of DOC due to the test substance. Allowance is made for the endogenous activity of the inoculum by running parallel blank tests with inoculum but without test substance, although the endogenous activity of cells in the presence of the substance will not exactly match that in the endogenous control. A reference substance is run in parallel to check the operation of the procedures.
- degradation is followed by the determination of parameters, such as DOC, CO 2 production, and oxygen uptake, and measurements are taken at sufficiently frequent intervals to allow the identification of the beginning and end of biodegradation. With automatic respirometers the measurement is continuous. DOC is sometimes measured in addition to another parameter but this is usually done only at the beginning and the end of the test. Specific chemical analysis may also be used to assess primary degradation of the test substance, and to determine the concentration of any intermediate substances formed (obligatory in the MITI test).
- parameters such as DOC, CO 2 production, and oxygen uptake
- test Normally, the tests last for 28 days. Tests however may be ended before 28 days, i.e., as soon as the biodegradation curve has reached a plateau for at least 3 determinations. Tests may also be prolonged beyond 28 days when the curve shows that biodegradation has started but that the plateau has not been reached by day 28.
- the inoculum may be derived from a variety of sources: activated sludge, unchlorinated sewage effluents, surface waters and soils, or from a mixture of these.
- a measured volume of inoculated mineral medium containing a known concentration of the test substance (10-40 mg DOC/1) as the nominal sole source of organic carbon is aerated in the dark or diffused light at 22 ⁇ 2° C.
- Degradation is followed by DOC analysis at frequent intervals over a 28-day period.
- the degree of biodegradation is calculated by expressing the concentration of DOC removed (corrected for that in the blank inoculum control) as a percentage of the concentration initially present.
- the degree of primary biodegradation may also be calculated from supplemental chemical analysis made at the beginning and end of incubation.
- the percentage degradation may be calculated by:
- a measured volume of inoculated mineral medium containing a known concentration of test chemical (100 mg/liter of the test substance, to give at least 50-100 mg theoretical oxygen demand/liter) as the nominal sole source of organic carbon, is stirred in a closed flask at a constant temperature ( ⁇ 1° C. or closer) for up to 28 days.
- the consumption of oxygen may be determined either by measuring the quantity of oxygen (produced electrolytically) required to maintain constant gas volume in the respirometer flask, or from the change in volume or pressure (or a combination of the two) in the apparatus.
- Evolved carbon dioxide is absorbed in a solution of potassium hydroxide or another suitable absorbent.
- the amount of oxygen taken up by the test chemical is expressed as a percentage of ThOD (theoretical oxygen demand) or COD (chemical oxygen demand).
- ThOD theoretical oxygen demand
- COD chemical oxygen demand
- primary biodegradation may also be calculated from supplemental specific analysis made at the beginning and end of incubation, and ultimate biodegradation by DOC analysis.
- the oxygen uptake by a stirred solution, or suspension, of the test chemical in a mineral medium, inoculated with specially grown, unadapted micro-organisms is measured automatically over a period of 28 days in a darkened, enclosed respirometer at 25 ⁇ 1° C. Evolved carbon dioxide is absorbed by soda lime. Biodegradability is expressed as the percentage oxygen uptake (corrected for blank uptake) of the theoretical oxygen uptake (ThOD). The percentage of primary biodegradability is also calculated from supplemental specific chemical analysis made at the beginning and end of incubation and, optionally, by DOC analysis.
- the purpose of the Zahn-Wellens Test is the evaluation of the potential ultimate biodegradability of water-soluble, non-volatile organic substances when exposed to relatively high concentrations of micro-organisms in a static test.
- DOC dissolved organic carbon
- COD chemical oxygen demand
- a simultaneous use of a specific analytical method may allow the assessment of the primary biodegradation of the substance (disappearance of the parent chemical structure).
- the method is applicable only to those organic test substances which, at the concentration used in the test are soluble in water under the test conditions, have negligible vapor pressure under the test conditions, are not inhibitory to bacteria, are adsorbed within the test system only to a limited extent, and are not lost by foaming from the test solution.
- Activated sludge, mineral nutrients and the test material as the sole carbon source in an aqueous solution are placed together in a one to four liter glass vessel equipped with an agitator and an aerator.
- the mixture is agitated and aerated at 20 to 25° C. under diffuse illumination or in a dark room for up to 28 days.
- the degradation process is monitored by determination of the DOC (or COD) values in the filtered solution at daily or other appropriate regular time intervals.
- the ratio of eliminated DOC (or COD) after each interval to the value three hours after the start is expressed as percentage biodegradation and serves as the measure of the extent of degradation at this time. The result is plotted versus time to give the biodegradation curve.
- the activated sludge simulation test is used to determine the primary biodegradability of a substance in an activated sludge plant model, at a concentration of about 20 mg/liter. This allows the assessment of the primary biodegradability of the substance (disappearance of the parent chemical structure). Another purpose of the method is the determination of ultimate biodegradability by the measurement of the removal of the substance and any metabolites in an activated sludge plant model at a concentration corresponding to >12 mg DOC/liter (or approximately 40 mg COD/liter); wherein 20 mg DOC/liter seems to be optimal.
- test substance is added to the influent (synthetic or domestic sewage) of one of the units, while the other blank unit receives the sewage alone.
- influent synthetic or domestic sewage
- blank unit receives the sewage alone.
- primary biodegradation with specific analysis in the influent and effluent, only one unit may be used.
- the sludge growth/stabilization period is the period during which the concentration of the activated sludge suspended solids and the performance of the units' progress to a steady state under the operating conditions used.
- the running-in period is the period which lasts from the time the test substance is first added to the time when its removal reaches a plateau (relatively constant value). This period must not exceed six weeks.
- the evaluation period is a three week period, i.e., three weeks from the time that the removal of the test substance reaches a relatively constant, and usually high, value. For those substances which show little or no degradation in the first six weeks, the evaluation period is taken as the following three weeks.
- Influent without substance to be tested must pass through an aeration vessel either at the rate of one liter per hour or a rate of one-half liter per hour thereby providing a mean retention time of either three or six hours.
- the rate of aeration should be regulated so that the content of the vessel is kept constantly in suspension while the dissolved oxygen content is at least 2 mg/liter.
- the sludge which has accumulated around the top of the aeration vessel must be returned to the mixed liquor at least once each day by brushing or some other appropriate means.
- the effluent is collected in a second vessel for 20 to 24 hours, and a sample is taken after thorough mixing.
- the chemical oxygen demand (COD) or the dissolved organic carbon (DOC) of the filtrate of the accumulated effluent is measured at least twice weekly, as well as that of the filtered influent (using a membrane of pore size 0.45 ⁇ m, wherein the first 20 ml (approximately) of the filtrate are discarded).
- COD or DOC dissolved organic carbon
- test material approximately 10 to 20 mg DOC/liter or 40 mg COD/liter
- concentration approximately 10 to 20 mg DOC/liter or 40 mg COD/liter
- This concentration may be reached progressively. If there are no toxic effects of the test substance on the activated sludge, higher concentrations may also be tested.
- the blank unit is fed only with influent without added substances. Adequate volumes of the effluents are taken for analysis and filtered through membrane filters (0.45 ⁇ m), the first 20 ml (approximately) of filtrate being discarded.
- the filtered samples have to be analyzed on the same day, otherwise they must be preserved by any suitable method, for example, by using 0.05 ml of a 1% mercuric chloride (HgCl 2 ) solution for each 10 ml of filtrate or by storing them at 2 to 4° C. up to 24 hours, or below ⁇ 18° C. for longer periods.
- HgCl 2 1% mercuric chloride
- the running-in time, with addition of test substance, should not exceed six weeks and the evaluation period should not be shorter than three weeks, so that about 14 to 20 determinations are available for calculation of the final result.
- the activated sludge respiration inhibition test assesses the effect of a test substance on micro-organisms by measuring the respiration rate under defined conditions in the presence of different concentrations of the test substance.
- the purpose of this method is to provide a rapid screening method whereby substances which may adversely affect aerobic microbial treatment may be identified, and to indicate suitable non-inhibitory concentrations of test substances to be used in biodegradability tests.
- Two controls without the test substance are included in the test design, one at the start and the other at the end of the test series. Each batch of activated sludge should also be checked using a reference substance.
- the activated sludge respiration inhibition method is most readily applied to substances which, due to their water solubility and low volatility, are likely to remain in water. For substances with limited solubility in the test media, it may not be possible to determine the EC 50 . Results based on oxygen uptake may lead to erroneous conclusions if the test substance has the propensity to uncouple oxidative phosphorylation. It may be useful to have the following information to perform the test: water solubility, vapor pressure, structural formula, and the purity of the test substance.
- 3,5-dichlorophenol as a known inhibitor of respiration, be used as a reference substance and tested for EC 50 on each batch of activated sludge as a means of checking that the sensitivity of the sludge is not abnormal.
- At least five concentrations spaced by a constant factor preferably not exceeding 3.2, are used.
- 16 ml of the synthetic sewage feed are made up to 300 ml with water.
- 200 ml of microbial inoculum are added and the total mixture (500 ml) poured into a first vessel (first control C1).
- the test vessels should be aerated continuously so as to ensure that the dissolved O 2 does not fall below 2.5 mg/liter and that, immediately before the measurement of the respiration rate, the O 2 concentration is about 6.5 mg/liter.
- a second control is prepared (C2). After three hours the pH is recorded, and a well-mixed sample of the contents of the first vessel is poured into the measuring apparatus and the respiration rate is measured over a period of up to 10 minutes. This determination is repeated on the contents of each vessel at 15-minute intervals, in such a way that the contact time in each vessel is three hours.
- the reference substance may be tested on each batch of microbial inoculum in the same way.
- the modified SCAS test is used to evaluate the potential ultimate biodegradability of water-soluble, non-volatile organic substances when exposed to relatively high concentrations of micro-organisms over a long time period. The viability of the microorganisms is maintained over this period by daily addition of a settled sewage feed.
- the conditions provided by the test are highly favorable to the selection and/or adaptation of microorganisms capable of degrading the test compound, however the procedure may also be used to produce acclimatized inocula for use in other tests.
- the measure of the concentration of dissolved organic carbon is used to assess the ultimate biodegradability of the test substances. It is preferable to determine DOC after acidification and purging rather than as the difference of C total ⁇ C inorganic .
- the method is applicable only to those organic test substances which, at the concentration used in the test are soluble in water (at least 20 mg dissolved organic carbon/liter), have negligible vapor pressure, are not inhibitory to bacteria, do not significantly adsorb within the test system, and are not lost by foaming from the test solution.
- the organic carbon content of the test substance must be established prior to running the test.
- Activated sludge from a sewage treatment plant is placed in a semi-continuous activated sludge (SCAS) unit.
- SCAS semi-continuous activated sludge
- the test compound and settled domestic sewage are added, and the mixture is aerated for 23 hours.
- the aeration is then stopped, the sludge allowed to settle, the mixture supernatant liquor is removed.
- the sludge remaining in the aeration chamber is then mixed with a further aliquot of test compound and sewage and the cycle is repeated.
- Biodegradation is established by determining the dissolved organic carbon content of the supernatant liquor. This value is compared with that found for the liquor obtained from a control tube dosed with settled sewage only.
- the dissolved organic carbon in the supernatant liquors is determined daily, although less frequent analyses may be used.
- the liquors are filtered through washed 0.45 ⁇ m membrane filters or centrifuged.
- Membrane filters are suitable if it is assured that they neither release carbon nor absorb the substance in the filtration step.
- the temperature of the sample must not exceed 40° C. while it is in the centrifuge.
- the length of the test for compounds showing little or no biodegradation is indeterminate, but experience suggests that this should be at least 12 weeks in general, but not longer than 26 weeks.
- Bioaccumulation is defined as the increase in concentration of a test substance in or on an organism or specified tissues thereof relative to the concentration of the substance in the surrounding medium.
- bioaccumulation and “bioconcentration” are used interchangeably to refer to the same criteria.
- the bioconcentration factor (“BCF”) is calculated as the concentration of test substance in an organism (or specified tissues thereof) divided by the concentration of the substance in the surrounding medium. Both the uptake and deputation of substances by organisms, and the respective rates thereof, are considered in calculating bioaccumulation.
- P OW octanol-water partition coefficient
- the criterion for acceptable bioaccumulation is defined in European Council Directive 76/548/EEC Annex XIII section 1.2, which is herein incorporated by reference, as a substance having a bioconcentration factor higher than 2000.
- the bioconcentration factor of a material may be determined by test procedures set forth in European Council Directive 76/548 EEC Annex V, section C.13 flow-through fish test, which is incorporated in full herein by reference.
- the flow-through fish test consists of two phases: the exposure (uptake) phase and the post-exposure (depuration) phase.
- the uptake phase separate groups of fish of one species are exposed to at least two concentrations of the test substance. They are then transferred to a medium free of the test substance for the depuration phase.
- a depuration phase is always necessary unless uptake of the substance during the uptake phase has been insignificant (e.g., the BCF is less than 10).
- the concentration of the test substance in/on the fish (or specified tissue thereof) is followed through both phases of the test.
- a control group of fish is held under identical conditions except for the absence of the test substance, to relate possible adverse effects observed in the bioconcentration test to a matching control group and to obtain background concentrations of test substance.
- the uptake phase is run for 28 days unless it is demonstrated that equilibrium has been reached earlier.
- the depuration period is then begun by transferring the fish to the same medium but without the test substance in another clean vessel.
- the bioconcentration factor is calculated preferably both as the ratio (BCF SS ) of concentration of the fish (C f ) and in the water (C w ) at apparent steady-state and as a kinetic bioconcentration factor, BCF K as the ratio of the rate constants of uptake (k 1 ) and depuration (k 2 ) assuming first-order kinetics.
- the uptake phase should be extended until steady-state is reached, or 60 days, whichever comes first; the depuration phase is then begun.
- the BCF is expressed as a function of the total wet weight of the fish.
- specified tissues or organs e.g. muscle, liver
- the fish may be divided into edible (fillet) and non-edible (viscera) fractions.
- fat e.g., fillet
- viscera non-edible fractions.
- bioconcentration should be expressed in relation to lipid content in addition to whole body weight.
- the lipid content is determined on the same biological material as is used to determine the concentration of the test substance, when feasible.
- the toxicity criterion is defined in European Council Directive 76/548/EEC Annex XIII section 1.3, which is herein incorporated by reference, as a substance having a long-term no-observed effect concentration (NOEC) for marine or freshwater organisms less than 0.01 mg/L. Substances that are classified as carcinogenic, mutagenic, or toxic for reproduction may also be considered as toxic.
- NOEC no-observed effect concentration
- the toxicity of a material may be determined by test procedures, such as the acute toxicity for fish test, the acute toxicity for Daphnia test, and the algal inhibition test, set forth in European Council Directive 76/548/EEC Annex V, sections C.1, C.2, and C.3, which are incorporated in full herein by reference. These acute tests may be used for first cut screening (if LC50 ⁇ 1 ppm), however chronic toxicity tests (usually in Daphnia but also other organisms) may be used for definitive Toxicity.
- the purpose of the acute toxicity for fish test is to determine the acute lethal toxicity of a substance to fish in fresh water. It is desirable to have, as far as possible, information on the water solubility, vapor pressure, chemical stability, dissociation constants, and biodegradability of the substance to help in the selection of the most appropriate test method (static, semi-static, or flow-through) for ensuring satisfactorily constant concentrations of the test substance over the period of the test.
- Acute toxicity is the discernible adverse effect induced in an organism within a short time (days) of exposure to a substance.
- acute toxicity is expressed as the median lethal concentration (LC 50 ), the concentration in water which kills 50% of a test batch of fish within a continuous period of exposure which must be stated.
- LC 50 median lethal concentration
- the static test is a toxicity test in which no flow of test solution occurs. The solutions remain unchanged throughout the duration of the test.
- the semi-static test is a test without flow of test solution, but with regular batchwise renewal of test solutions after prolonged periods (e.g. 24 hours).
- the flow-through test is a toxicity test in which the water is renewed constantly in the test chambers, the chemical under test being transported with the water used to renew the test medium.
- At least 7 fish per concentration being tested are exposed to the substance for a duration of 96 hours in tanks of suitable capacity. At least five concentrations differing by a constant factor not exceeding 2.2, and as far as possible spanning the range of 0 to 100% mortality, should be tested for each substance.
- the fish may not be fed during the test. The fish are inspected after the first 2 to 4 hours and afterward at least at 24-hour intervals. Fish are considered dead if touching of the caudal peduncle produces no reaction, and no breathing movements are visible. Dead fish are removed when observed and mortalities are recorded. Records are kept of visible abnormalities (e.g. loss of equilibrium, changes in swimming behavior, respiratory function, pigmentation, etc.). Measurements of pH, dissolved oxygen and temperature must be carried out daily.
- the acute toxicity for Daphnia test is similar to the acute toxicity for fish test, but the purpose is to determine the median effective concentration for immobilization (EC 50 ) of a substance to Daphnia in fresh water.
- EC 50 median effective concentration for immobilization
- the Daphnia are exposed to the test substance added to water at a range of concentrations for 48 hours. Under otherwise identical test conditions, and an adequate range of test substance concentrations, different concentrations of a test substance exert different average degrees of effect on the swimming ability of Daphnia. Different concentrations result in different percentages of Daphnia being no longer capable of swimming at the end of the test.
- concentrations causing zero or 100% immobilization are derived directly from the test observations whereas the 48-hour EC 50 may be determined by calculation if possible. A static system is used for this method, hence test solutions are not renewed during the exposure period.
- Stock solutions of the required strength are prepared by dissolving the substance in deionized water or water.
- the chosen test concentrations are prepared by dilution of the stock solution. If high concentrations are tested, the substance may be dissolved in the dilution water directly.
- the substances are normally only tested up to the limit of solubility. For some substances (e.g. substances having low solubility in water, or high P OW , or those forming stable dispersion rather than true solution in water), it is acceptable to run a test concentration above the solubility limit of the substance to ensure that the maximum soluble/stable concentration has been obtained. It is important, however, that this concentration will not otherwise disturb the test system. (e.g. film of the substance on the water surface preventing the oxygenation of the water, etc.).
- Daphnia magna is the preferred test species although Daphnia pulex is also permitted.
- the test animals shall be less than 24 hours old at the beginning of the test, laboratory bred, free from overt disease, and with a known history (e.g. breeding, any pretreatments, etc.).
- the Daphnia are exposed to the substance for 48 hours. At least 20 animals at each test concentration, preferably divided into four batches of five animals each or two batches of 10, are required. At least 2 ml of test solutions should be provided for each animal.
- the test solution should be prepared immediately before introduction of the Daphnia, preferably without using any solvent other than water. The concentrations are made up in a geometric series, at a concentration ratio not exceeding 2.2. Concentrations sufficient to give 0 and 100% immobilization after 48 hours and a range of intermediate degrees of immobilizations permitting calculation of the 48 hour EC50 should be tested together with controls.
- the test temperature should be between 18 and 22° C., but for each single test it should be constant within ⁇ 1° C.
- test solutions must not be bubble-aerated, and the animals may not be fed during the test.
- the pH and the oxygen concentration of the controls and of all the test concentrations should be measured at the end of the test; the pH of the test solutions should not be modified.
- Volatile compounds should be tested in completely filled closed containers, large enough to prevent lack of oxygen. The Daphnia are inspected at least after 24 hours exposure and again after 48 hours.
- the algal inhibition test may be used to determine the effects of a substance on the growth of a unicellular green algal species. Relatively brief (72 hours) tests may assess effects over several generations. This method may be adapted for use with several different unicellular algal species. The method is most easily applied to water-soluble substances which, under the conditions of the test, are likely to remain in the water.
- Exponentially-growing cultures of selected green algae are exposed to various concentrations of the test substance over several generations under defined conditions.
- the test solutions are incubated for a period of 72 hours, during which the cell density in each solution is measured at least every 24 hours.
- the inhibition of growth in relation to a control culture is determined.
- Test cultures containing the desired concentrations of test substance and the desired quantity of algal inoculum are prepared by adding aliquots of stock solutions of the test substance to suitable amounts of pre-prepared algal cultures.
- the culture flasks are shaken and placed in the culturing apparatus.
- the algal cells are kept in suspension by shaking, stirring, or bubbling with air, in order to improve gas exchange and reduce pH variation in the test solutions.
- the cultures are maintained at a temperature in the range of 21 to 25° C., controlled at ⁇ 2° C.
- the cell density in each flask is determined at least at 24, 48 and 72 hours after the start of the test.
- Filtered algal medium containing the appropriate concentration of the test chemical is used to determine the background when using cell density measurements other than direct counting methods.
- a suitable fuel or fuel additive composition may use functional components that may not exhibit at least one of persistence, bioaccumulation, or toxicity when tested according to the procedures set forth above. Accordingly, a functional component that is found to be persistent, bioaccumulative, and toxic may not be included in fuel formulations of the present disclosure.
- a functional component may be non-persistent but may be bioaccumulative and toxic. In another embodiment, a functional component may be non-bioaccumulative but may be persistent and toxic. In another embodiment, a functional component may be non-toxic but may be persistent and bioaccumulative.
- a functional component may be non-persistent and non-bioaccumulative but may be toxic. In another embodiment, a functional component may be non-persistent and non-toxic but may be bioaccumulative. In another embodiment, a functional component may be non-bioaccumulative and non-toxic but may be persistent.
- a functional component may be non-persistent, non-bioaccumulative, and non-toxic.
- Suitable embodiments may comprise additive compositions containing one or more of the following: acid plume reducing agents, anti-icing agents, biocides, carrier fluids, combustion improvers, corrosion inhibitors, diluents, dust suppressants, electrostatic precipitator activating agents, fluxing agents, fouling modifiers, hygroscopic agents, ignition improvers, markers or customer-specific “tags,” reodorants, mercury scavengers, nitrogen oxide (NO x ) scavengers, NO x reducing agents, slag modifiers, sulfur oxide (SO 2 /SO 3 ) scavengers, and surfactants.
- Suitable embodiments may comprise one or more of methyl cyclopentadienyl manganese tricarbonyl, cyclopentadienyl manganese tricarbonyl, octane enhancer materials, alkyl nitrates, glycols, phenates, salicylates, sulfonates, alkali detergents and alkaline earth metal-containing detergents, tall oil fatty acids, 2-ethyl hexyl nitrate, manganese carboxylates, copper carboxylates, magnesium carboxylates, magnesium sulfonates, ferrocene, calcium nitrate, perlite, aluminum trihydrate, copper oxychloride, cerium oxides, hydroxides, and carboxylates, platinum group metal organics and inorganics, aluminum silicate, magnesium silicate, vermiculite, aluminum sulfonate, aluminum carboxylate, magnesium oxide, and magnesium hydroxide.
- Suitable embodiments may comprise additive compositions comprising one or more metal compounds.
- the presence of metal atoms may be useful for realizing many desired additive functions, including combustion improvement, slag modification, acid neutralization, and many others.
- the metal compounds or metal ions may be inorganic metal compounds and/or organometallic compounds.
- the elemental or ionic metals may be selected from, but not limited to, one or more of the following: sodium, potassium, magnesium, calcium, barium, strontium, titanium, cerium, chromium, molybdenum, manganese, iron, zinc, yttrium, lanthanum, zirconium, ruthenium, tungsten, rhenium, osmium, iridium, boron, aluminum, silicon, tin, rubidium, cobalt, rhodium, nickel, palladium, platinum, copper, and silver compounds, and mixtures thereof.
- the inorganic metal compound may be selected from, but not limited to, one or more of the following: fluorides, chlorides, bromides, iodides, oxides, nitrates, sulfates, phosphates, carbonates, hydrides, nitrides, and mixtures thereof.
- the organometallic compounds may be selected from, but not limited to, one or more of: alcohols, aldehydes, ketones, esters, anhydrides, sulfonates, phosphonates, chelates, phenates, crown ethers, carboxylic acids, amides, and mixtures thereof.
- organometallic compounds containing one or more carbonyl groups, ethers or poly ethers, aminos, alkylaminos, acetamidos, alkoxides, alkyls, cyanos, furfuryls, carboxylates, acetylacetonates, and other organic ligands able to coordinate with or bond with a metal, metal compound, or metal ion.
- Example 2 (Wt. % based on (Wt. % based on Component finished fuel) finished fuel) manganese carboxylate 0.00001-0.5 0.0001-0.1 magnesium sulfonate 0.00001-2.0 0.0001-0.01 surfactant 0.00001-1.0 0.0001-1.0 aromatic solvent 0-10.0 0.0001-10.0 petroleum coke Balance Balance
- Suitable fuels may comprise any known solid fuel or mixtures thereof.
- Suitable solid fuels may include, but are not limited to, coal, coke, coke breeze, carbonaceous char, petroleum pitch, petroleum coke, refuse derived fuel (RDF), municipal solid waste (MSW), biomass, bagasse, wood, wood pellets, wood bark, wood by-products, wood wastes, sawdust, hog fuel, black liquor solids, waste tires, charcoal, peat, corn, corn cobs, wheat, rye, and other grains, coffee grounds, tobacco wastes, and the like.
- This additive may also be water based by substituting an aqueous medium for the organic solvent, and adjusting the surfactant to meet the handling goals, for example, utilizing a clear solution, an emulsion, or a slurry.
- Suitable solid fuels may be combined with one or more liquid fuels and/or water as an adjuvant, process aid, ignition promoter, dust suppressant, diluent, viscosity modifier, and/or flow enhancer.
- Such liquid fuels may comprise, but are not limited to, one or more of gasoline, diesel fuel, middle distillate fuel, biodiesel fuel, an alcohol, such as but not limited to an ethanol, bioethanol, a biobutanol, coal, an aviation fuel, jet fuel, marine fuel, burner fuel, home heating oil, a gas-to-liquid (GTL) base oil, a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, an ester, a vegetable oil, and a mixture thereof.
- GTL gas-to-liquid
- Suitable coal may comprise any naturally occurring coal.
- coal may comprise lignite, jet, sub-bituminous, bituminous, and anthracite.
- Coal may be pulverized and/or crushed. Further, it may be fed into a burner as a dry powder or slurry.
- Suitable coal may be coal that is converted into liquid-fuels like gasoline or diesel by several different processes.
- the Fischer-Tropsch process of indirect synthesis of liquid hydrocarbons may be used to gasify coal to make syngas (a balanced purified mixture of CO and H 2 gas).
- the syngas may then be reductively polymerized on Fischer-Tropsch catalysts to make hydrocarbons which are further processed into gasoline, diesel, jet fuel, oxygenantes, lubricant base stocks, waxes, and other chemicals.
- Syngas can also be converted to methanol and ethanol, which can be used as a fuel, fuel additive, or further processed into gasoline.
- Several other processes exist to liquefy coal such as, but not limited to direct liquefaction by hydrogenation and low temperature carbonization.
- Suitable coal sources for liquefaction may comprise lignite, anthracite, sub-bituminous, and/or bituminous coal.
- the coal may be “pulverized coal” which is either already small enough or has been subjected to mechanical particle size reduction such that the resulting pulverized material can be conveyed via fluidization with air through a pipe into the combustion chamber of a furnace or boiler.
- the pulverized coal useful herein may be at least 50% under 200 mesh (74 microns), or as another example the coal useful herein is at least 60% under 200 mesh, or as an even further example, at least 70% under 200 mesh.
- Suitable biomass fuels may include living and/or dead biological material.
- Suitable biomass fuel sources may include, but are not limited to, plant matter, biodegradable wastes, municipal wastes, and industrial wastes. Biomass may be grown from several plants, including miscanthus, switchgrass, hemp, corn, poplar, willow, and sugarcane.
- Suitable petroleum coke may comprise a carbonization product (such as a carbonaceous solid) of high-boiling hydrocarbon fractions (heavy residues) obtained in petroleum processing (such as those derived from oil refinery coker units or other cracking processes).
- petroleum coke may include products such as green (or raw), calcined, or needle petroleum coke.
- the additives or additive package may be used with a liquid carrier or induction aid.
- Suitable carrier fluids may include any base oil as defined herein.
- Suitable solvents may comprise low aromatic Group I and/or Group II basestocks with a cSt of 4 at 100° C. Examples of solvents include 1) GP II 100 SN, 98 VI at about 4.0 cSt at 100° C. from Motiva and b) GP I 150 SN, 88 VI with 4.5 cSt at 100° C. from ExxonMobil.
- suitable carrier fluids can be of various types, such as for example liquid poly-alpha-olefin oligomers, mineral oils, liquid poly(oxyalkylene) compounds, liquid alcohols or polyols, polyalkenes, liquid esters, and similar liquid carriers.—Further, a suitable carrier fluid may comprise water. Mixtures of two or more such carriers can be employed.
- Liquid carriers can include butane not limited to 1) a mineral oil or a blend of mineral oils that have a viscosity index of less than about 120, 2) one or more poly-alpha-olefin oligomers, 3) one or more poly(oxyalkylene) compounds having an average molecular weight in the range of about 500 to about 3000, 4) polyalkenes, 5) polyalkyl-substituted hydroxyaromatic compounds or 6) mixtures thereof.
- the mineral oil carriers that can be used include paraffinic, naphthenic, and asphaltic oils, and can be derived from various petroleum crude oils and processed in any suitable manner.
- the mineral oils may be solvent extracted or hydrotreated oils. Reclaimed mineral oils can also be used. Hydrotreated oils may also be used.
- Suitable combustion improvers may comprise one or more of a manganese compound, an iron compound (including, for example, ferrocene), platinum-group metals, calcium, cerium oxide, copper, and the like.
- suitable combustion improvers include manganese carboxylate and ferrocene.
- a non-limiting example of a useful manganese compound is an alkylcycloalkyldienyl manganese tricarbonyl, such as methylcyclopentadienyl manganese tricarbonyl. It generally is added in treat rates of about 0.001 gram to about 1.0 gram of manganese per kilogram of fuel.
- Cyclopentadienyl manganese tricarbonyl compounds such as methylcyclopentadienyl manganese tricarbonyl are suitable combustion improvers because of their outstanding ability to reduce tailpipe emissions such as NO x and smog forming precursors and to significantly improve the octane quality of gasolines, both of the conventional variety and of the “reformulated” types
- Suitable combustion improvers may be derived from a metal-containing compound.
- Metal-containing compounds or metal ions may be inorganic metal compounds and/or organometallic compounds.
- the elemental or ionic metals can be one or more of the following group: sodium, potassium, magnesium, calcium, barium, strontium, titanium, cerium, chromium, molybdenum, manganese, iron, rubidium, cobalt, rhodium, nickel, palladium, platinum, copper, and silver compounds, and mixtures thereof.
- the inorganic metal compound can be selected from the group consisting of fluorides, chlorides, bromides, iodides, oxides, nitrates, sulfates, phosphates, carbonates, hydrides, nitrides, and mixtures thereof.
- the organometallic compound can be selected from the group consisting of alcohols, aldehydes, ketones, esters, anhydrides, sulfonates, phosphonates, chelates, phenates, crown ethers, carboxylic acids, amides, and mixtures thereof. Particularly useful are organometallic compounds containing one or more carbonyl groups, ethers or poly ethers, and other organic ligands able to coordinate with or bond with a metal, metal compound, or metal ion.
- Combustion additives may comprise a metal-containing catalyst.
- the additive may further comprise a ligand for complexing with the catalyst, and a solvent for carrying the catalyst/ligand complex.
- the catalyst may be comprised of one or more metals, such as, but not limited to, manganese, calcium, magnesium, potassium, zinc, and/or aluminum.
- the ligand may comprise one or more of, but not limited to, fossil fuel derived carboxylates, natural product carboxylates, genetically engineered natural products derived carboxylates, synthetic carboxylates, and/or mixtures thereof.
- Single metals may be derivatized to be used as combustion catalysts, such as, but not limited to Ca, Cr, Mn, Fe, Co, Cu, Sr, Y, Ru, Rh, Pd, La, Re, Os, Ir, Pt, and Ce.
- the respective carboxylates can be made from the appropriate metal starting material (oxide, hydroxide, etc.) and carboxylic acid and a solvent.
- Multimetallics may also be used.
- a co-catalyst may be used such as, for example, a magnesium carboxylate.
- a second co-catalyst may be used such as, for example, one derived from the alkali metal group (Li, Na, K, etc.).
- Suitable slag modifiers may comprise one of more individual compounds of magnesium, copper, manganese, aluminum, silicon, and the like.
- suitable slag modifiers include magnesium sulfonate and copper oxychloride.
- Other suitable slag modifiers may comprise one or more multimetallic compounds or minerals.
- suitable multimetallic slag modifiers include vermiculite and perlite. Slag modifiers are generally added in treat rates of about 0.001 gram to about 100 grams of metal per kilogram of fuel. The specific treat rate can be dictated by the amount of ash present in the fuel and the physical and chemical properties including chemical composition and melting temperature characteristics, of said ash.
- a particularly suitable additive solution may comprise a combination of a combustion improver and a slag modifier.
- Many problems handling or otherwise managing slag accumulation and/or removal from the boiler are exacerbated by poor combustion that results in a high level of unburned carbon in the slag.
- the presence of a combustion improver in the additive formulation reduces the amount of unburned carbon in the slag, thereby increasing the effectiveness of the slag modifier additive chemistry.
- Suitable slag modifiers may be derived from a metal-containing compound.
- the metal-containing compounds or metal ions may be inorganic metal compounds and/or organometallic compounds.
- the elemental or ionic metals can be one or more of the following group: magnesium, calcium, strontium, titanium, manganese, iron, aluminum, silicon, and copper compounds, and mixtures thereof.
- the inorganic metal compound can be selected from the group consisting of fluorides, chlorides, bromides, iodides, oxides, nitrates, sulfates, phosphates, carbonates, hydrides, nitrides, and mixtures thereof.
- the organometallic compound can be selected from the group consisting of alcohols, aldehydes, ketones, esters, anhydrides, sulfonates, phosphonates, chelates, phenates, crown ethers, carboxylic acids, amides, and mixtures thereof. Particularly useful are organometallic compounds containing one or more carbonyl groups, ethers or poly ethers, and other organic ligands able to coordinate with or bond with a metal, metal compound, or metal ion. Further, a suitable slag modifier may be derived from a multimetallic compound or mineral including vermiculite and perlite.
- Suitable fouling modifiers may comprise one or more individual compounds of magnesium, copper, manganese, aluminum, and the like. Examples of such fouling modifiers include magnesium hydroxide and magnesium oxide. Other suitable fouling modifiers may comprise one or more multimetallic compounds or minerals. Examples of suitable multimetallic fouling modifiers include vermiculite and perlite. Fouling modifiers are generally added in treat rates of about 0.001 gram to about 100 grams of metal per kilogram of fuel. The specific treat rate can be dictated by the amount of ash present in the fuel and the chemical and physical properties, especially chemical composition and melting temperature characteristics, of said ash.
- Suitable fouling modifiers may be derived from a metal-containing compound.
- the metal-containing compounds or metal ions may be inorganic metal compounds and/or organometallic compounds.
- the elemental or ionic metals can be one or more of the following group: magnesium, calcium, manganese, aluminum, copper compounds, and mixtures thereof.
- the inorganic metal compound can be selected from the group consisting of fluorides, chlorides, bromides, iodides, oxides, nitrates, sulfates, phosphates, carbonates, hydrides, nitrides, and mixtures thereof.
- the organometallic compound can be selected from the group consisting of alcohols, aldehydes, ketones, esters, anhydrides, sulfonates, phosphonates, chelates, phenates, crown ethers, carboxylic acids, amides, and mixtures thereof. Particularly useful are organometallic compounds containing one or more carbonyl groups, ethers or poly ethers, and other organic ligands able to coordinate with or bond with a metal, metal compound, or metal ion.
- Suitable fluxing agents may comprise one of more individual compounds of iron, sodium, potassium, and the like.
- One examples of a suitable fluxing agent is iron oxide.
- suitable anti-icing agents may comprise ether polymers, glycols, and alcohols.
- Suitable hygroscopic agents may comprise, for example but not limited to, glycerin, glycerol, urea, ethanol, methanol, concentrated sulfuric acid, magnesium oxide, magnesium sulfate, magnesium sulfonate, calcium carbonate, calcium carbonate, calcium silicates, silica gel, activated alumina, various zeolites, montmorillonite clay, and concentrated sodium hydroxide (lye).
- Suitable corrosion inhibitors may comprise one or more individual compounds of magnesium in particular. Examples of such corrosion inhibitors include magnesium hydroxide and magnesium oxide. Other suitable corrosion inhibitors may comprise one or more multimetallic compounds or minerals. Examples of suitable multimetallic corrosion inhibitors include vermiculite and perlite. Corrosion inhibitors are generally added in treat rates of about 0.001 gram to about 100 grams of metal per kilogram of fuel. The specific treat rate is dictated by the physical and chemical properties of the flue gas and flyash.
- the additive compositions may comprise other suitable components such as a manganese-containing compound for the reduction of carbon present in fly ash resulting from the combustion of coal. Further, additives for improving the performance and durability of electrostatic precipitators may be necessary in some embodiments. Suitable electrostatic precipitators may comprise sodium, lithium, potassium, manganese, and the like.
- the additive composition may comprise other suitable components such as those described in US 2005-0257724 A1, herein incorporated by reference, for the additive-induced control of NOx emissions in a coal burning utility furnace.
- Such additive may comprise a metal-containing combustion catalyst that may include one or more of the following metals: manganese, potassium, calcium, strontium, chromium, iron, cobalt, copper, lanthanide, cerium, platinum, palladium, rhodium, ruthenium, iridium, and osmium.
- Suitable manganese tricarbonyl compounds which can be used include cyclopentadienyl manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, dimethylcyclopentadienyl manganese tricarbonyl, trimethylcyclopentadienyl manganese tricarbonyl, tetramethylcyclopentadienyl manganese tricarbonyl, pentamethylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl manganese tricarbonyl, diethylcyclopentadienyl manganese tricarbonyl, propylcyclopentadienyl manganese tricarbonyl, isopropylcyclopentadienyl manganese tricarbonyl, tert-butylcyclopentadienyl manganese tricarbonyl, octylcyclopentadienyl manganese tricarbonyl, do
- the additive composition may comprise other suitable components such as those described in U.S. Ser. No. 11/743,707, herein incorporated by reference, for the removal of mercury-containing materials from emissions, such as flue gas, resulting from combustion devices.
- the additive composition may comprise other suitable components such as those described in US 2004-0118032, herein incorporated by reference, for the reduction of inhibition of corrosion in an atmospheric burner unit.
- the additive components may comprise a fuel-borne organometallic combustion system containing manganese, or a manganese precursor source, or derivative.
- the system may further contain a catalyst package that may comprise one or more individual organometallic compounds of lithium, sodium, potassium, magnesium, calcium, strontium, barium, molybdenum, iron, cobalt, platinum, cerium, and combinations, mixtures, or precursors thereof.
- the additive composition may comprise other suitable components such as those described in U.S. Pat. No. 7,094,274, herein incorporated by reference, for the improved efficiency of and reduction of back-corona discharge on electrostatic precipitators.
- the additive components may comprise manganese or a manganese-containing compound or precursor.
- suitable manganese-containing compounds include, but are not limited to, methyl cyclopentadienyl manganese tricarbonyl, manganese sulfonate, manganese phenate, manganese salicylate, cyclopentadienyl manganese tricarbonyl, alkyl cyclopentadienyl manganese tricarbonyl, organic manganese tricarbonyl derivatives, alkyl cyclopentadienyl manganese derivatives, bis-cyclopentadienyl manganese, bis-alkyl cyclopentadienyl manganese, neutral and overbased manganese salicylates, neutral and overbased manganese phenates, neutral and overbased manganese sulfonates, manganese carboxylates, and combinations and mixtures thereof.
- the additive composition may comprise oxygenates such as, but not limited to, methanol, ethanol, isopropanol, t-butanol, mixed alcohols, ethers such as methyl tertiary butyl ether, tertiary amyl methyl ether, ethyl tertiary butyl ether and mixed ethers; polyethers such as 2-methoxy ethyl ether (diglyme), triglyme; polyols; poyether alcohols such as di(ethylene glycol) monomethyl ether, and mixtures thereof.
- oxygenates such as, but not limited to, methanol, ethanol, isopropanol, t-butanol, mixed alcohols, ethers such as methyl tertiary butyl ether, tertiary amyl methyl ether, ethyl tertiary butyl ether and mixed ethers; polyethers such as 2-methoxy ethyl ether
- additive components described above may be supplied in the form of solutions of active ingredient(s) in an inert diluent or solvent, such as a diluent oil.
- an inert diluent or solvent such as a diluent oil.
- concentrations of each additive component are expressed in terms of active additive, i.e., the amount of solvent or diluent that may be associated with such component as received is excluded.
- the individual components employed may be separately blended into or combined with the fuel or carrier fluid or may be blended therein in various sub-combinations, if desired. Ordinarily, the particular sequence of such blending steps is not crucial. Moreover, such components may be blended or combined in the form of separate solutions in a diluent. It may be preferable, however, to blend the additive components used in the form of a concentrate, as this simplifies the blending operations, reduces the likelihood of blending errors, and takes advantage of the compatibility and solubility characteristics afforded by the overall concentrate.
- Additive concentrates may thus be formulated to contain all of the additive components and if desired, some of the base fuel component, in amounts proportioned to yield finished fuel blends consistent with the concentrations described above.
- the additive concentrate will contain one or more diluents such as light carrier oils, to facilitate handling and blending of the concentrate.
- concentrates containing up to about 50 wt. % of one or more diluents or solvents may be used, provided the solvents are not present in amounts that interfere with the low and high temperature and flash point characteristics and the performance of the finished additive formulation.
- Such additive concentrates are suitably devoid of materials or components that are bioaccumulative, toxic, and/or persistent as indicated by the tests described above.
- materials include but are not limited to, certain alkanes, alkoxy alkylamines, alkyl methacrylates, alkyl phenols, alkylphenols, polyoxyalkyl alkylamines, aryl amines, aryl phosphites, branched alkyl phenols, branched alkyl polysulfides, branched long-chain alkyl amines, long-chain alkenyl alkyl amine, long-chain alkenyl alkylene amines, long-chain alkenyl amines, long-chain alkoxylated amines, long-chain alkyl alkoxylated alcohols, long-chain alkyl alkylene amines, long-chain alkyl amines, long-chain alkyl methacrylates, long-chain alkyoxylated amines, long-chain
- Fuels and fuel additives of the embodiments herein may be formulated to provide enhanced fuel properties for various applications.
- a fuel composition according to the present disclosure may be used for combustion for the production of power as well as stationary burners, power plants, industrial plants, home heating operations, and the like.
- composition of the present disclosure may be manufactured in the United States of America or Canada.
- composition of the present disclosure may be transported to Europe by ship, air, rail, or truck.
- each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated the following claims.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Fuel additive packages and fuel compositions, suitable for use with solid fuels, having environmentally compatible characteristics as defined by European Council Directive 67/548/EEC is disclosed. Such additive packages and compositions may include components selected from non-persistent materials, non-bioaccumulative materials, and/or or non-toxic materials.
Description
- The present disclosure relates to the field of fuel additives, fuels, and fuel compositions, specifically environmentally-friendly fuel additives and fuel additive compositions suitable for use with solid fuels.
- As concern for the environment grows worldwide, the safety of the various chemical substances used in fuel compositions and fuel additive concentrates is becoming more of a concern for manufacturers and distributors. It is paramount for the industry to examine the use of functional fuel additive components that are also compatible with environmental regulations. In particular, substances that are persistent in the environment, bioaccumulative, and toxic may be banned from use. Hence, there exists a need for fuel additive compositions and fuel formulations containing such additive compositions that incorporate more environmentally acceptable materials.
- In some embodiments disclosed herein, an environmentally compatible fuel additive composition suitable for use with a solid fuel may comprise at least one functional component, wherein the component is selected from the group consisting of a non-persistent material, a non-bioaccumulative material, and a non-toxic material. In some embodiments, the additive composition may be substantially devoid of any component that is persistent, bioaccumulative, and toxic.
- In another embodiment, an environmentally compatible solid fuel composition, may comprise a) a major amount of a solid fuel; and b) a minor amount of an additive composition. The additive composition may comprise at least one of a functional component, wherein the component comprises at least one of: i) an acceptable level biodegradation of at least one of: 1) a half-life in marine water of less than 60 days; 2) a half-life in fresh or estuarine water of less than 40 days; 3) a half-life in marine sediment of less than 180 days; 4) a half-life in fresh or estuarine water sediment less than 120 days; or 5) a half-life in soil less than 120 days, as determined by a biodegradation test; ii) a bioconcentration factor below 2000 in a bioconcentration factor test; or iii) is devoid of a toxic effect at an aqueous concentration below 0.01 mg/L on a toxicity test.
- In another embodiment, a method of making an environmentally compatible solid fuel composition may comprise combining a major amount of a solid fuel and a minor amount of an additive composition. The additive composition may comprise at least one functional component wherein the component is selected from: i) a material having an acceptable level biodegradation of at least one of: 1) a half-life in marine water of less than 60 days; 2) a half-life in fresh or estuarine water of less than 40 days; 3) a half-life in marine sediment of less than 180 days; 4) a half-life in fresh or estuarine water sediment less than 120 days; or 5) a half-life in soil less than 120 days, as determined by a biodegradation test; ii) a material having a bioconcentration factor below 2000 in a bioconcentration factor test; or iii) a material that is devoid of a toxic effect at an aqueous concentration below 0.01 mg/L on a toxicity test. The solid fuel composition may comply with European Council Directive 67/548/EEC.
- In another embodiment, an environmentally compatible solid fuel composition may comprise a major amount of a solid fuel and a minor amount of an additive composition. The additive composition may comprise at least one functional component, wherein the component is at least selected from the group consisting of non-persistent materials, non-bioaccumulative materials, and non-toxic materials, and the additive composition is substantially devoid of any component that is persistent, bioaccumulative, and toxic.
- An advantage of embodiments of the disclosure is that an impact on the environment by the use of materials disclosed herein may be lessened. A further advantage is that accidental or inadvertent spills of the additive compositions and/or fuel compositions may not pose long term threats to humans and wildlife. Still further advantages of the compositions and methods described herein may be acceptable to national and state regulatory agencies.
- As used herein, the terms “fuel composition,” and “fuel” are considered synonymous, fully interchangeable terminology referring to the finished fuel product comprising a major amount of a solid fuel plus a minor amount of a fuel additive composition. “Solid fuel” herein can in one embodiment be selected from the group consisting of coal, coke, coke breeze, carbonaceous char, petroleum pitch, petroleum coke, refuse derived fuel (RDF), municipal solid waste (MSW), biomass, bagasse, wood, wood pellets, wood bark, wood by-products, wood wastes, sawdust, hog fuel, black liquor solids, waste tires, charcoal, peat, corn, corn cobs, wheat, rye, and other grains, coffee grounds, and tobacco wastes.
- As used herein, the terms “additive package,” “additive concentrate,” and “additive composition” are considered synonymous, fully interchangeable terminology referring to the portion of the fuel composition excluding the solid fuel.
- As used herein, a “functional” component means a component that is used in a fuel formulation to provide a measurable change in a characteristic or property of a fuel containing the component or in a property of the system delivering the fuel, or the system combusting the fuel, or the system exhausting the products from the combustion of the fuel.
- As used herein, the terms “agent” and “additive” are considered synonymous, fully interchangeable terminology referring to any single component of a fuel composition excluding the major amount of solid fuel in the mixture.
- As used herein, the term “substantially devoid” means containing no more than, for example, a trace amount, an innocuous amount, or a contaminant amount.
- As used herein, the term “NOx” refers to, for example, the chemical species nitric oxide (NO) and/or nitrogen dioxide (NO2) which may be emitted from combustion sources. In some instances NOx may define dinitrogen monoxide (N2O), dinitrogen trioxide (N2O3), dinitrogen tetroxide (N2O4), and/or dinitrogen pentoxide N2O5).
- Additional objects and advantages of the disclosure will be set forth in part in the description which follows, and/or can be learned by practice of the disclosure. The objects and advantages of the disclosure will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims.
- It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure, as claimed.
- Exemplary embodiments of the disclosure will now be provided to illustrate limited aspects of the preferred embodiments thereof, including various examples and illustrations of the formulation and use of the disclosed embodiments. It will be understood that these embodiments are presented solely for the purpose of illustrating the embodiments and shall not be considered as a limitation upon the scope thereof.
- European Council Directive 76/548/EEC, incorporated herein by reference, provides regulatory guidance for the registration and evaluation of chemical substances that may be exposed to the environment during the normal course of use. Guidelines and testing procedures are enumerated therein, so that the potential environmental impact of any substance may be quantified.
- A number of diagnostic tests have been developed to measure the effects of certain chemical substances upon various aspects of the environment. In particular, three main parameters are used to classify such substances: namely, persistence, bioaccumulation, and toxicity.
- The persistence of a substance in the environment may be inversely related to the biodegradability of the substance. Biodegradability is the ability of microbes occurring in an environment to break down a substance into simpler substances. The persistence, or biodegradability, criterion is defined in European Council Directive 76/548/EEC Annex XIII section 1.1, which is herein incorporated by reference, as a substance fulfilling one of the following criteria: having a half-life in marine water longer than 60 days, having a half-life in fresh or estuarine water longer than 40 days, having a half-life in marine sediment longer than 180 days, having a half-life in fresh or estuarine water sediment longer than 120 days, or having a half-life in soil longer than 120 days.
- A material's persistence in the environment may be determined by a number of different test procedures, including the following tests: a dissolved organic carbon (DOC) die-away test, a modified OECD screening dissolved organic carbon die-away test, a carbon dioxide evolution test, a manometric respirometry test, a closed bottle test, a MITI test, a Zahn-Wellens test, an activated sludge simulation test, an activated sludge respiration inhibition test, and a modified SCAS test. The above test procedures are set forth in European Council Directive 76/548/EEC Annex V, sections C.4, C.9, C.10, C.11, and C.12, which are incorporated in full herein by reference, and are summarized below.
- Six test methods are described that permit the screening of chemicals for ready biodegradability in an aerobic aqueous medium:
- (a) Dissolved Organic Carbon (DOC) Die-Away (Method C.4-A)
- (b) Modified OECD Screening—DOC Die-Away (Method C.4-B)
- (c) Carbon dioxide (CO2) Evolution (Method C.4-C)
- (d) Manometric Respirometry (Method C.4-D)
- (e) Closed Bottle (Method C.4-E)
- (f) MITI (Ministry of International Trade and Industry—Japan) (Method C.4-F)
- For example, a solution, or suspension, of the test substance in a mineral medium is introduced into an inoculum and incubated under aerobic conditions in the dark or in diffuse light. The amount of dissolved organic carbon (DOC) in the test solution due to microbial inoculum should be kept as low as possible compared to the amount of DOC due to the test substance. Allowance is made for the endogenous activity of the inoculum by running parallel blank tests with inoculum but without test substance, although the endogenous activity of cells in the presence of the substance will not exactly match that in the endogenous control. A reference substance is run in parallel to check the operation of the procedures.
- In general, degradation is followed by the determination of parameters, such as DOC, CO2 production, and oxygen uptake, and measurements are taken at sufficiently frequent intervals to allow the identification of the beginning and end of biodegradation. With automatic respirometers the measurement is continuous. DOC is sometimes measured in addition to another parameter but this is usually done only at the beginning and the end of the test. Specific chemical analysis may also be used to assess primary degradation of the test substance, and to determine the concentration of any intermediate substances formed (obligatory in the MITI test).
- Normally, the tests last for 28 days. Tests however may be ended before 28 days, i.e., as soon as the biodegradation curve has reached a plateau for at least 3 determinations. Tests may also be prolonged beyond 28 days when the curve shows that biodegradation has started but that the plateau has not been reached by day 28.
- The inoculum may be derived from a variety of sources: activated sludge, unchlorinated sewage effluents, surface waters and soils, or from a mixture of these.
- In the dissolved organic carbon die-away test and the modified OECD screening dissolved organic carbon die-away test, a measured volume of inoculated mineral medium containing a known concentration of the test substance (10-40 mg DOC/1) as the nominal sole source of organic carbon is aerated in the dark or diffused light at 22±2° C. Degradation is followed by DOC analysis at frequent intervals over a 28-day period. The degree of biodegradation is calculated by expressing the concentration of DOC removed (corrected for that in the blank inoculum control) as a percentage of the concentration initially present. The degree of primary biodegradation may also be calculated from supplemental chemical analysis made at the beginning and end of incubation.
- In the carbon dioxide evolution test a measured volume of inoculated mineral medium containing a known concentration of the test chemical (10-20 mg DOC or total organic carbon (TOC) per liter) as the nominal sole source of organic carbon is aerated by the passage of carbon dioxide-free air at a controlled rate in the dark or in diffuse light. Degradation is followed over 28 days by determining the carbon dioxide produced, which is trapped in barium or sodium hydroxide and which is measured by titration of the residual hydroxide or as inorganic carbon. The amount of carbon dioxide produced from the test chemical (corrected for that derived from the blank inoculum) is expressed as a percentage of theoretical maximum carbon dioxide produced (ThCO2). The degree of biodegradation may also be calculated from supplemental DOC analysis made at the beginning and end of incubation.
- The percentage degradation may be calculated by:
-
% degradation=(mg CO2 produced×100)/(ThCO2×mg test chemical added) - In the manometric respirometry test a measured volume of inoculated mineral medium, containing a known concentration of test chemical (100 mg/liter of the test substance, to give at least 50-100 mg theoretical oxygen demand/liter) as the nominal sole source of organic carbon, is stirred in a closed flask at a constant temperature (±1° C. or closer) for up to 28 days. The consumption of oxygen may be determined either by measuring the quantity of oxygen (produced electrolytically) required to maintain constant gas volume in the respirometer flask, or from the change in volume or pressure (or a combination of the two) in the apparatus. Evolved carbon dioxide is absorbed in a solution of potassium hydroxide or another suitable absorbent. The amount of oxygen taken up by the test chemical (corrected for uptake by a blank inoculum, run in parallel) is expressed as a percentage of ThOD (theoretical oxygen demand) or COD (chemical oxygen demand). Optionally, primary biodegradation may also be calculated from supplemental specific analysis made at the beginning and end of incubation, and ultimate biodegradation by DOC analysis.
- In the closed bottle test a solution of the test chemical in mineral medium, usually at 2-5 mg/liter, is inoculated with a relatively small number of micro-organisms from a mixed population and kept in completely full closed bottles in the dark at constant temperature. Degradation is followed by analysis of dissolved oxygen over a 28-day period. The amount of oxygen taken up by the test chemical, corrected for uptake by a blank inoculum run in parallel as a control, is expressed as a percentage of ThOD or COD.
- In the MITI test, the oxygen uptake by a stirred solution, or suspension, of the test chemical in a mineral medium, inoculated with specially grown, unadapted micro-organisms, is measured automatically over a period of 28 days in a darkened, enclosed respirometer at 25±1° C. Evolved carbon dioxide is absorbed by soda lime. Biodegradability is expressed as the percentage oxygen uptake (corrected for blank uptake) of the theoretical oxygen uptake (ThOD). The percentage of primary biodegradability is also calculated from supplemental specific chemical analysis made at the beginning and end of incubation and, optionally, by DOC analysis.
- The purpose of the Zahn-Wellens Test is the evaluation of the potential ultimate biodegradability of water-soluble, non-volatile organic substances when exposed to relatively high concentrations of micro-organisms in a static test. The substances to be studied are used in concentrations corresponding to DOC-values in the range of 50 to 400 mg/liter or COD-values in the range of 100 to 1000 mg/liter (DOC=dissolved organic carbon; COD=chemical oxygen demand). These relatively high concentrations have the advantage of analytical reliability. Compounds with toxic properties may delay or inhibit the degradation process. In this method, the measure of the concentration of dissolved organic carbon or the chemical oxygen demand is used to assess the ultimate biodegradability of the test substance. A simultaneous use of a specific analytical method may allow the assessment of the primary biodegradation of the substance (disappearance of the parent chemical structure). The method is applicable only to those organic test substances which, at the concentration used in the test are soluble in water under the test conditions, have negligible vapor pressure under the test conditions, are not inhibitory to bacteria, are adsorbed within the test system only to a limited extent, and are not lost by foaming from the test solution.
- Activated sludge, mineral nutrients and the test material as the sole carbon source in an aqueous solution are placed together in a one to four liter glass vessel equipped with an agitator and an aerator. The mixture is agitated and aerated at 20 to 25° C. under diffuse illumination or in a dark room for up to 28 days. The degradation process is monitored by determination of the DOC (or COD) values in the filtered solution at daily or other appropriate regular time intervals. The ratio of eliminated DOC (or COD) after each interval to the value three hours after the start is expressed as percentage biodegradation and serves as the measure of the extent of degradation at this time. The result is plotted versus time to give the biodegradation curve.
- The activated sludge simulation test is used to determine the primary biodegradability of a substance in an activated sludge plant model, at a concentration of about 20 mg/liter. This allows the assessment of the primary biodegradability of the substance (disappearance of the parent chemical structure). Another purpose of the method is the determination of ultimate biodegradability by the measurement of the removal of the substance and any metabolites in an activated sludge plant model at a concentration corresponding to >12 mg DOC/liter (or approximately 40 mg COD/liter); wherein 20 mg DOC/liter seems to be optimal.
- For the determination of ultimate biodegradability, two activated sludge pilot units are run in parallel. The test substance is added to the influent (synthetic or domestic sewage) of one of the units, while the other blank unit receives the sewage alone. For the determination of primary biodegradation with specific analysis in the influent and effluent, only one unit may be used.
- The sludge growth/stabilization period is the period during which the concentration of the activated sludge suspended solids and the performance of the units' progress to a steady state under the operating conditions used.
- The running-in period is the period which lasts from the time the test substance is first added to the time when its removal reaches a plateau (relatively constant value). This period must not exceed six weeks.
- The evaluation period is a three week period, i.e., three weeks from the time that the removal of the test substance reaches a relatively constant, and usually high, value. For those substances which show little or no degradation in the first six weeks, the evaluation period is taken as the following three weeks.
- Influent without substance to be tested must pass through an aeration vessel either at the rate of one liter per hour or a rate of one-half liter per hour thereby providing a mean retention time of either three or six hours. The rate of aeration should be regulated so that the content of the vessel is kept constantly in suspension while the dissolved oxygen content is at least 2 mg/liter.
- The sludge which has accumulated around the top of the aeration vessel must be returned to the mixed liquor at least once each day by brushing or some other appropriate means. The effluent is collected in a second vessel for 20 to 24 hours, and a sample is taken after thorough mixing.
- In order to monitor and control the efficiency of the process, the chemical oxygen demand (COD) or the dissolved organic carbon (DOC) of the filtrate of the accumulated effluent is measured at least twice weekly, as well as that of the filtered influent (using a membrane of pore size 0.45 □m, wherein the first 20 ml (approximately) of the filtrate are discarded). The reduction in COD or DOC should level off when a roughly regular daily degradation is obtained.
- The operating conditions of the running-in period are maintained and sufficient stock solution (approximately 1%) of the test material is added to the influent of the test unit so that the desired concentration of test material (approximately 10 to 20 mg DOC/liter or 40 mg COD/liter) in the sewage is obtained. This may be done by mixing the stock solution to the sewage daily or by means of a separate pumping system. This concentration may be reached progressively. If there are no toxic effects of the test substance on the activated sludge, higher concentrations may also be tested.
- The blank unit is fed only with influent without added substances. Adequate volumes of the effluents are taken for analysis and filtered through membrane filters (0.45 □m), the first 20 ml (approximately) of filtrate being discarded.
- The filtered samples have to be analyzed on the same day, otherwise they must be preserved by any suitable method, for example, by using 0.05 ml of a 1% mercuric chloride (HgCl2) solution for each 10 ml of filtrate or by storing them at 2 to 4° C. up to 24 hours, or below −18° C. for longer periods.
- The running-in time, with addition of test substance, should not exceed six weeks and the evaluation period should not be shorter than three weeks, so that about 14 to 20 determinations are available for calculation of the final result.
- The activated sludge respiration inhibition test assesses the effect of a test substance on micro-organisms by measuring the respiration rate under defined conditions in the presence of different concentrations of the test substance. The purpose of this method is to provide a rapid screening method whereby substances which may adversely affect aerobic microbial treatment may be identified, and to indicate suitable non-inhibitory concentrations of test substances to be used in biodegradability tests. Two controls without the test substance are included in the test design, one at the start and the other at the end of the test series. Each batch of activated sludge should also be checked using a reference substance.
- The activated sludge respiration inhibition method is most readily applied to substances which, due to their water solubility and low volatility, are likely to remain in water. For substances with limited solubility in the test media, it may not be possible to determine the EC50. Results based on oxygen uptake may lead to erroneous conclusions if the test substance has the propensity to uncouple oxidative phosphorylation. It may be useful to have the following information to perform the test: water solubility, vapor pressure, structural formula, and the purity of the test substance.
- It is recommended that 3,5-dichlorophenol, as a known inhibitor of respiration, be used as a reference substance and tested for EC50 on each batch of activated sludge as a means of checking that the sensitivity of the sludge is not abnormal.
- At least five concentrations, spaced by a constant factor preferably not exceeding 3.2, are used. At time ‘0’, 16 ml of the synthetic sewage feed are made up to 300 ml with water. 200 ml of microbial inoculum are added and the total mixture (500 ml) poured into a first vessel (first control C1). The test vessels should be aerated continuously so as to ensure that the dissolved O2 does not fall below 2.5 mg/liter and that, immediately before the measurement of the respiration rate, the O2 concentration is about 6.5 mg/liter.
- At time ‘15 minutes’ (15 minutes is an arbitrary, but convenient, interval) the above is repeated, except that 100 ml of the test substance stock solution are added to the 16 ml of synthetic sewage before adding water to 300 ml and microbial inoculum to make a volume of 500 ml. This mixture is then poured into a second vessel and aerated as above. This process is repeated at 15-minute intervals with different volumes of the test substance stock solution to give a series of vessels containing different concentrations of the test substance.
- Finally, a second control is prepared (C2). After three hours the pH is recorded, and a well-mixed sample of the contents of the first vessel is poured into the measuring apparatus and the respiration rate is measured over a period of up to 10 minutes. This determination is repeated on the contents of each vessel at 15-minute intervals, in such a way that the contact time in each vessel is three hours. The reference substance may be tested on each batch of microbial inoculum in the same way.
- The modified SCAS test is used to evaluate the potential ultimate biodegradability of water-soluble, non-volatile organic substances when exposed to relatively high concentrations of micro-organisms over a long time period. The viability of the microorganisms is maintained over this period by daily addition of a settled sewage feed.
- The conditions provided by the test are highly favorable to the selection and/or adaptation of microorganisms capable of degrading the test compound, however the procedure may also be used to produce acclimatized inocula for use in other tests.
- According to the method, the measure of the concentration of dissolved organic carbon is used to assess the ultimate biodegradability of the test substances. It is preferable to determine DOC after acidification and purging rather than as the difference of Ctotal−Cinorganic.
- The method is applicable only to those organic test substances which, at the concentration used in the test are soluble in water (at least 20 mg dissolved organic carbon/liter), have negligible vapor pressure, are not inhibitory to bacteria, do not significantly adsorb within the test system, and are not lost by foaming from the test solution. The organic carbon content of the test substance must be established prior to running the test.
- Activated sludge from a sewage treatment plant is placed in a semi-continuous activated sludge (SCAS) unit. The test compound and settled domestic sewage are added, and the mixture is aerated for 23 hours. The aeration is then stopped, the sludge allowed to settle, the mixture supernatant liquor is removed. The sludge remaining in the aeration chamber is then mixed with a further aliquot of test compound and sewage and the cycle is repeated.
- Biodegradation is established by determining the dissolved organic carbon content of the supernatant liquor. This value is compared with that found for the liquor obtained from a control tube dosed with settled sewage only.
- Ideally, the dissolved organic carbon in the supernatant liquors is determined daily, although less frequent analyses may be used. Before analysis the liquors are filtered through washed 0.45 μm membrane filters or centrifuged. Membrane filters are suitable if it is assured that they neither release carbon nor absorb the substance in the filtration step. The temperature of the sample must not exceed 40° C. while it is in the centrifuge. The length of the test for compounds showing little or no biodegradation is indeterminate, but experience suggests that this should be at least 12 weeks in general, but not longer than 26 weeks.
- Bioaccumulation, or bioconcentration, is defined as the increase in concentration of a test substance in or on an organism or specified tissues thereof relative to the concentration of the substance in the surrounding medium. As used herein, the terms “bioaccumulation” and “bioconcentration” are used interchangeably to refer to the same criteria. The bioconcentration factor (“BCF”) is calculated as the concentration of test substance in an organism (or specified tissues thereof) divided by the concentration of the substance in the surrounding medium. Both the uptake and deputation of substances by organisms, and the respective rates thereof, are considered in calculating bioaccumulation.
- One predictive factor for bioaccumulation may be a substance's octanol-water partition coefficient (POW). The POW is a substance's solubility in n-octanol and water at equilibrium. The logarithm of POW may be an indication of a substance's potential for bioaccumulation in aquatic organisms.
- The criterion for acceptable bioaccumulation is defined in European Council Directive 76/548/EEC Annex XIII section 1.2, which is herein incorporated by reference, as a substance having a bioconcentration factor higher than 2000. The bioconcentration factor of a material may be determined by test procedures set forth in European Council Directive 76/548 EEC Annex V, section C.13 flow-through fish test, which is incorporated in full herein by reference.
- The flow-through fish test consists of two phases: the exposure (uptake) phase and the post-exposure (depuration) phase. During the uptake phase, separate groups of fish of one species are exposed to at least two concentrations of the test substance. They are then transferred to a medium free of the test substance for the depuration phase. A depuration phase is always necessary unless uptake of the substance during the uptake phase has been insignificant (e.g., the BCF is less than 10). The concentration of the test substance in/on the fish (or specified tissue thereof) is followed through both phases of the test. In addition to the two test concentrations, a control group of fish is held under identical conditions except for the absence of the test substance, to relate possible adverse effects observed in the bioconcentration test to a matching control group and to obtain background concentrations of test substance.
- The uptake phase is run for 28 days unless it is demonstrated that equilibrium has been reached earlier. The depuration period is then begun by transferring the fish to the same medium but without the test substance in another clean vessel. Where possible the bioconcentration factor is calculated preferably both as the ratio (BCFSS) of concentration of the fish (Cf) and in the water (Cw) at apparent steady-state and as a kinetic bioconcentration factor, BCFK as the ratio of the rate constants of uptake (k1) and depuration (k2) assuming first-order kinetics.
- If a steady-state is not achieved within 28 days, the uptake phase should be extended until steady-state is reached, or 60 days, whichever comes first; the depuration phase is then begun.
- The BCF is expressed as a function of the total wet weight of the fish. However, for special purposes, specified tissues or organs (e.g. muscle, liver), may be used if the fish are sufficiently large or the fish may be divided into edible (fillet) and non-edible (viscera) fractions. Since, for many organic substances, there is a clear relationship between the potential for bioconcentration and lipophilicity, there is also a corresponding relationship between the lipid content of the test fish and the observed bioconcentration of such substances. Thus, to reduce this source of variability in test results for those substances with high lipophilicity (i.e. with log POW>3), bioconcentration should be expressed in relation to lipid content in addition to whole body weight.
- The lipid content is determined on the same biological material as is used to determine the concentration of the test substance, when feasible.
- The toxicity criterion is defined in European Council Directive 76/548/EEC Annex XIII section 1.3, which is herein incorporated by reference, as a substance having a long-term no-observed effect concentration (NOEC) for marine or freshwater organisms less than 0.01 mg/L. Substances that are classified as carcinogenic, mutagenic, or toxic for reproduction may also be considered as toxic.
- The toxicity of a material may be determined by test procedures, such as the acute toxicity for fish test, the acute toxicity for Daphnia test, and the algal inhibition test, set forth in European Council Directive 76/548/EEC Annex V, sections C.1, C.2, and C.3, which are incorporated in full herein by reference. These acute tests may be used for first cut screening (if LC50<1 ppm), however chronic toxicity tests (usually in Daphnia but also other organisms) may be used for definitive Toxicity.
- The purpose of the acute toxicity for fish test is to determine the acute lethal toxicity of a substance to fish in fresh water. It is desirable to have, as far as possible, information on the water solubility, vapor pressure, chemical stability, dissociation constants, and biodegradability of the substance to help in the selection of the most appropriate test method (static, semi-static, or flow-through) for ensuring satisfactorily constant concentrations of the test substance over the period of the test.
- Additional information (for instance structural formula, degree of purity, nature and percentage of significant impurities, presence and amounts of additives, and n-octanol/water partition coefficient) should be taken into consideration in both the planning of the test and interpretation of the results.
- Acute toxicity is the discernible adverse effect induced in an organism within a short time (days) of exposure to a substance. In the present test, acute toxicity is expressed as the median lethal concentration (LC50), the concentration in water which kills 50% of a test batch of fish within a continuous period of exposure which must be stated.
- Three types of procedure may be used. The static test is a toxicity test in which no flow of test solution occurs. The solutions remain unchanged throughout the duration of the test. The semi-static test is a test without flow of test solution, but with regular batchwise renewal of test solutions after prolonged periods (e.g. 24 hours). The flow-through test is a toxicity test in which the water is renewed constantly in the test chambers, the chemical under test being transported with the water used to renew the test medium.
- At least 7 fish per concentration being tested are exposed to the substance for a duration of 96 hours in tanks of suitable capacity. At least five concentrations differing by a constant factor not exceeding 2.2, and as far as possible spanning the range of 0 to 100% mortality, should be tested for each substance. The fish may not be fed during the test. The fish are inspected after the first 2 to 4 hours and afterward at least at 24-hour intervals. Fish are considered dead if touching of the caudal peduncle produces no reaction, and no breathing movements are visible. Dead fish are removed when observed and mortalities are recorded. Records are kept of visible abnormalities (e.g. loss of equilibrium, changes in swimming behavior, respiratory function, pigmentation, etc.). Measurements of pH, dissolved oxygen and temperature must be carried out daily.
- The acute toxicity for Daphnia test is similar to the acute toxicity for fish test, but the purpose is to determine the median effective concentration for immobilization (EC50) of a substance to Daphnia in fresh water. As with the toxicity for fish test, it is desirable to have, as far as possible, information on the water solubility, vapor pressure, chemical stability, dissociation constants, and biodegradability of the test substance before starting the test. Additional information (for instance structural formula, degree of purity, nature and percentage of significant impurities, presence and amount of additives, and n-octanol/water partition coefficient) should be taken into consideration in both the planning of the test and interpretation of the results.
- The Daphnia are exposed to the test substance added to water at a range of concentrations for 48 hours. Under otherwise identical test conditions, and an adequate range of test substance concentrations, different concentrations of a test substance exert different average degrees of effect on the swimming ability of Daphnia. Different concentrations result in different percentages of Daphnia being no longer capable of swimming at the end of the test. The concentrations causing zero or 100% immobilization are derived directly from the test observations whereas the 48-hour EC50 may be determined by calculation if possible. A static system is used for this method, hence test solutions are not renewed during the exposure period.
- Stock solutions of the required strength are prepared by dissolving the substance in deionized water or water. The chosen test concentrations are prepared by dilution of the stock solution. If high concentrations are tested, the substance may be dissolved in the dilution water directly.
- The substances are normally only tested up to the limit of solubility. For some substances (e.g. substances having low solubility in water, or high POW, or those forming stable dispersion rather than true solution in water), it is acceptable to run a test concentration above the solubility limit of the substance to ensure that the maximum soluble/stable concentration has been obtained. It is important, however, that this concentration will not otherwise disturb the test system. (e.g. film of the substance on the water surface preventing the oxygenation of the water, etc.).
- Daphnia magna is the preferred test species although Daphnia pulex is also permitted. The test animals shall be less than 24 hours old at the beginning of the test, laboratory bred, free from overt disease, and with a known history (e.g. breeding, any pretreatments, etc.).
- The Daphnia are exposed to the substance for 48 hours. At least 20 animals at each test concentration, preferably divided into four batches of five animals each or two batches of 10, are required. At least 2 ml of test solutions should be provided for each animal. The test solution should be prepared immediately before introduction of the Daphnia, preferably without using any solvent other than water. The concentrations are made up in a geometric series, at a concentration ratio not exceeding 2.2. Concentrations sufficient to give 0 and 100% immobilization after 48 hours and a range of intermediate degrees of immobilizations permitting calculation of the 48 hour EC50 should be tested together with controls. The test temperature should be between 18 and 22° C., but for each single test it should be constant within ±1° C. The test solutions must not be bubble-aerated, and the animals may not be fed during the test. The pH and the oxygen concentration of the controls and of all the test concentrations should be measured at the end of the test; the pH of the test solutions should not be modified. Volatile compounds should be tested in completely filled closed containers, large enough to prevent lack of oxygen. The Daphnia are inspected at least after 24 hours exposure and again after 48 hours.
- For each period where observations were recorded (24 and 48 h), the percentage mortality is plotted against concentration on logarithmic-probability paper. In those cases where the slope of the concentration/percentage response curve is too steep to permit calculation of the EC50, a graphical estimate of this value is sufficient. When two immediately consecutive concentrations at a ratio of 2.2 give only 0 and 100% immobilization these two values are sufficient to indicate the range within which the EC50 falls.
- The algal inhibition test may be used to determine the effects of a substance on the growth of a unicellular green algal species. Relatively brief (72 hours) tests may assess effects over several generations. This method may be adapted for use with several different unicellular algal species. The method is most easily applied to water-soluble substances which, under the conditions of the test, are likely to remain in the water.
- Exponentially-growing cultures of selected green algae are exposed to various concentrations of the test substance over several generations under defined conditions. The test solutions are incubated for a period of 72 hours, during which the cell density in each solution is measured at least every 24 hours. The inhibition of growth in relation to a control culture is determined.
- Test cultures containing the desired concentrations of test substance and the desired quantity of algal inoculum are prepared by adding aliquots of stock solutions of the test substance to suitable amounts of pre-prepared algal cultures.
- The culture flasks are shaken and placed in the culturing apparatus. The algal cells are kept in suspension by shaking, stirring, or bubbling with air, in order to improve gas exchange and reduce pH variation in the test solutions. The cultures are maintained at a temperature in the range of 21 to 25° C., controlled at ±2° C.
- The cell density in each flask is determined at least at 24, 48 and 72 hours after the start of the test. Filtered algal medium containing the appropriate concentration of the test chemical is used to determine the background when using cell density measurements other than direct counting methods.
- A suitable fuel or fuel additive composition, according to one embodiment of the present disclosure, may use functional components that may not exhibit at least one of persistence, bioaccumulation, or toxicity when tested according to the procedures set forth above. Accordingly, a functional component that is found to be persistent, bioaccumulative, and toxic may not be included in fuel formulations of the present disclosure.
- In another embodiment, a functional component may be non-persistent but may be bioaccumulative and toxic. In another embodiment, a functional component may be non-bioaccumulative but may be persistent and toxic. In another embodiment, a functional component may be non-toxic but may be persistent and bioaccumulative.
- In another embodiment, a functional component may be non-persistent and non-bioaccumulative but may be toxic. In another embodiment, a functional component may be non-persistent and non-toxic but may be bioaccumulative. In another embodiment, a functional component may be non-bioaccumulative and non-toxic but may be persistent.
- In another embodiment, a functional component may be non-persistent, non-bioaccumulative, and non-toxic.
- Suitable embodiments may comprise additive compositions containing one or more of the following: acid plume reducing agents, anti-icing agents, biocides, carrier fluids, combustion improvers, corrosion inhibitors, diluents, dust suppressants, electrostatic precipitator activating agents, fluxing agents, fouling modifiers, hygroscopic agents, ignition improvers, markers or customer-specific “tags,” reodorants, mercury scavengers, nitrogen oxide (NOx) scavengers, NOx reducing agents, slag modifiers, sulfur oxide (SO2/SO3) scavengers, and surfactants.
- Suitable embodiments may comprise one or more of methyl cyclopentadienyl manganese tricarbonyl, cyclopentadienyl manganese tricarbonyl, octane enhancer materials, alkyl nitrates, glycols, phenates, salicylates, sulfonates, alkali detergents and alkaline earth metal-containing detergents, tall oil fatty acids, 2-ethyl hexyl nitrate, manganese carboxylates, copper carboxylates, magnesium carboxylates, magnesium sulfonates, ferrocene, calcium nitrate, perlite, aluminum trihydrate, copper oxychloride, cerium oxides, hydroxides, and carboxylates, platinum group metal organics and inorganics, aluminum silicate, magnesium silicate, vermiculite, aluminum sulfonate, aluminum carboxylate, magnesium oxide, and magnesium hydroxide.
- Suitable embodiments may comprise additive compositions comprising one or more metal compounds. The presence of metal atoms may be useful for realizing many desired additive functions, including combustion improvement, slag modification, acid neutralization, and many others. The metal compounds or metal ions may be inorganic metal compounds and/or organometallic compounds. The elemental or ionic metals may be selected from, but not limited to, one or more of the following: sodium, potassium, magnesium, calcium, barium, strontium, titanium, cerium, chromium, molybdenum, manganese, iron, zinc, yttrium, lanthanum, zirconium, ruthenium, tungsten, rhenium, osmium, iridium, boron, aluminum, silicon, tin, rubidium, cobalt, rhodium, nickel, palladium, platinum, copper, and silver compounds, and mixtures thereof. The inorganic metal compound may be selected from, but not limited to, one or more of the following: fluorides, chlorides, bromides, iodides, oxides, nitrates, sulfates, phosphates, carbonates, hydrides, nitrides, and mixtures thereof. The organometallic compounds may be selected from, but not limited to, one or more of: alcohols, aldehydes, ketones, esters, anhydrides, sulfonates, phosphonates, chelates, phenates, crown ethers, carboxylic acids, amides, and mixtures thereof. Also suitable are organometallic compounds containing one or more carbonyl groups, ethers or poly ethers, aminos, alkylaminos, acetamidos, alkoxides, alkyls, cyanos, furfuryls, carboxylates, acetylacetonates, and other organic ligands able to coordinate with or bond with a metal, metal compound, or metal ion.
- An exemplary solid fuel composition containing functional components, wherein each component is selected from non-persistent, non-bioaccumulative, and non-toxic materials is illustrated in the following table.
-
TABLE 1 Fuel Additives Example 1 Example 2 (Wt. % based on (Wt. % based on Component finished fuel) finished fuel) manganese carboxylate 0.00001-0.5 0.0001-0.1 magnesium sulfonate 0.00001-2.0 0.0001-0.01 surfactant 0.00001-1.0 0.0001-1.0 aromatic solvent 0-10.0 0.0001-10.0 petroleum coke Balance Balance - The conventional additives indicated in Table I may be combined with one or more solid fuels. Suitable fuels may comprise any known solid fuel or mixtures thereof. Suitable solid fuels may include, but are not limited to, coal, coke, coke breeze, carbonaceous char, petroleum pitch, petroleum coke, refuse derived fuel (RDF), municipal solid waste (MSW), biomass, bagasse, wood, wood pellets, wood bark, wood by-products, wood wastes, sawdust, hog fuel, black liquor solids, waste tires, charcoal, peat, corn, corn cobs, wheat, rye, and other grains, coffee grounds, tobacco wastes, and the like. This additive may also be water based by substituting an aqueous medium for the organic solvent, and adjusting the surfactant to meet the handling goals, for example, utilizing a clear solution, an emulsion, or a slurry.
- Suitable solid fuels may be combined with one or more liquid fuels and/or water as an adjuvant, process aid, ignition promoter, dust suppressant, diluent, viscosity modifier, and/or flow enhancer. Such liquid fuels may comprise, but are not limited to, one or more of gasoline, diesel fuel, middle distillate fuel, biodiesel fuel, an alcohol, such as but not limited to an ethanol, bioethanol, a biobutanol, coal, an aviation fuel, jet fuel, marine fuel, burner fuel, home heating oil, a gas-to-liquid (GTL) base oil, a Group I base oil, a Group II base oil, a Group III base oil, a Group IV base oil, an ester, a vegetable oil, and a mixture thereof.
- Suitable coal may comprise any naturally occurring coal. For example, coal may comprise lignite, jet, sub-bituminous, bituminous, and anthracite. Coal may be pulverized and/or crushed. Further, it may be fed into a burner as a dry powder or slurry.
- Suitable coal may be coal that is converted into liquid-fuels like gasoline or diesel by several different processes. For example, the Fischer-Tropsch process of indirect synthesis of liquid hydrocarbons may be used to gasify coal to make syngas (a balanced purified mixture of CO and H2 gas). The syngas may then be reductively polymerized on Fischer-Tropsch catalysts to make hydrocarbons which are further processed into gasoline, diesel, jet fuel, oxygenantes, lubricant base stocks, waxes, and other chemicals. Syngas can also be converted to methanol and ethanol, which can be used as a fuel, fuel additive, or further processed into gasoline. Several other processes exist to liquefy coal, such as, but not limited to direct liquefaction by hydrogenation and low temperature carbonization.
- Suitable coal sources for liquefaction may comprise lignite, anthracite, sub-bituminous, and/or bituminous coal. The coal may be “pulverized coal” which is either already small enough or has been subjected to mechanical particle size reduction such that the resulting pulverized material can be conveyed via fluidization with air through a pipe into the combustion chamber of a furnace or boiler. The pulverized coal useful herein may be at least 50% under 200 mesh (74 microns), or as another example the coal useful herein is at least 60% under 200 mesh, or as an even further example, at least 70% under 200 mesh.
- Suitable biomass fuels may include living and/or dead biological material. Suitable biomass fuel sources may include, but are not limited to, plant matter, biodegradable wastes, municipal wastes, and industrial wastes. Biomass may be grown from several plants, including miscanthus, switchgrass, hemp, corn, poplar, willow, and sugarcane.
- Suitable petroleum coke (or pet coke) may comprise a carbonization product (such as a carbonaceous solid) of high-boiling hydrocarbon fractions (heavy residues) obtained in petroleum processing (such as those derived from oil refinery coker units or other cracking processes). Further, petroleum coke may include products such as green (or raw), calcined, or needle petroleum coke.
- In some embodiments, the additives or additive package may be used with a liquid carrier or induction aid. Suitable carrier fluids may include any base oil as defined herein. Suitable solvents may comprise low aromatic Group I and/or Group II basestocks with a cSt of 4 at 100° C. Examples of solvents include 1) GP II 100 SN, 98 VI at about 4.0 cSt at 100° C. from Motiva and b) GP I 150 SN, 88 VI with 4.5 cSt at 100° C. from ExxonMobil. Further suitable carrier fluids can be of various types, such as for example liquid poly-alpha-olefin oligomers, mineral oils, liquid poly(oxyalkylene) compounds, liquid alcohols or polyols, polyalkenes, liquid esters, and similar liquid carriers.—Further, a suitable carrier fluid may comprise water. Mixtures of two or more such carriers can be employed.
- Liquid carriers can include butane not limited to 1) a mineral oil or a blend of mineral oils that have a viscosity index of less than about 120, 2) one or more poly-alpha-olefin oligomers, 3) one or more poly(oxyalkylene) compounds having an average molecular weight in the range of about 500 to about 3000, 4) polyalkenes, 5) polyalkyl-substituted hydroxyaromatic compounds or 6) mixtures thereof. The mineral oil carriers that can be used include paraffinic, naphthenic, and asphaltic oils, and can be derived from various petroleum crude oils and processed in any suitable manner. For example, the mineral oils may be solvent extracted or hydrotreated oils. Reclaimed mineral oils can also be used. Hydrotreated oils may also be used.
- Suitable combustion improvers may comprise one or more of a manganese compound, an iron compound (including, for example, ferrocene), platinum-group metals, calcium, cerium oxide, copper, and the like. Examples of suitable combustion improvers include manganese carboxylate and ferrocene. For example, a non-limiting example of a useful manganese compound is an alkylcycloalkyldienyl manganese tricarbonyl, such as methylcyclopentadienyl manganese tricarbonyl. It generally is added in treat rates of about 0.001 gram to about 1.0 gram of manganese per kilogram of fuel.
- Cyclopentadienyl manganese tricarbonyl compounds such as methylcyclopentadienyl manganese tricarbonyl are suitable combustion improvers because of their outstanding ability to reduce tailpipe emissions such as NOx and smog forming precursors and to significantly improve the octane quality of gasolines, both of the conventional variety and of the “reformulated” types
- Suitable combustion improvers may be derived from a metal-containing compound. Metal-containing compounds or metal ions may be inorganic metal compounds and/or organometallic compounds. The elemental or ionic metals can be one or more of the following group: sodium, potassium, magnesium, calcium, barium, strontium, titanium, cerium, chromium, molybdenum, manganese, iron, rubidium, cobalt, rhodium, nickel, palladium, platinum, copper, and silver compounds, and mixtures thereof. The inorganic metal compound can be selected from the group consisting of fluorides, chlorides, bromides, iodides, oxides, nitrates, sulfates, phosphates, carbonates, hydrides, nitrides, and mixtures thereof. The organometallic compound can be selected from the group consisting of alcohols, aldehydes, ketones, esters, anhydrides, sulfonates, phosphonates, chelates, phenates, crown ethers, carboxylic acids, amides, and mixtures thereof. Particularly useful are organometallic compounds containing one or more carbonyl groups, ethers or poly ethers, and other organic ligands able to coordinate with or bond with a metal, metal compound, or metal ion.
- Combustion additives may comprise a metal-containing catalyst. The additive may further comprise a ligand for complexing with the catalyst, and a solvent for carrying the catalyst/ligand complex. The catalyst may be comprised of one or more metals, such as, but not limited to, manganese, calcium, magnesium, potassium, zinc, and/or aluminum. The ligand may comprise one or more of, but not limited to, fossil fuel derived carboxylates, natural product carboxylates, genetically engineered natural products derived carboxylates, synthetic carboxylates, and/or mixtures thereof.
- Single metals may be derivatized to be used as combustion catalysts, such as, but not limited to Ca, Cr, Mn, Fe, Co, Cu, Sr, Y, Ru, Rh, Pd, La, Re, Os, Ir, Pt, and Ce. The respective carboxylates can be made from the appropriate metal starting material (oxide, hydroxide, etc.) and carboxylic acid and a solvent.
- Multimetallics may also be used. When using multimetallics, a co-catalyst may be used such as, for example, a magnesium carboxylate. In some instances, a second co-catalyst may be used such as, for example, one derived from the alkali metal group (Li, Na, K, etc.).
- Suitable slag modifiers may comprise one of more individual compounds of magnesium, copper, manganese, aluminum, silicon, and the like. Examples of suitable slag modifiers include magnesium sulfonate and copper oxychloride. Other suitable slag modifiers may comprise one or more multimetallic compounds or minerals. Examples of suitable multimetallic slag modifiers include vermiculite and perlite. Slag modifiers are generally added in treat rates of about 0.001 gram to about 100 grams of metal per kilogram of fuel. The specific treat rate can be dictated by the amount of ash present in the fuel and the physical and chemical properties including chemical composition and melting temperature characteristics, of said ash.
- A particularly suitable additive solution may comprise a combination of a combustion improver and a slag modifier. Many problems handling or otherwise managing slag accumulation and/or removal from the boiler are exacerbated by poor combustion that results in a high level of unburned carbon in the slag. The presence of a combustion improver in the additive formulation reduces the amount of unburned carbon in the slag, thereby increasing the effectiveness of the slag modifier additive chemistry.
- Suitable slag modifiers may be derived from a metal-containing compound. The metal-containing compounds or metal ions may be inorganic metal compounds and/or organometallic compounds. The elemental or ionic metals can be one or more of the following group: magnesium, calcium, strontium, titanium, manganese, iron, aluminum, silicon, and copper compounds, and mixtures thereof. The inorganic metal compound can be selected from the group consisting of fluorides, chlorides, bromides, iodides, oxides, nitrates, sulfates, phosphates, carbonates, hydrides, nitrides, and mixtures thereof. The organometallic compound can be selected from the group consisting of alcohols, aldehydes, ketones, esters, anhydrides, sulfonates, phosphonates, chelates, phenates, crown ethers, carboxylic acids, amides, and mixtures thereof. Particularly useful are organometallic compounds containing one or more carbonyl groups, ethers or poly ethers, and other organic ligands able to coordinate with or bond with a metal, metal compound, or metal ion. Further, a suitable slag modifier may be derived from a multimetallic compound or mineral including vermiculite and perlite.
- Suitable fouling modifiers may comprise one or more individual compounds of magnesium, copper, manganese, aluminum, and the like. Examples of such fouling modifiers include magnesium hydroxide and magnesium oxide. Other suitable fouling modifiers may comprise one or more multimetallic compounds or minerals. Examples of suitable multimetallic fouling modifiers include vermiculite and perlite. Fouling modifiers are generally added in treat rates of about 0.001 gram to about 100 grams of metal per kilogram of fuel. The specific treat rate can be dictated by the amount of ash present in the fuel and the chemical and physical properties, especially chemical composition and melting temperature characteristics, of said ash.
- Suitable fouling modifiers may be derived from a metal-containing compound. The metal-containing compounds or metal ions may be inorganic metal compounds and/or organometallic compounds. The elemental or ionic metals can be one or more of the following group: magnesium, calcium, manganese, aluminum, copper compounds, and mixtures thereof. The inorganic metal compound can be selected from the group consisting of fluorides, chlorides, bromides, iodides, oxides, nitrates, sulfates, phosphates, carbonates, hydrides, nitrides, and mixtures thereof. The organometallic compound can be selected from the group consisting of alcohols, aldehydes, ketones, esters, anhydrides, sulfonates, phosphonates, chelates, phenates, crown ethers, carboxylic acids, amides, and mixtures thereof. Particularly useful are organometallic compounds containing one or more carbonyl groups, ethers or poly ethers, and other organic ligands able to coordinate with or bond with a metal, metal compound, or metal ion.
- Suitable fluxing agents may comprise one of more individual compounds of iron, sodium, potassium, and the like. One examples of a suitable fluxing agent is iron oxide.
- Various compounds known for anti-icing and/or freezing point depression may be utilized in the present embodiments. For example, suitable anti-icing agents may comprise ether polymers, glycols, and alcohols.
- Various compounds known for hygroscopic effects may be used in the present embodiments. Suitable hygroscopic agents may comprise, for example but not limited to, glycerin, glycerol, urea, ethanol, methanol, concentrated sulfuric acid, magnesium oxide, magnesium sulfate, magnesium sulfonate, calcium carbonate, calcium carbonate, calcium silicates, silica gel, activated alumina, various zeolites, montmorillonite clay, and concentrated sodium hydroxide (lye).
- Suitable corrosion inhibitors may comprise one or more individual compounds of magnesium in particular. Examples of such corrosion inhibitors include magnesium hydroxide and magnesium oxide. Other suitable corrosion inhibitors may comprise one or more multimetallic compounds or minerals. Examples of suitable multimetallic corrosion inhibitors include vermiculite and perlite. Corrosion inhibitors are generally added in treat rates of about 0.001 gram to about 100 grams of metal per kilogram of fuel. The specific treat rate is dictated by the physical and chemical properties of the flue gas and flyash.
- The additive compositions may comprise other suitable components such as a manganese-containing compound for the reduction of carbon present in fly ash resulting from the combustion of coal. Further, additives for improving the performance and durability of electrostatic precipitators may be necessary in some embodiments. Suitable electrostatic precipitators may comprise sodium, lithium, potassium, manganese, and the like.
- The additive composition may comprise other suitable components such as those described in US 2005-0257724 A1, herein incorporated by reference, for the additive-induced control of NOx emissions in a coal burning utility furnace. Such additive may comprise a metal-containing combustion catalyst that may include one or more of the following metals: manganese, potassium, calcium, strontium, chromium, iron, cobalt, copper, lanthanide, cerium, platinum, palladium, rhodium, ruthenium, iridium, and osmium. Suitable manganese tricarbonyl compounds which can be used include cyclopentadienyl manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, dimethylcyclopentadienyl manganese tricarbonyl, trimethylcyclopentadienyl manganese tricarbonyl, tetramethylcyclopentadienyl manganese tricarbonyl, pentamethylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl manganese tricarbonyl, diethylcyclopentadienyl manganese tricarbonyl, propylcyclopentadienyl manganese tricarbonyl, isopropylcyclopentadienyl manganese tricarbonyl, tert-butylcyclopentadienyl manganese tricarbonyl, octylcyclopentadienyl manganese tricarbonyl, dodecylcyclopentadienyl manganese tricarbonyl, ethylmethylcyclopentadienyl manganese tricarbonyl, indenyl manganese tricarbonyl, and the like, including mixtures of two or more such compounds.
- The additive composition may comprise other suitable components such as those described in U.S. Ser. No. 11/743,707, herein incorporated by reference, for the removal of mercury-containing materials from emissions, such as flue gas, resulting from combustion devices.
- The additive composition may comprise other suitable components such as those described in US 2004-0118032, herein incorporated by reference, for the reduction of inhibition of corrosion in an atmospheric burner unit. The additive components may comprise a fuel-borne organometallic combustion system containing manganese, or a manganese precursor source, or derivative. The system may further contain a catalyst package that may comprise one or more individual organometallic compounds of lithium, sodium, potassium, magnesium, calcium, strontium, barium, molybdenum, iron, cobalt, platinum, cerium, and combinations, mixtures, or precursors thereof.
- The additive composition may comprise other suitable components such as those described in U.S. Pat. No. 7,094,274, herein incorporated by reference, for the improved efficiency of and reduction of back-corona discharge on electrostatic precipitators. The additive components may comprise manganese or a manganese-containing compound or precursor. Examples of suitable manganese-containing compounds include, but are not limited to, methyl cyclopentadienyl manganese tricarbonyl, manganese sulfonate, manganese phenate, manganese salicylate, cyclopentadienyl manganese tricarbonyl, alkyl cyclopentadienyl manganese tricarbonyl, organic manganese tricarbonyl derivatives, alkyl cyclopentadienyl manganese derivatives, bis-cyclopentadienyl manganese, bis-alkyl cyclopentadienyl manganese, neutral and overbased manganese salicylates, neutral and overbased manganese phenates, neutral and overbased manganese sulfonates, manganese carboxylates, and combinations and mixtures thereof. Further, the additive composition may comprise oxygenates such as, but not limited to, methanol, ethanol, isopropanol, t-butanol, mixed alcohols, ethers such as methyl tertiary butyl ether, tertiary amyl methyl ether, ethyl tertiary butyl ether and mixed ethers; polyethers such as 2-methoxy ethyl ether (diglyme), triglyme; polyols; poyether alcohols such as di(ethylene glycol) monomethyl ether, and mixtures thereof.
- Some of the additive components described above may be supplied in the form of solutions of active ingredient(s) in an inert diluent or solvent, such as a diluent oil. Unless expressly stated to the contrary, the amounts and concentrations of each additive component are expressed in terms of active additive, i.e., the amount of solvent or diluent that may be associated with such component as received is excluded.
- It will be appreciated that the individual components employed may be separately blended into or combined with the fuel or carrier fluid or may be blended therein in various sub-combinations, if desired. Ordinarily, the particular sequence of such blending steps is not crucial. Moreover, such components may be blended or combined in the form of separate solutions in a diluent. It may be preferable, however, to blend the additive components used in the form of a concentrate, as this simplifies the blending operations, reduces the likelihood of blending errors, and takes advantage of the compatibility and solubility characteristics afforded by the overall concentrate.
- Additive concentrates may thus be formulated to contain all of the additive components and if desired, some of the base fuel component, in amounts proportioned to yield finished fuel blends consistent with the concentrations described above. In most cases, the additive concentrate will contain one or more diluents such as light carrier oils, to facilitate handling and blending of the concentrate. Thus concentrates containing up to about 50 wt. % of one or more diluents or solvents may be used, provided the solvents are not present in amounts that interfere with the low and high temperature and flash point characteristics and the performance of the finished additive formulation.
- Such additive concentrates are suitably devoid of materials or components that are bioaccumulative, toxic, and/or persistent as indicated by the tests described above. Examples of such materials, include but are not limited to, certain alkanes, alkoxy alkylamines, alkyl methacrylates, alkyl phenols, alkylphenols, polyoxyalkyl alkylamines, aryl amines, aryl phosphites, branched alkyl phenols, branched alkyl polysulfides, branched long-chain alkyl amines, long-chain alkenyl alkyl amine, long-chain alkenyl alkylene amines, long-chain alkenyl amines, long-chain alkoxylated amines, long-chain alkyl alkoxylated alcohols, long-chain alkyl alkylene amines, long-chain alkyl amines, long-chain alkyl methacrylates, long-chain alkyoxylated amines, long-chain hydroxyalkyl amines, polyaryls, and polyolefin polyamines.
- Fuels and fuel additives of the embodiments herein may be formulated to provide enhanced fuel properties for various applications. A fuel composition according to the present disclosure may be used for combustion for the production of power as well as stationary burners, power plants, industrial plants, home heating operations, and the like.
- In one embodiment, a composition of the present disclosure may be manufactured in the United States of America or Canada.
- In a further embodiment, a composition of the present disclosure may be transported to Europe by ship, air, rail, or truck.
- At numerous places throughout this specification, reference has been made to a number of U.S. patents. All such cited documents are expressly incorporated in full into this disclosure as if fully set forth herein.
- Other embodiments of the present disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the embodiments disclosed herein. As used throughout the specification and claims, “a” and/or “an” may refer to one or more than one. Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, percent, ratio, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated the following claims.
- The foregoing embodiments are susceptible to considerable variation in practice. Accordingly, the embodiments are not intended to be limited to the specific exemplifications set forth hereinabove. Rather, the foregoing embodiments are within the spirit and scope of the appended claims, including the equivalents thereof available as a matter of law.
- The patentees do not intend to dedicate any disclosed embodiments to the public, and to the extent any disclosed modifications or alterations may not literally fall within the scope of the claims, they are considered to be part hereof under the doctrine of equivalents.
Claims (25)
1. An environmentally compatible fuel additive composition suitable for use with a solid fuel, the additive composition comprising at least one functional component, wherein the component is selected from the group consisting of a non-persistent material, a non-bioaccumulative material, and a non-toxic material, and the additive composition is substantially devoid of any component that is persistent, bioaccumulative, and toxic.
2. The fuel additive composition of claim 1 , wherein the functional component comprises one or more materials selected from the group consisting of: acid plume reducing agents, anti-icing agents, biocides, carrier fluids, combustion improvers, corrosion inhibitors, diluents, dust suppressants, electrostatic precipitator activating agents, fluxing agents, fouling modifiers, hygroscopic agents, ignition improvers, markers or customer-specific “tags,” reodorants, mercury scavengers, nitrogen oxide (NOx) scavengers, NOx, reducing agents, slag modifiers, sulfur oxide (SO2/SO3) scavengers, and surfactants.
3. The fuel additive composition of claim 1 , wherein the non-persistent material is determined by a biodegradation test selected from the group consisting of: a dissolved organic carbon die-away test, a modified OECD screening dissolved organic carbon die-away test, a carbon dioxide evolution test, a manometric respirometry test, a closed bottle test, a MITI test, a Zahn-Wellens test, an activated sludge simulation test, an activated sludge respiration inhibition test, and a modified SCAS test.
4. The fuel additive composition of claim 1 , wherein non-persistent material is a material having an acceptable score on a biodegradation test selected from at least one of the following:
a) a half-life in marine water is less than 60 days;
b) a half-life in fresh or estuarine water is less than 40 days;
c) a half-life in marine sediment is less than 180 days;
d) a half-life in fresh or estuarine water sediment less than 120 days; or
e) a half-life in soil less than 120 days.
5. The fuel additive composition of claim 1 , wherein the non-bioaccumulative material is determined by a bioconcentration factor test comprising a flow-through fish test.
6. The fuel additive composition of claim 5 , wherein the non-bioaccumulative material has a bioconcentration factor test result below 2000.
7. The fuel additive composition of claim 1 , wherein the non-toxic material is determined by a toxicity test selected from the group consisting of an acute toxicity for fish test, an acute toxicity for Daphnia test, and an algal inhibition test.
8. The fuel additive composition of claim 7 , wherein passing the non-toxic material is devoid of a toxic effect at an aqueous concentration below 0.01 mg/L on a toxicity test.
9. The fuel additive composition of claim 1 , wherein the at least one functional component comprises one or more of a member selected from the group consisting of: methyl cyclopentadienyl manganese tricarbonyl, cyclopentadienyl manganese tricarbonyl, octane enhancer materials, alkyl nitrates, glycols, phenates, salicylates, sulfonates, alkali detergents and alkaline earth metal-containing detergents, tall oil fatty acids, 2-ethyl hexyl nitrate, manganese carboxylates, copper carboxylates, magnesium carboxylates, magnesium sulfonates, ferrocene, calcium nitrate, perlite, aluminum trihydrate, copper oxychloride, cerium oxides, hydroxides, and carboxylates, platinum group metal organics and inorganics, aluminum silicate, magnesium silicate, vermiculite, aluminum sulfonate, aluminum carboxylate, magnesium oxide, and magnesium hydroxide.
10. The fuel additive composition of claim 1 , wherein the at least one functional component comprises one or more metal-containing compounds selected from the group consisting of: sodium compounds, potassium compounds, magnesium compounds, calcium compounds, barium compounds, strontium compounds, titanium compounds, cerium compounds, chromium compounds, molybdenum compounds, manganese compounds, iron compounds, zinc compounds, yttrium compounds, lanthanum compounds, zirconium compounds, ruthenium compounds, tungsten compounds, rhenium compounds, osmium compounds, iridium compounds, boron compounds, aluminum compounds, silicon compounds, tin compounds, rubidium compounds, cobalt compounds, rhodium compounds, nickel compounds, palladium compounds, platinum compounds, copper compounds, silver compounds, inorganic fluoride compounds, inorganic chloride compounds, inorganic bromide compounds, inorganic iodide compounds, inorganic oxide compounds, inorganic nitrate compounds, inorganic sulfate compounds, inorganic phosphate compounds, inorganic carbonate compounds, inorganic hydride compounds, inorganic nitride compounds, organometallic alcohol compounds, organometallic aldehyde compounds, organometallic ketone compounds, organometallic ester compounds, organometallic anhydride compounds, organometallic sulfonate compounds, organometallic phosphonate compounds, organometallic chelate compounds, organometallic phenate compounds, organometallic crown ether compounds, organometallic carboxylic acid compounds, organometallic amide compounds, organometallic compounds containing one or more carbonyl groups, ethers, or poly ethers, aminos, alkylaminos, acetamidos, alkoxides, alkyls, cyanos, furfuryls, carboxylates, acetylacetonates, and other organic ligands able to coordinate with or bond with a metal, metal compound, or metal ion, and mixtures thereof.
11. The fuel additive composition of claim 2 , wherein the combustion improver is selected from the group consisting of: sodium compounds, potassium compounds, magnesium compounds, calcium compounds, barium compounds, strontium compounds, titanium compounds, cerium compounds, chromium compounds, molybdenum compounds, manganese compounds, iron compounds, rubidium compounds, cobalt compounds, rhodium compounds, nickel compounds, palladium compounds, platinum compounds, copper compounds, silver compounds, inorganic fluoride compounds, inorganic chloride compounds, inorganic bromide compounds, inorganic iodide compounds, inorganic oxide compounds, inorganic nitrate compounds, inorganic sulfate compounds, inorganic phosphate compounds, inorganic carbonate compounds, inorganic hydride compounds, inorganic nitride compounds, organometallic alcohol compounds, organometallic aldehyde compounds, organometallic ketone compounds, organometallic ester compounds, organometallic anhydride compounds, organometallic sulfonate compounds, organometallic phosphonate compounds, organometallic chelate compounds, organometallic phenate compounds, organometallic crown ether compounds, organometallic carboxylic acid compounds, organometallic amide compounds, organometallic compounds containing one or more carbonyl groups, ethers, or poly ethers, and other organic ligands able to coordinate with or bond with a metal, metal compound, or metal ion, and mixtures thereof.
12. The fuel additive composition of claim 2 , wherein the slag modifier is selected from the group consisting of: magnesium compounds, calcium compounds, strontium compounds, titanium compounds, manganese compounds, aluminum compounds, silicon compounds, iron compounds, copper compounds, inorganic fluoride compounds, inorganic chloride compounds, inorganic bromide compounds, inorganic iodide compounds, inorganic oxide compounds, inorganic nitrate compounds, inorganic sulfate compounds, inorganic phosphate compounds, inorganic carbonate compounds, inorganic hydride compounds, inorganic nitride compounds, organometallic alcohol compounds, organometallic aldehyde compounds, organometallic ketone compounds, organometallic ester compounds, organometallic anhydride compounds, organometallic sulfonate compounds, organometallic phosphonate compounds, organometallic chelate compounds, organometallic phenate compounds, organometallic crown ether compounds, organometallic carboxylic acid compounds, organometallic amide compounds, organometallic compounds containing one or more carbonyl groups, ethers or poly ethers, and other organic ligands able to coordinate with or bond with a metal, metal compound, or metal ion, vermiculite, perlite, and mixtures thereof.
13. The fuel additive composition of claim 2 , wherein the fouling modifier is selected form the group consisting of: magnesium compounds, calcium compounds, manganese compounds, aluminum compounds, copper compounds, inorganic fluoride compounds, inorganic chloride compounds, inorganic bromide compounds, inorganic iodide compounds, inorganic oxide compounds, inorganic nitrate compounds, inorganic sulfate compounds, inorganic phosphate compounds, inorganic carbonate compounds, inorganic hydride compounds, inorganic nitride compounds, organometallic alcohol compounds, organometallic aldehyde compounds, organometallic ketone compounds, organometallic ester compounds, organometallic anhydride compounds, organometallic sulfonate compounds, organometallic phosphonate compounds, organometallic chelate compounds, organometallic phenate compounds, organometallic crown ether compounds, organometallic carboxylic acid compounds, organometallic amide compounds, organometallic compounds containing one or more carbonyl groups, ethers or poly ethers, and other organic ligands able to coordinate with or bond with a metal, metal compound, or metal ion, vermiculite, perlite, and mixtures thereof.
14. The fuel additive composition of claim 2 , wherein the fluxing agent is selected from the group consisting of one or more individual compounds of iron, sodium, and potassium.
15. The fuel additive composition of claim 2 , wherein the anti-icing agent is selected from the group comprising ether polymers, glycols, and alcohols.
16. The fuel additive composition of claim 2 , wherein the hygroscopic agent is selected from the group consisting of: glycerin, glycerol, urea, ethanol, methanol, concentrated sulfuric acid, magnesium oxides, magnesium sulfate, magnesium sulfonate, calcium carbonate, calcium silicates, silica gel, activated alumina, zeolites, montmorillonite clay, and concentrated sodium hydroxide.
17. The fuel additive composition of claim 2 , wherein the corrosion inhibitor is selected from the group consisting of magnesium oxide and magnesium hydroxide, and mixtures and solutions thereof.
18. The fuel additive composition of claim 2 , wherein the corrosion inhibitor is selected from the multimetallic compounds and minerals including vermiculite and perlite.
19. The fuel additive composition of claim 2 , wherein the solid fuel comprises one or more of the group selected from: coal, coke, coke breeze, carbonaceous char, petroleum pitch, petroleum coke, refuse derived fuel (RDF), municipal solid waste (MSW), biomass, bagasse, wood, wood pellets, wood bark, wood by-products, wood wastes, sawdust, hog fuel, black liquor solids, waste tires, charcoal, peat, corn, corn cobs, wheat, rye, and other grains, coffee grounds, and tobacco wastes.
20. An environmentally compatible solid fuel composition, comprising:
a) a major amount of a solid fuel; and
b) a minor amount of an additive composition, comprising at least one of a functional component, wherein the component comprises at least one of:
i) an acceptable level biodegradation of at least one of:
1) a half-life in marine water of less than 60 days;
2) a half-life in fresh or estuarine water of less than 40 days;
3) a half-life in marine sediment of less than 180 days;
4) a half-life in fresh or estuarine water sediment less than 120 days; or
5) a half-life in soil less than 120 days, as determined by a biodegradation test;
ii) a bioconcentration factor below 2000 in a bioconcentration factor test; or
iii) is devoid of a toxic effect at an aqueous concentration below 0.01 mg/L on a toxicity test.
21. The solid fuel composition of claim 20 , wherein the functional component comprises at least one material selected from the group consisting of: acid plume reducing agents, anti-icing agents, biocides, carrier fluids, combustion improvers, corrosion inhibitors, diluents, dust suppressants, electrostatic precipitator activating agents, fluxing agents, fouling modifiers, hygroscopic agents, ignition improvers, markers or customer-specific “tags,” reodorants, mercury scavengers, nitrogen oxide (NOx) scavengers, NOx, reducing agents, slag modifiers, sulfur oxide (SO2/SO3) scavengers, and surfactants.
22. The solid fuel composition of claim 20 , wherein the solid fuel is selected from the group consisting of coal, coke, coke breeze, carbonaceous char, petroleum pitch, petroleum coke, refuse derived fuel (RDF), municipal solid waste (MSW), biomass, bagasse, wood, wood pellets, wood bark, wood by-products, wood wastes, sawdust, hog fuel, black liquor solids, waste tires, charcoal, peat, corn, corn cobs, wheat, rye, and other grains, coffee grounds, and tobacco wastes.
23. A method of making an environmentally compatible solid fuel composition, comprising combining a major amount of a solid fuel and a minor amount of an additive composition, wherein the additive composition comprises at least one functional component wherein the component is selected from:
i) a material having an acceptable level biodegradation of at least one of:
1) a half-life in marine water of less than 60 days;
2) a half-life in fresh or estuarine water of less than 40 days;
3) a half-life in marine sediment of less than 180 days;
4) a half-life in fresh or estuarine water sediment less than 120 days; or
5) a half-life in soil less than 120 days, as determined by a biodegradation test;
ii) a material having a bioconcentration factor below 2000 in a bioconcentration factor test; or
iii) a material that is devoid of a toxic effect at an aqueous concentration below 0.01 mg/L on a toxicity test, and
wherein the solid fuel composition complies with European Council Directive 67/548/EEC.
24. The method of claim 23 , wherein the functional component further comprises a material selected from the group consisting of: acid plume reducing agents, anti-icing agents, biocides, carrier fluids, combustion improvers, corrosion inhibitors, diluents, dust suppressants, electrostatic precipitator activating agents, fluxing agents, fouling modifiers, hygroscopic agents, ignition improvers, markers or customer-specific “tags,” reodorants, mercury scavengers, nitrogen oxide (NOx) scavengers, NOx reducing agents, slag modifiers, sulfur oxide (SO2/SO3) scavengers, and surfactants.
25. An environmentally compatible solid fuel composition comprising:
a) a major amount of a solid fuel; and
b) a minor amount of an additive composition comprising at least one functional component, wherein the component is at least selected from the group consisting of non-persistent materials, non-bioaccumulative materials, and non-toxic materials, and the additive composition is substantially devoid of any component that is persistent, bioaccumulative, and toxic.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/856,205 US20090071067A1 (en) | 2007-09-17 | 2007-09-17 | Environmentally-Friendly Additives And Additive Compositions For Solid Fuels |
EP08163571A EP2039739A1 (en) | 2007-09-17 | 2008-09-03 | Environmentally-friendly additives and additive compositions for solid fuels |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/856,205 US20090071067A1 (en) | 2007-09-17 | 2007-09-17 | Environmentally-Friendly Additives And Additive Compositions For Solid Fuels |
Publications (1)
Publication Number | Publication Date |
---|---|
US20090071067A1 true US20090071067A1 (en) | 2009-03-19 |
Family
ID=40011080
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/856,205 Abandoned US20090071067A1 (en) | 2007-09-17 | 2007-09-17 | Environmentally-Friendly Additives And Additive Compositions For Solid Fuels |
Country Status (2)
Country | Link |
---|---|
US (1) | US20090071067A1 (en) |
EP (1) | EP2039739A1 (en) |
Cited By (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100006014A1 (en) * | 2008-07-11 | 2010-01-14 | Fuel Tech, Inc. | Targeted reagent injection for slag control from combustion of coals high in iron and/or calcium |
US20100299990A1 (en) * | 2009-06-01 | 2010-12-02 | Allen Aradi | Nanoparticle Catalyst Compounds and/or Volatile Organometallic Compounds and Method of Using the Same for Biomass Gasification |
US20100303705A1 (en) * | 2009-06-01 | 2010-12-02 | Allen Aradi | Method of using volatile organometallics as biomass gasification catalysts |
US20110078917A1 (en) * | 2009-10-01 | 2011-04-07 | Bland Richard W | Coal fine drying method and system |
CN102191110A (en) * | 2011-04-19 | 2011-09-21 | 宜兴市科奇化工有限公司 | Fire coal combustion improver |
CN102212405A (en) * | 2010-04-01 | 2011-10-12 | 马中胜 | Coal-saving catalytic synergistic agent |
CN102533301A (en) * | 2012-01-13 | 2012-07-04 | 曹金贵 | Coking coal modifier |
CN102533370A (en) * | 2010-12-10 | 2012-07-04 | 淮南市源泉环保科技有限公司 | Paper making sludge environmentally-friendly briquette and production method thereof |
CN102585965A (en) * | 2012-02-27 | 2012-07-18 | 宜兴市创新精细化工有限公司 | Additive capable of improving coal combustion efficiency and reducing NOx emission simultaneously |
CN101649239B (en) * | 2009-09-17 | 2012-09-05 | 于江善 | Composite coal-saving agent |
CN102746906A (en) * | 2012-07-20 | 2012-10-24 | 杨如平 | High-proportion methanol fuel for diesel and additives thereof |
US8302325B2 (en) | 2010-09-30 | 2012-11-06 | Ross Technology Corporation | Methods and compositions for drying coal |
WO2012155413A1 (en) * | 2011-05-16 | 2012-11-22 | 科威国际技术转移有限公司 | Biomass fluid fuel and preparation method thereof |
CN102827666A (en) * | 2012-09-20 | 2012-12-19 | 赵冠军 | Liquid coal combustion improver |
WO2012173922A3 (en) * | 2011-06-13 | 2013-04-04 | Nalco Company | Method for reducing slag in biomass combustion |
CN103031174A (en) * | 2011-09-30 | 2013-04-10 | 湖南晟通科技集团有限公司 | Liquid state coal-saving additive |
US8758710B2 (en) | 2010-06-15 | 2014-06-24 | E.T. Energy Corp. | Process for treating a flue gas |
CN104164272A (en) * | 2014-09-02 | 2014-11-26 | 河南炬能能源科技有限公司 | Energy fuel and preparation method thereof |
CN104357124A (en) * | 2014-10-15 | 2015-02-18 | 宁夏宝塔石化科技实业发展有限公司 | Environment-friendly fire coal combustion improver |
CN104498130A (en) * | 2014-11-21 | 2015-04-08 | 河南高能能源有限公司 | High energy fuel special for boiler |
US9004284B2 (en) | 2009-10-01 | 2015-04-14 | Vitrinite Services, Llc | Mineral slurry drying method and system |
CN104962334A (en) * | 2015-06-16 | 2015-10-07 | 中南大学 | Biomass char composite fuel for iron ore sintering |
CN105238495A (en) * | 2015-10-30 | 2016-01-13 | 湖南和易环保科技有限公司 | Additive for eliminating dioxin produced in garbage incineration, and production process and application process thereof |
CN105238491A (en) * | 2015-10-15 | 2016-01-13 | 阳开金 | Coal-saving combustion improver and preparation method thereof |
CN105695035A (en) * | 2016-02-26 | 2016-06-22 | 天津水泥工业设计研究院有限公司 | Inferior coal catalysis sulphur-fixing agent used in cement industry and preparing and using methods thereof |
CN106118800A (en) * | 2016-08-03 | 2016-11-16 | 安徽中缘新材料科技有限公司 | A kind of preparation method of clean coal burning catalyst |
CN106118798A (en) * | 2016-08-03 | 2016-11-16 | 安徽中缘新材料科技有限公司 | A kind of clean coal burning catalyst |
CN106190425A (en) * | 2016-08-03 | 2016-12-07 | 安徽中缘新材料科技有限公司 | A kind of preparation method of environment-friendly high-efficiency clean coal burning catalyst |
CN106244287A (en) * | 2016-08-03 | 2016-12-21 | 安徽中缘新材料科技有限公司 | A kind of clean coal burning catalyst |
US20170089572A1 (en) * | 2015-09-25 | 2017-03-30 | Fuel Tech, Inc. | Process and Apparatus for Reducing Acid Plume |
CN111100720A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Coal powder treatment method, coal powder product and coal powder gasification method |
CN111961512A (en) * | 2020-07-10 | 2020-11-20 | 广西夏阳环保科技有限公司 | Special briquette for lime for aerated concrete and preparation method thereof |
CN112619204A (en) * | 2020-12-31 | 2021-04-09 | 浙江锦华新材料股份有限公司 | Deep dehydration drying agent and application thereof in synthesis of methyl tributyl ketoxime silane |
CN114634834A (en) * | 2022-03-30 | 2022-06-17 | 湖南昌迪环境科技有限公司 | Fire coal additive and application thereof |
US20220352529A1 (en) * | 2019-07-03 | 2022-11-03 | Audi Ag | Fuel cell plate, bipolar plate and fuel cell device |
KR102468473B1 (en) * | 2021-10-18 | 2022-11-18 | 세이프코리아 주식회사 | Biomass solid fuel using coffee gourd |
CN115418258A (en) * | 2022-09-14 | 2022-12-02 | 滁州智慧城市环保科技有限责任公司 | Boiler coking inhibitor and preparation method thereof |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102643705B (en) * | 2012-05-14 | 2014-04-02 | 清远市卫尔信化工建材有限公司 | Coal combustion-supporting hydrogel as well as preparation method and application thereof |
CN103013611A (en) * | 2012-12-26 | 2013-04-03 | 济南三农能源科技有限公司 | Biomass curing-forming fuel and preparation method thereof |
CN103131519A (en) * | 2013-02-07 | 2013-06-05 | 洛阳大泽节能环保科技有限公司 | Boiler fire coal sulfur fixation composition method |
CN103131513A (en) * | 2013-02-07 | 2013-06-05 | 洛阳大泽节能环保科技有限公司 | Thermal power plant fire coal combustion supporting and sulfur fixation composition method |
CN103320195B (en) * | 2013-05-29 | 2016-02-10 | 上海绿达节能科技有限公司 | A kind of coal additive |
CN103351906A (en) * | 2013-07-24 | 2013-10-16 | 王保行 | Catalytic combustion-supporting additive for pulverized coal boiler of fuel electric plant |
RU2547902C1 (en) * | 2014-02-12 | 2015-04-10 | Общество с Ограниченной Ответственностью Строительное научно-техническое малое предприятие "ЭЗИП" | Fuel composition |
CN103773550B (en) * | 2014-02-20 | 2015-05-20 | 枣庄市荣宝莱建材科技发展有限公司 | Liquid propellant for coal gangue power generation |
CN103773551A (en) * | 2014-02-20 | 2014-05-07 | 枣庄市荣宝莱建材科技发展有限公司 | Liquid combustion improver of coal gangue and preparation method of liquid combustion improver |
CN104987907A (en) * | 2015-06-30 | 2015-10-21 | 广西科技大学 | Novel moulded coal and preparation method thereof |
CN105154147A (en) * | 2015-10-14 | 2015-12-16 | 无棣华信石油技术服务有限公司 | Compound antistatic agent for petroleum products and preparation method of compound antistatic agent |
CN108753397B (en) * | 2018-06-11 | 2020-05-08 | 白婷婷 | Biological coal |
CN111748396A (en) * | 2020-06-05 | 2020-10-09 | 中节能(连云港)清洁技术发展有限公司 | Coke inhibitor and preparation method and application thereof |
CN115197764A (en) * | 2022-07-15 | 2022-10-18 | 北京宝莱尔科技有限公司 | Coking inhibitor and mixing arrangement |
Citations (96)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1815022A (en) * | 1930-05-03 | 1931-07-14 | Standard Oil Dev Co | Hydrocarbon oil and process for manufacturing the same |
US2015748A (en) * | 1933-06-30 | 1935-10-01 | Standard Oil Dev Co | Method for producing pour inhibitors |
US2191498A (en) * | 1935-11-27 | 1940-02-27 | Socony Vacuum Oil Co Inc | Mineral oil composition and method of making |
US2197263A (en) * | 1939-02-23 | 1940-04-16 | Socony Vacuum Oil Co Inc | Grease composition |
US2284409A (en) * | 1940-03-08 | 1942-05-26 | Pittsburgh Corning Corp | Fitting for tempered glass panels |
US2284410A (en) * | 1940-08-22 | 1942-05-26 | John F Farmer | Adjustable end slide grille |
US2387501A (en) * | 1944-04-04 | 1945-10-23 | Du Pont | Hydrocarbon oil |
US2425755A (en) * | 1944-06-01 | 1947-08-19 | Carbide & Carbon Chem Corp | Mixtures of polyoxyalkylene monohydroxy compounds and methods of making such mixtures |
US2425845A (en) * | 1945-04-21 | 1947-08-19 | Carbide & Carbon Chem Corp | Mixtures of polyoxyalkylene diols and methods of making such mixtures |
US2448664A (en) * | 1944-05-30 | 1948-09-07 | Carbide & Carbon Chem Corp | Polyoxypropylene compounds |
US2457139A (en) * | 1946-02-26 | 1948-12-28 | Carbide & Carbon Chem Corp | Esters of polyoxyalkylene diols |
US2459112A (en) * | 1945-07-06 | 1949-01-11 | Socony Vacuum Oil Co Inc | Mineral oil composition |
US2564561A (en) * | 1944-05-20 | 1951-08-14 | Socony Vacuum Oil Co Inc | Grease composition |
US2655479A (en) * | 1949-01-03 | 1953-10-13 | Standard Oil Dev Co | Polyester pour depressants |
US2666746A (en) * | 1952-08-11 | 1954-01-19 | Standard Oil Dev Co | Lubricating oil composition |
US2721878A (en) * | 1951-08-18 | 1955-10-25 | Exxon Research Engineering Co | Strong acid as a polymerization modifier in the production of liquid polymers |
US2721877A (en) * | 1951-08-22 | 1955-10-25 | Exxon Research Engineering Co | Lubricating oil additives and a process for their preparation |
US2749311A (en) * | 1952-12-04 | 1956-06-05 | Standard Oil Co | Corrosion inhibitors and compositions containing the same |
US2760933A (en) * | 1952-11-25 | 1956-08-28 | Standard Oil Co | Lubricants |
US2765289A (en) * | 1953-04-29 | 1956-10-02 | Standard Oil Co | Corrosion inhibitors and compositions containing the same |
US2850453A (en) * | 1955-04-26 | 1958-09-02 | Standard Oil Co | Corrosion inhibited oil compositions |
US2910439A (en) * | 1955-12-22 | 1959-10-27 | Standard Oil Co | Corrosion inhibited compositions |
US2962442A (en) * | 1957-01-03 | 1960-11-29 | Socony Mobil Oil Co Inc | Preparation of aldehyde-polyamine-hydroxyaromatic compound condensates and hydrocarbon fractions containing the same |
US2984550A (en) * | 1956-09-06 | 1961-05-16 | Nalco Chemical Co | Color stabilization of petroleum oils and compositions therefor |
US2999065A (en) * | 1960-11-07 | 1961-09-05 | Socony Mobil Oil Co Inc | Lubricant containing a calcium saltcalcium soaps mixture and process for forming same |
US2999066A (en) * | 1960-12-28 | 1961-09-05 | Socony Mobil Oil Co Inc | Lubricant containing a calcium saltcalcium soap mixture and process for forming same |
US3036003A (en) * | 1957-08-07 | 1962-05-22 | Sinclair Research Inc | Lubricating oil composition |
US3061420A (en) * | 1955-02-11 | 1962-10-30 | Exxon Research Engineering Co | Motor fuel |
US3087936A (en) * | 1961-08-18 | 1963-04-30 | Lubrizol Corp | Reaction product of an aliphatic olefinpolymer-succinic acid producing compound with an amine and reacting the resulting product with a boron compound |
US3166516A (en) * | 1960-10-28 | 1965-01-19 | Nalco Chemical Co | Process for breaking petroleum emulsions |
US3172892A (en) * | 1959-03-30 | 1965-03-09 | Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine | |
US3184411A (en) * | 1962-09-28 | 1965-05-18 | California Research Corp | Lubricants for reducing corrosion |
US3184474A (en) * | 1962-09-05 | 1965-05-18 | Exxon Research Engineering Co | Reaction product of alkenyl succinic acid or anhydride with polyamine and polyhydricmaterial |
US3197405A (en) * | 1962-07-09 | 1965-07-27 | Lubrizol Corp | Phosphorus-and nitrogen-containing compositions and process for preparing the same |
US3197496A (en) * | 1961-08-09 | 1965-07-27 | Lubrizol Corp | Polyphosphorus ester derivatives of o, o-dihydrocarbyl-s-hydroxylalkyl phosphorodithioates |
US3202678A (en) * | 1959-08-24 | 1965-08-24 | California Research Corp | Alkenyl succinimides of tetraethylene pentamine |
US3216936A (en) * | 1964-03-02 | 1965-11-09 | Lubrizol Corp | Process of preparing lubricant additives |
US3236770A (en) * | 1960-09-28 | 1966-02-22 | Sinclair Research Inc | Transaxle lubricant |
US3250715A (en) * | 1964-02-04 | 1966-05-10 | Lubrizol Corp | Terpolymer product and lubricating composition containing it |
US3269993A (en) * | 1960-12-30 | 1966-08-30 | Monsanto Co | Antifoamants of isotactic alkyl methacrylate polymers |
US3272746A (en) * | 1965-11-22 | 1966-09-13 | Lubrizol Corp | Lubricating composition containing an acylated nitrogen compound |
US3281428A (en) * | 1963-04-29 | 1966-10-25 | Lubrizol Corp | Reaction product of certain acylated nitrogen containing intermediates and a boron compound |
US3282955A (en) * | 1963-04-29 | 1966-11-01 | Lubrizol Corp | Reaction products of acylated nitrogen intermediates and a boron compound |
US3331776A (en) * | 1962-10-04 | 1967-07-18 | Shell Oil Co | Lubricating oil composition |
US3338832A (en) * | 1963-04-29 | 1967-08-29 | Lubrizol Corp | Lubricating oil containing reaction product of certain acylated nitrogen containing intermediates and a boron compound |
US3342735A (en) * | 1965-04-23 | 1967-09-19 | Texaco Inc | Alkenyl succinic anhydride-amine-ps reaction product |
US3344069A (en) * | 1965-07-01 | 1967-09-26 | Lubrizol Corp | Lubricant additive and lubricant containing same |
US3368972A (en) * | 1965-01-06 | 1968-02-13 | Mobil Oil Corp | High molecular weight mannich bases as engine oil additives |
US3381022A (en) * | 1963-04-23 | 1968-04-30 | Lubrizol Corp | Polymerized olefin substituted succinic acid esters |
US3403102A (en) * | 1963-05-17 | 1968-09-24 | Lubrizol Corp | Lubricant containing phosphorus acid esters |
US3413347A (en) * | 1966-01-26 | 1968-11-26 | Ethyl Corp | Mannich reaction products of high molecular weight alkyl phenols, aldehydes and polyaminopolyalkyleneamines |
US3442808A (en) * | 1966-11-01 | 1969-05-06 | Standard Oil Co | Lubricating oil additives |
US3448047A (en) * | 1967-04-05 | 1969-06-03 | Standard Oil Co | Lube oil dispersants |
US3454497A (en) * | 1966-11-14 | 1969-07-08 | Shell Oil Co | Lubricating compositions |
US3459661A (en) * | 1967-01-20 | 1969-08-05 | Shell Oil Co | Lubricating compositions containing metal salts of particular condensation products |
US3493520A (en) * | 1968-06-04 | 1970-02-03 | Sinclair Research Inc | Ashless lubricating oil detergents |
US3502607A (en) * | 1966-10-31 | 1970-03-24 | Celanese Corp | Art of making dyeable polyacrylonitrile products |
US3511780A (en) * | 1966-02-09 | 1970-05-12 | Exxon Research Engineering Co | Oil-soluble ashless dispersant-detergent-inhibitors |
US3513093A (en) * | 1963-06-17 | 1970-05-19 | Lubrizol Corp | Lubricant containing nitrogen-containing and phosphorus-containing succinic derivatives |
US3522179A (en) * | 1963-04-23 | 1970-07-28 | Lubrizol Corp | Lubricating composition containing esters of hydrocarbon-substituted succinic acid |
US3533945A (en) * | 1963-11-13 | 1970-10-13 | Lubrizol Corp | Lubricating oil composition |
US3539633A (en) * | 1965-10-22 | 1970-11-10 | Standard Oil Co | Di-hydroxybenzyl polyamines |
US3558743A (en) * | 1968-06-04 | 1971-01-26 | Joseph A Verdol | Ashless,oil-soluble detergents |
US3576743A (en) * | 1969-04-11 | 1971-04-27 | Lubrizol Corp | Lubricant and fuel additives and process for making the additives |
US3586629A (en) * | 1968-09-16 | 1971-06-22 | Mobil Oil Corp | Metal salts as lubricant additives |
US3591598A (en) * | 1968-11-08 | 1971-07-06 | Standard Oil Co | Certain condensation products derived from mannich bases |
US3600372A (en) * | 1968-06-04 | 1971-08-17 | Standard Oil Co | Carbon disulfide treated mannich condensation products |
US3632511A (en) * | 1969-11-10 | 1972-01-04 | Lubrizol Corp | Acylated nitrogen-containing compositions processes for their preparationand lubricants and fuels containing the same |
US3634515A (en) * | 1968-11-08 | 1972-01-11 | Standard Oil Co | Alkylene polyamide formaldehyde |
US3649229A (en) * | 1969-12-17 | 1972-03-14 | Mobil Oil Corp | Liquid hydrocarbon fuels containing high molecular weight mannich bases |
USRE27331E (en) * | 1966-12-19 | 1972-04-11 | Sulfurized diels-alder adducts and lubricants containing the same | |
US3658836A (en) * | 1964-04-16 | 1972-04-25 | Monsanto Co | Hydroxyboroxin-amine salts |
US3663561A (en) * | 1969-12-29 | 1972-05-16 | Standard Oil Co | 2-hydrocarbyldithio - 5 - mercapto-1,3,4-thiadiazoles and their preparation |
US3676089A (en) * | 1969-11-06 | 1972-07-11 | Texaco Inc | Motor fuel composition |
US3692503A (en) * | 1969-02-26 | 1972-09-19 | Apollo Chem | Activated manganese containing additive for fuels |
US3697574A (en) * | 1965-10-22 | 1972-10-10 | Standard Oil Co | Boron derivatives of high molecular weight mannich condensation products |
US3703536A (en) * | 1967-11-24 | 1972-11-21 | Standard Oil Co | Preparation of oil-soluble boron derivatives of an alkylene polyamine-substituted phenol-formaldehyde addition product |
US3704308A (en) * | 1965-10-22 | 1972-11-28 | Standard Oil Co | Boron-containing high molecular weight mannich condensation |
US3718663A (en) * | 1967-11-24 | 1973-02-27 | Standard Oil Co | Preparation of oil-soluble boron derivatives of an alkylene polyamine-urea or thiourea-succinic anhydride addition product |
US3725480A (en) * | 1968-11-08 | 1973-04-03 | Standard Oil Co | Ashless oil additives |
US3726882A (en) * | 1968-11-08 | 1973-04-10 | Standard Oil Co | Ashless oil additives |
US3736357A (en) * | 1965-10-22 | 1973-05-29 | Standard Oil Co | High molecular weight mannich condensation products from two different alkyl-substituted hydroxy-aromatic compounds |
US3751365A (en) * | 1965-10-22 | 1973-08-07 | Standard Oil Co | Concentrates and crankcase oils comprising oil solutions of boron containing high molecular weight mannich reaction condensation products |
US3756953A (en) * | 1965-10-22 | 1973-09-04 | Standard Oil Co | Vatives of high molecular weight mannich reaction condensation concentrate and crankcase oils comprising oil solutions of boron deri |
US3763244A (en) * | 1971-11-03 | 1973-10-02 | Ethyl Corp | Process for producing a c6-c16 normal alpha-olefin oligomer having a pour point below about- f. |
US3780128A (en) * | 1971-11-03 | 1973-12-18 | Ethyl Corp | Synthetic lubricants by oligomerization and hydrogenation |
US3837820A (en) * | 1971-09-01 | 1974-09-24 | Apollo Chem | Combustion control by additives introduced in both hot and cold zones |
US4047875A (en) * | 1975-11-24 | 1977-09-13 | Petrolite Corporation | Inhibition of corrosion in fuels with Mg/Si/Mn combinations |
US5595966A (en) * | 1990-07-24 | 1997-01-21 | Ethyl Petroleum Additives Limited | Biodegradable lubricants and functional fluids |
US20040118032A1 (en) * | 2002-12-18 | 2004-06-24 | Aradi Allen A. | Manganese compounds to inhibit both low-and high-temperature corrosion in utility and industrial furnace systems |
US20050090409A1 (en) * | 2003-10-24 | 2005-04-28 | Devlin Mark T. | Lubricant compositions |
US20050090410A1 (en) * | 2003-10-24 | 2005-04-28 | Devlin Mark T. | Lubricant compositions |
US20050108923A1 (en) * | 2003-11-25 | 2005-05-26 | Factor Stephen A. | Mixed metal catalyst additive and method for use in hydrocarbonaceous fuel combustion system |
US20050257724A1 (en) * | 2004-05-24 | 2005-11-24 | Guinther Gregory H | Additive-induced control of NOx emissions in a coal burning utility furnace |
US7094274B2 (en) * | 2003-04-17 | 2006-08-22 | Afton Chemical Intangibles Llc | Use of manganese compounds to improve the efficiency of and reduce back-corona discharge on electrostatic precipitators |
US7270063B2 (en) * | 2004-11-16 | 2007-09-18 | Afton Chemical Corporation | Methods and apparatuses for removing mercury-containing material from emissions of combustion devices, and flue gas and flyash resulting therefrom |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2144060C1 (en) * | 1996-12-20 | 2000-01-10 | Поханг Айрон энд Стил Ко., Лтд. | Method for increasing combustibility of coal used in cast iron production process |
WO2002050220A1 (en) * | 2000-12-21 | 2002-06-27 | Ve Gruppen A/S | Method and system for production of fuel pellets and fuel pellet |
US20050011413A1 (en) * | 2003-07-18 | 2005-01-20 | Roos Joseph W. | Lowering the amount of carbon in fly ash from burning coal by a manganese additive to the coal |
US20050016062A1 (en) * | 2003-07-24 | 2005-01-27 | Carla Bonnell-Rickard | Fire log made of recycled materials and a method and an apparatus for manufacturing the same |
-
2007
- 2007-09-17 US US11/856,205 patent/US20090071067A1/en not_active Abandoned
-
2008
- 2008-09-03 EP EP08163571A patent/EP2039739A1/en not_active Withdrawn
Patent Citations (99)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1815022A (en) * | 1930-05-03 | 1931-07-14 | Standard Oil Dev Co | Hydrocarbon oil and process for manufacturing the same |
US2015748A (en) * | 1933-06-30 | 1935-10-01 | Standard Oil Dev Co | Method for producing pour inhibitors |
US2191498A (en) * | 1935-11-27 | 1940-02-27 | Socony Vacuum Oil Co Inc | Mineral oil composition and method of making |
US2197263A (en) * | 1939-02-23 | 1940-04-16 | Socony Vacuum Oil Co Inc | Grease composition |
US2284409A (en) * | 1940-03-08 | 1942-05-26 | Pittsburgh Corning Corp | Fitting for tempered glass panels |
US2284410A (en) * | 1940-08-22 | 1942-05-26 | John F Farmer | Adjustable end slide grille |
US2387501A (en) * | 1944-04-04 | 1945-10-23 | Du Pont | Hydrocarbon oil |
US2564561A (en) * | 1944-05-20 | 1951-08-14 | Socony Vacuum Oil Co Inc | Grease composition |
US2448664A (en) * | 1944-05-30 | 1948-09-07 | Carbide & Carbon Chem Corp | Polyoxypropylene compounds |
US2425755A (en) * | 1944-06-01 | 1947-08-19 | Carbide & Carbon Chem Corp | Mixtures of polyoxyalkylene monohydroxy compounds and methods of making such mixtures |
US2425845A (en) * | 1945-04-21 | 1947-08-19 | Carbide & Carbon Chem Corp | Mixtures of polyoxyalkylene diols and methods of making such mixtures |
US2459112A (en) * | 1945-07-06 | 1949-01-11 | Socony Vacuum Oil Co Inc | Mineral oil composition |
US2457139A (en) * | 1946-02-26 | 1948-12-28 | Carbide & Carbon Chem Corp | Esters of polyoxyalkylene diols |
US2655479A (en) * | 1949-01-03 | 1953-10-13 | Standard Oil Dev Co | Polyester pour depressants |
US2721878A (en) * | 1951-08-18 | 1955-10-25 | Exxon Research Engineering Co | Strong acid as a polymerization modifier in the production of liquid polymers |
US2721877A (en) * | 1951-08-22 | 1955-10-25 | Exxon Research Engineering Co | Lubricating oil additives and a process for their preparation |
US2666746A (en) * | 1952-08-11 | 1954-01-19 | Standard Oil Dev Co | Lubricating oil composition |
US2760933A (en) * | 1952-11-25 | 1956-08-28 | Standard Oil Co | Lubricants |
US2749311A (en) * | 1952-12-04 | 1956-06-05 | Standard Oil Co | Corrosion inhibitors and compositions containing the same |
US2765289A (en) * | 1953-04-29 | 1956-10-02 | Standard Oil Co | Corrosion inhibitors and compositions containing the same |
US3061420A (en) * | 1955-02-11 | 1962-10-30 | Exxon Research Engineering Co | Motor fuel |
US2850453A (en) * | 1955-04-26 | 1958-09-02 | Standard Oil Co | Corrosion inhibited oil compositions |
US2910439A (en) * | 1955-12-22 | 1959-10-27 | Standard Oil Co | Corrosion inhibited compositions |
US2984550A (en) * | 1956-09-06 | 1961-05-16 | Nalco Chemical Co | Color stabilization of petroleum oils and compositions therefor |
US2962442A (en) * | 1957-01-03 | 1960-11-29 | Socony Mobil Oil Co Inc | Preparation of aldehyde-polyamine-hydroxyaromatic compound condensates and hydrocarbon fractions containing the same |
US3036003A (en) * | 1957-08-07 | 1962-05-22 | Sinclair Research Inc | Lubricating oil composition |
US3172892A (en) * | 1959-03-30 | 1965-03-09 | Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine | |
US3219666A (en) * | 1959-03-30 | 1965-11-23 | Derivatives of succinic acids and nitrogen compounds | |
US3202678A (en) * | 1959-08-24 | 1965-08-24 | California Research Corp | Alkenyl succinimides of tetraethylene pentamine |
US3236770A (en) * | 1960-09-28 | 1966-02-22 | Sinclair Research Inc | Transaxle lubricant |
US3166516A (en) * | 1960-10-28 | 1965-01-19 | Nalco Chemical Co | Process for breaking petroleum emulsions |
US2999065A (en) * | 1960-11-07 | 1961-09-05 | Socony Mobil Oil Co Inc | Lubricant containing a calcium saltcalcium soaps mixture and process for forming same |
US2999066A (en) * | 1960-12-28 | 1961-09-05 | Socony Mobil Oil Co Inc | Lubricant containing a calcium saltcalcium soap mixture and process for forming same |
US3269993A (en) * | 1960-12-30 | 1966-08-30 | Monsanto Co | Antifoamants of isotactic alkyl methacrylate polymers |
US3197496A (en) * | 1961-08-09 | 1965-07-27 | Lubrizol Corp | Polyphosphorus ester derivatives of o, o-dihydrocarbyl-s-hydroxylalkyl phosphorodithioates |
US3087936A (en) * | 1961-08-18 | 1963-04-30 | Lubrizol Corp | Reaction product of an aliphatic olefinpolymer-succinic acid producing compound with an amine and reacting the resulting product with a boron compound |
US3254025A (en) * | 1961-08-18 | 1966-05-31 | Lubrizol Corp | Boron-containing acylated amine and lubricating compositions containing the same |
US3197405A (en) * | 1962-07-09 | 1965-07-27 | Lubrizol Corp | Phosphorus-and nitrogen-containing compositions and process for preparing the same |
US3184474A (en) * | 1962-09-05 | 1965-05-18 | Exxon Research Engineering Co | Reaction product of alkenyl succinic acid or anhydride with polyamine and polyhydricmaterial |
US3184411A (en) * | 1962-09-28 | 1965-05-18 | California Research Corp | Lubricants for reducing corrosion |
US3331776A (en) * | 1962-10-04 | 1967-07-18 | Shell Oil Co | Lubricating oil composition |
US3381022A (en) * | 1963-04-23 | 1968-04-30 | Lubrizol Corp | Polymerized olefin substituted succinic acid esters |
US3522179A (en) * | 1963-04-23 | 1970-07-28 | Lubrizol Corp | Lubricating composition containing esters of hydrocarbon-substituted succinic acid |
US3281428A (en) * | 1963-04-29 | 1966-10-25 | Lubrizol Corp | Reaction product of certain acylated nitrogen containing intermediates and a boron compound |
US3282955A (en) * | 1963-04-29 | 1966-11-01 | Lubrizol Corp | Reaction products of acylated nitrogen intermediates and a boron compound |
US3338832A (en) * | 1963-04-29 | 1967-08-29 | Lubrizol Corp | Lubricating oil containing reaction product of certain acylated nitrogen containing intermediates and a boron compound |
US3403102A (en) * | 1963-05-17 | 1968-09-24 | Lubrizol Corp | Lubricant containing phosphorus acid esters |
US3513093A (en) * | 1963-06-17 | 1970-05-19 | Lubrizol Corp | Lubricant containing nitrogen-containing and phosphorus-containing succinic derivatives |
US3533945A (en) * | 1963-11-13 | 1970-10-13 | Lubrizol Corp | Lubricating oil composition |
US3250715A (en) * | 1964-02-04 | 1966-05-10 | Lubrizol Corp | Terpolymer product and lubricating composition containing it |
US3216936A (en) * | 1964-03-02 | 1965-11-09 | Lubrizol Corp | Process of preparing lubricant additives |
US3658836A (en) * | 1964-04-16 | 1972-04-25 | Monsanto Co | Hydroxyboroxin-amine salts |
US3368972A (en) * | 1965-01-06 | 1968-02-13 | Mobil Oil Corp | High molecular weight mannich bases as engine oil additives |
US3342735A (en) * | 1965-04-23 | 1967-09-19 | Texaco Inc | Alkenyl succinic anhydride-amine-ps reaction product |
US3344069A (en) * | 1965-07-01 | 1967-09-26 | Lubrizol Corp | Lubricant additive and lubricant containing same |
US3697574A (en) * | 1965-10-22 | 1972-10-10 | Standard Oil Co | Boron derivatives of high molecular weight mannich condensation products |
US3751365A (en) * | 1965-10-22 | 1973-08-07 | Standard Oil Co | Concentrates and crankcase oils comprising oil solutions of boron containing high molecular weight mannich reaction condensation products |
US3736357A (en) * | 1965-10-22 | 1973-05-29 | Standard Oil Co | High molecular weight mannich condensation products from two different alkyl-substituted hydroxy-aromatic compounds |
US3756953A (en) * | 1965-10-22 | 1973-09-04 | Standard Oil Co | Vatives of high molecular weight mannich reaction condensation concentrate and crankcase oils comprising oil solutions of boron deri |
US3539633A (en) * | 1965-10-22 | 1970-11-10 | Standard Oil Co | Di-hydroxybenzyl polyamines |
US3704308A (en) * | 1965-10-22 | 1972-11-28 | Standard Oil Co | Boron-containing high molecular weight mannich condensation |
US3272746A (en) * | 1965-11-22 | 1966-09-13 | Lubrizol Corp | Lubricating composition containing an acylated nitrogen compound |
US3725277A (en) * | 1966-01-26 | 1973-04-03 | Ethyl Corp | Lubricant compositions |
US3413347A (en) * | 1966-01-26 | 1968-11-26 | Ethyl Corp | Mannich reaction products of high molecular weight alkyl phenols, aldehydes and polyaminopolyalkyleneamines |
US3511780A (en) * | 1966-02-09 | 1970-05-12 | Exxon Research Engineering Co | Oil-soluble ashless dispersant-detergent-inhibitors |
US3502607A (en) * | 1966-10-31 | 1970-03-24 | Celanese Corp | Art of making dyeable polyacrylonitrile products |
US3442808A (en) * | 1966-11-01 | 1969-05-06 | Standard Oil Co | Lubricating oil additives |
US3454497A (en) * | 1966-11-14 | 1969-07-08 | Shell Oil Co | Lubricating compositions |
USRE27331E (en) * | 1966-12-19 | 1972-04-11 | Sulfurized diels-alder adducts and lubricants containing the same | |
US3459661A (en) * | 1967-01-20 | 1969-08-05 | Shell Oil Co | Lubricating compositions containing metal salts of particular condensation products |
US3448047A (en) * | 1967-04-05 | 1969-06-03 | Standard Oil Co | Lube oil dispersants |
US3703536A (en) * | 1967-11-24 | 1972-11-21 | Standard Oil Co | Preparation of oil-soluble boron derivatives of an alkylene polyamine-substituted phenol-formaldehyde addition product |
US3718663A (en) * | 1967-11-24 | 1973-02-27 | Standard Oil Co | Preparation of oil-soluble boron derivatives of an alkylene polyamine-urea or thiourea-succinic anhydride addition product |
US3600372A (en) * | 1968-06-04 | 1971-08-17 | Standard Oil Co | Carbon disulfide treated mannich condensation products |
US3558743A (en) * | 1968-06-04 | 1971-01-26 | Joseph A Verdol | Ashless,oil-soluble detergents |
US3493520A (en) * | 1968-06-04 | 1970-02-03 | Sinclair Research Inc | Ashless lubricating oil detergents |
US3586629A (en) * | 1968-09-16 | 1971-06-22 | Mobil Oil Corp | Metal salts as lubricant additives |
US3634515A (en) * | 1968-11-08 | 1972-01-11 | Standard Oil Co | Alkylene polyamide formaldehyde |
US3726882A (en) * | 1968-11-08 | 1973-04-10 | Standard Oil Co | Ashless oil additives |
US3591598A (en) * | 1968-11-08 | 1971-07-06 | Standard Oil Co | Certain condensation products derived from mannich bases |
US3725480A (en) * | 1968-11-08 | 1973-04-03 | Standard Oil Co | Ashless oil additives |
US3692503A (en) * | 1969-02-26 | 1972-09-19 | Apollo Chem | Activated manganese containing additive for fuels |
US3576743A (en) * | 1969-04-11 | 1971-04-27 | Lubrizol Corp | Lubricant and fuel additives and process for making the additives |
US3676089A (en) * | 1969-11-06 | 1972-07-11 | Texaco Inc | Motor fuel composition |
US3632511A (en) * | 1969-11-10 | 1972-01-04 | Lubrizol Corp | Acylated nitrogen-containing compositions processes for their preparationand lubricants and fuels containing the same |
US3649229A (en) * | 1969-12-17 | 1972-03-14 | Mobil Oil Corp | Liquid hydrocarbon fuels containing high molecular weight mannich bases |
US3663561A (en) * | 1969-12-29 | 1972-05-16 | Standard Oil Co | 2-hydrocarbyldithio - 5 - mercapto-1,3,4-thiadiazoles and their preparation |
US3837820A (en) * | 1971-09-01 | 1974-09-24 | Apollo Chem | Combustion control by additives introduced in both hot and cold zones |
US3763244A (en) * | 1971-11-03 | 1973-10-02 | Ethyl Corp | Process for producing a c6-c16 normal alpha-olefin oligomer having a pour point below about- f. |
US3780128A (en) * | 1971-11-03 | 1973-12-18 | Ethyl Corp | Synthetic lubricants by oligomerization and hydrogenation |
US4047875A (en) * | 1975-11-24 | 1977-09-13 | Petrolite Corporation | Inhibition of corrosion in fuels with Mg/Si/Mn combinations |
US5595966A (en) * | 1990-07-24 | 1997-01-21 | Ethyl Petroleum Additives Limited | Biodegradable lubricants and functional fluids |
US20040118032A1 (en) * | 2002-12-18 | 2004-06-24 | Aradi Allen A. | Manganese compounds to inhibit both low-and high-temperature corrosion in utility and industrial furnace systems |
US7094274B2 (en) * | 2003-04-17 | 2006-08-22 | Afton Chemical Intangibles Llc | Use of manganese compounds to improve the efficiency of and reduce back-corona discharge on electrostatic precipitators |
US20050090409A1 (en) * | 2003-10-24 | 2005-04-28 | Devlin Mark T. | Lubricant compositions |
US20050090410A1 (en) * | 2003-10-24 | 2005-04-28 | Devlin Mark T. | Lubricant compositions |
US20050108923A1 (en) * | 2003-11-25 | 2005-05-26 | Factor Stephen A. | Mixed metal catalyst additive and method for use in hydrocarbonaceous fuel combustion system |
US20050257724A1 (en) * | 2004-05-24 | 2005-11-24 | Guinther Gregory H | Additive-induced control of NOx emissions in a coal burning utility furnace |
US7270063B2 (en) * | 2004-11-16 | 2007-09-18 | Afton Chemical Corporation | Methods and apparatuses for removing mercury-containing material from emissions of combustion devices, and flue gas and flyash resulting therefrom |
Cited By (45)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100006014A1 (en) * | 2008-07-11 | 2010-01-14 | Fuel Tech, Inc. | Targeted reagent injection for slag control from combustion of coals high in iron and/or calcium |
US8241599B2 (en) * | 2009-06-01 | 2012-08-14 | Afton Chemical Corporation | Method of using volatile organometallics as biomass gasification catalysts |
US20100299990A1 (en) * | 2009-06-01 | 2010-12-02 | Allen Aradi | Nanoparticle Catalyst Compounds and/or Volatile Organometallic Compounds and Method of Using the Same for Biomass Gasification |
US20100303705A1 (en) * | 2009-06-01 | 2010-12-02 | Allen Aradi | Method of using volatile organometallics as biomass gasification catalysts |
WO2010141156A1 (en) * | 2009-06-01 | 2010-12-09 | Afton Chemical Corporation | Method of using volatile organometallics as biomass gasification catalysts |
US8404155B2 (en) * | 2009-06-01 | 2013-03-26 | Afton Chemical Corporation | Nanoparticle catalyst compounds and/or volatile organometallic compounds and method of using the same for biomass gasification |
CN101649239B (en) * | 2009-09-17 | 2012-09-05 | 于江善 | Composite coal-saving agent |
US20110078917A1 (en) * | 2009-10-01 | 2011-04-07 | Bland Richard W | Coal fine drying method and system |
US9004284B2 (en) | 2009-10-01 | 2015-04-14 | Vitrinite Services, Llc | Mineral slurry drying method and system |
US9759486B2 (en) | 2009-10-01 | 2017-09-12 | Vitrinite Services, Llc | Mineral slurry drying method and system |
CN102212405A (en) * | 2010-04-01 | 2011-10-12 | 马中胜 | Coal-saving catalytic synergistic agent |
US8758710B2 (en) | 2010-06-15 | 2014-06-24 | E.T. Energy Corp. | Process for treating a flue gas |
US8302325B2 (en) | 2010-09-30 | 2012-11-06 | Ross Technology Corporation | Methods and compositions for drying coal |
WO2012047335A1 (en) * | 2010-09-30 | 2012-04-12 | Vitrinite Services, Llc | Coal drying method and system |
CN102533370A (en) * | 2010-12-10 | 2012-07-04 | 淮南市源泉环保科技有限公司 | Paper making sludge environmentally-friendly briquette and production method thereof |
CN102191110A (en) * | 2011-04-19 | 2011-09-21 | 宜兴市科奇化工有限公司 | Fire coal combustion improver |
WO2012155413A1 (en) * | 2011-05-16 | 2012-11-22 | 科威国际技术转移有限公司 | Biomass fluid fuel and preparation method thereof |
WO2012173922A3 (en) * | 2011-06-13 | 2013-04-04 | Nalco Company | Method for reducing slag in biomass combustion |
US9920929B2 (en) | 2011-06-13 | 2018-03-20 | Ecolab Usa Inc. | Method for reducing slag in biomass combustion |
CN103031174A (en) * | 2011-09-30 | 2013-04-10 | 湖南晟通科技集团有限公司 | Liquid state coal-saving additive |
CN102533301A (en) * | 2012-01-13 | 2012-07-04 | 曹金贵 | Coking coal modifier |
CN102585965A (en) * | 2012-02-27 | 2012-07-18 | 宜兴市创新精细化工有限公司 | Additive capable of improving coal combustion efficiency and reducing NOx emission simultaneously |
CN102746906A (en) * | 2012-07-20 | 2012-10-24 | 杨如平 | High-proportion methanol fuel for diesel and additives thereof |
CN102827666A (en) * | 2012-09-20 | 2012-12-19 | 赵冠军 | Liquid coal combustion improver |
CN104164272A (en) * | 2014-09-02 | 2014-11-26 | 河南炬能能源科技有限公司 | Energy fuel and preparation method thereof |
CN104357124A (en) * | 2014-10-15 | 2015-02-18 | 宁夏宝塔石化科技实业发展有限公司 | Environment-friendly fire coal combustion improver |
CN104498130A (en) * | 2014-11-21 | 2015-04-08 | 河南高能能源有限公司 | High energy fuel special for boiler |
CN104962334A (en) * | 2015-06-16 | 2015-10-07 | 中南大学 | Biomass char composite fuel for iron ore sintering |
US20170089572A1 (en) * | 2015-09-25 | 2017-03-30 | Fuel Tech, Inc. | Process and Apparatus for Reducing Acid Plume |
US10197272B2 (en) * | 2015-09-25 | 2019-02-05 | Fuel Tech, Inc. | Process and apparatus for reducing acid plume |
CN105238491A (en) * | 2015-10-15 | 2016-01-13 | 阳开金 | Coal-saving combustion improver and preparation method thereof |
CN105238495A (en) * | 2015-10-30 | 2016-01-13 | 湖南和易环保科技有限公司 | Additive for eliminating dioxin produced in garbage incineration, and production process and application process thereof |
CN105695035A (en) * | 2016-02-26 | 2016-06-22 | 天津水泥工业设计研究院有限公司 | Inferior coal catalysis sulphur-fixing agent used in cement industry and preparing and using methods thereof |
CN106118798A (en) * | 2016-08-03 | 2016-11-16 | 安徽中缘新材料科技有限公司 | A kind of clean coal burning catalyst |
CN106244287A (en) * | 2016-08-03 | 2016-12-21 | 安徽中缘新材料科技有限公司 | A kind of clean coal burning catalyst |
CN106190425A (en) * | 2016-08-03 | 2016-12-07 | 安徽中缘新材料科技有限公司 | A kind of preparation method of environment-friendly high-efficiency clean coal burning catalyst |
CN106118800A (en) * | 2016-08-03 | 2016-11-16 | 安徽中缘新材料科技有限公司 | A kind of preparation method of clean coal burning catalyst |
CN111100720A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Coal powder treatment method, coal powder product and coal powder gasification method |
US11560524B2 (en) | 2018-10-29 | 2023-01-24 | China Petroleum & Chemical Corporation | Coal powder pretreatment method and coal powder gasification method |
US20220352529A1 (en) * | 2019-07-03 | 2022-11-03 | Audi Ag | Fuel cell plate, bipolar plate and fuel cell device |
CN111961512A (en) * | 2020-07-10 | 2020-11-20 | 广西夏阳环保科技有限公司 | Special briquette for lime for aerated concrete and preparation method thereof |
CN112619204A (en) * | 2020-12-31 | 2021-04-09 | 浙江锦华新材料股份有限公司 | Deep dehydration drying agent and application thereof in synthesis of methyl tributyl ketoxime silane |
KR102468473B1 (en) * | 2021-10-18 | 2022-11-18 | 세이프코리아 주식회사 | Biomass solid fuel using coffee gourd |
CN114634834A (en) * | 2022-03-30 | 2022-06-17 | 湖南昌迪环境科技有限公司 | Fire coal additive and application thereof |
CN115418258A (en) * | 2022-09-14 | 2022-12-02 | 滁州智慧城市环保科技有限责任公司 | Boiler coking inhibitor and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
EP2039739A1 (en) | 2009-03-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20090071067A1 (en) | Environmentally-Friendly Additives And Additive Compositions For Solid Fuels | |
US7862628B2 (en) | Mixed metal catalyst additive and method for use in hydrocarbonaceous fuel combustion system | |
US20090031614A1 (en) | Environmentally-Friendly Fuel Compositions | |
Badia et al. | New octane booster molecules for modern gasoline composition | |
US7410514B2 (en) | Liquid fuel composition having aliphatic organic non-hydrocarbon compounds, an aromatic hydrocarbon having an aromatic content of less than 15% by volume, an oxygenate, and water | |
US8211190B2 (en) | Fuel oil compositions | |
US6569909B1 (en) | Inhibition of biological degradation in fischer-tropsch products | |
CN101636476A (en) | Composition, method and use | |
JPH05194559A (en) | Organophosphates and their production | |
JP2003193074A (en) | Method for reducing nitrogen oxides in combustion waste gas and fuel composition | |
EP2025737A1 (en) | Environmentally-friendly fuel compositions | |
JPS6014073B2 (en) | Combustion aid for liquid fuel | |
CA2367517C (en) | Fuel oil compositions | |
CA3041781C (en) | Methods for preventing microbial growth and microbiologically influenced corrosion in a biodegradable and/or renewable fuel, hydraulic fluid and/or lubricant | |
CN102203224A (en) | Improvement in or relating to fuel additive compositions | |
PL224139B1 (en) | Fuel blend, particularly for engines with spark ignition | |
EP0350165A1 (en) | Method for preventing the growth of aerobic fungi in aqueous hydrocarbons | |
Zegeye | Optimization and Upgrading of Biogas from Brewery Waste for Boiler | |
Dodos et al. | Effect of secondary Aldimines on the oxidation and microbial stability of biodiesel fuel | |
RU2323249C1 (en) | Fuel composition | |
Yan | The Mechanism of Foaming in Deep-Pit Swine Manure Storage | |
Politanskii et al. | An antiknock additive of the new generation | |
BR102017004823A2 (en) | synthetic fuel and mixtures for automotive use, diesel formulation s 500 and s 10 derived from municipal solid waste and or biomass by catalytic depolymerization process. | |
PL201210B1 (en) | Fuel additive featuring biostatic properties | |
PL229044B1 (en) | Set of multi-functional additives to solid fuels containing biogenic components |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: AFTON CHEMICAL CORPORATION, VIRGINIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MACPHERSON, IAN;QUINN, THOMAS G.;MEFFERT, MICHAEL W.;REEL/FRAME:019833/0462 Effective date: 20070917 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |