AU2011226768B2 - Hydrophobically modified polyamine scale inhibitors - Google Patents
Hydrophobically modified polyamine scale inhibitors Download PDFInfo
- Publication number
- AU2011226768B2 AU2011226768B2 AU2011226768A AU2011226768A AU2011226768B2 AU 2011226768 B2 AU2011226768 B2 AU 2011226768B2 AU 2011226768 A AU2011226768 A AU 2011226768A AU 2011226768 A AU2011226768 A AU 2011226768A AU 2011226768 B2 AU2011226768 B2 AU 2011226768B2
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- Australia
- Prior art keywords
- optionally substituted
- nitrogen
- alkyl
- group
- aryl
- Prior art date
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- 229920000768 polyamine Polymers 0.000 title claims abstract description 32
- 239000002455 scale inhibitor Substances 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims description 86
- 150000001875 compounds Chemical class 0.000 claims description 49
- 229920002873 Polyethylenimine Polymers 0.000 claims description 41
- -1 ethylhexyl Chemical group 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 37
- 125000003342 alkenyl group Chemical group 0.000 claims description 26
- 125000003118 aryl group Chemical group 0.000 claims description 26
- 239000007795 chemical reaction product Substances 0.000 claims description 26
- 229910052665 sodalite Inorganic materials 0.000 claims description 24
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 22
- 229910021645 metal ion Inorganic materials 0.000 claims description 15
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 claims description 4
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 claims description 4
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 4
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 4
- 229940073608 benzyl chloride Drugs 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 4
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 claims description 3
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 claims description 3
- DBHYCIBSVGMTQT-UHFFFAOYSA-N 2,4-diamino-3,5,5-trimethylcyclohex-2-en-1-one Chemical compound CC1=C(N)C(=O)CC(C)(C)C1N DBHYCIBSVGMTQT-UHFFFAOYSA-N 0.000 claims description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 3
- CUFXMPWHOWYNSO-UHFFFAOYSA-N 2-[(4-methylphenoxy)methyl]oxirane Chemical compound C1=CC(C)=CC=C1OCC1OC1 CUFXMPWHOWYNSO-UHFFFAOYSA-N 0.000 claims description 3
- KAYAKFYASWYOEB-UHFFFAOYSA-N 3-octadec-1-enyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCCCCCC=CC1CC(=O)OC1=O KAYAKFYASWYOEB-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 claims description 3
- FLISWPFVWWWNNP-BQYQJAHWSA-N dihydro-3-(1-octenyl)-2,5-furandione Chemical compound CCCCCC\C=C\C1CC(=O)OC1=O FLISWPFVWWWNNP-BQYQJAHWSA-N 0.000 claims description 3
- 239000012634 fragment Substances 0.000 claims description 3
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000004131 Bayer process Methods 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005700 Putrescine Substances 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002655 kraft paper Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 77
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 57
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 21
- 229910000077 silane Inorganic materials 0.000 description 21
- 238000010998 test method Methods 0.000 description 19
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 16
- LWIOWIKKGKNURV-UHFFFAOYSA-N 2-[[5-nonyl-2-[4-nonyl-2-(oxiran-2-ylmethyl)phenoxy]phenyl]methyl]oxirane Chemical compound C1OC1CC1=CC(CCCCCCCCC)=CC=C1OC1=CC=C(CCCCCCCCC)C=C1CC1CO1 LWIOWIKKGKNURV-UHFFFAOYSA-N 0.000 description 13
- 159000000000 sodium salts Chemical class 0.000 description 12
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 11
- 230000009467 reduction Effects 0.000 description 11
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- 230000002209 hydrophobic effect Effects 0.000 description 10
- 238000011282 treatment Methods 0.000 description 10
- 101150101414 PRP1 gene Proteins 0.000 description 6
- 101100368710 Rattus norvegicus Tacstd2 gene Proteins 0.000 description 6
- 101100342406 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) PRS1 gene Proteins 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical group CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- AVKQYWUBGXNBCW-UHFFFAOYSA-N 2-[(4-nonylphenoxy)methyl]oxirane Chemical compound C1=CC(CCCCCCCCC)=CC=C1OCC1OC1 AVKQYWUBGXNBCW-UHFFFAOYSA-N 0.000 description 2
- ZAXCZCOUDLENMH-UHFFFAOYSA-N 3,3,3-tetramine Chemical compound NCCCNCCCNCCCN ZAXCZCOUDLENMH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 229920001600 hydrophobic polymer Polymers 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- OETHQSJEHLVLGH-UHFFFAOYSA-N metformin hydrochloride Chemical compound Cl.CN(C)C(=N)N=C(N)N OETHQSJEHLVLGH-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical group CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 239000000429 sodium aluminium silicate Substances 0.000 description 2
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical compound CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- YNUQSIZNWGETAI-UHFFFAOYSA-N 2-[10-(oxiran-2-yl)decyl]phenol Chemical compound C(C1CO1)CCCCCCCCCC1=C(C=CC=C1)O YNUQSIZNWGETAI-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- RXFCIXRFAJRBSG-UHFFFAOYSA-N 3,2,3-tetramine Chemical group NCCCNCCNCCCN RXFCIXRFAJRBSG-UHFFFAOYSA-N 0.000 description 1
- GXDMUOPCQNLBCZ-UHFFFAOYSA-N 3-(3-triethoxysilylpropyl)oxolane-2,5-dione Chemical compound CCO[Si](OCC)(OCC)CCCC1CC(=O)OC1=O GXDMUOPCQNLBCZ-UHFFFAOYSA-N 0.000 description 1
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000012042 active reagent Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
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- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
- 125000005518 carboxamido group Chemical group 0.000 description 1
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
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- 125000004663 dialkyl amino group Chemical group 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
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- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005553 heteroaryloxy group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XTBMQKZEIICCCS-UHFFFAOYSA-N hexane-1,5-diamine Chemical compound CC(N)CCCCN XTBMQKZEIICCCS-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- KKHUSADXXDNRPW-UHFFFAOYSA-N malonic anhydride Chemical compound O=C1CC(=O)O1 KKHUSADXXDNRPW-UHFFFAOYSA-N 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- IGSFQSTYARRVAJ-UHFFFAOYSA-N n'-benzylmethanediamine Chemical compound NCNCC1=CC=CC=C1 IGSFQSTYARRVAJ-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Chemical group 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
- C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Hydrophobically Modified Polyamine Scale Inhibitors Abstract Hydrophobically modified Si-containing polyamines are useful for treating scale in s industrial process streams. Preferred hydrophobically modified Si-containing polyamines are particularly useful for treating aluminosilicate scale in difficult-to-treat industrial process streams, such as in the Bayer alumina process streams, nuclear waste streams and kraft paper mill effluent streams.
Description
S&F Ref: 899539D1 AUSTRALIA PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT Name and Address Cytec Technology Corp, of 300 Delaware Avenue, of Applicant: Wilmington, Delaware, 19801, United States of America Actual Inventor(s): Howard I. Heitner Donald P. Spitzer Address for Service: Spruson & Ferguson St Martins Tower Level 35 31 Market Street Sydney NSW 2000 (CCN 3710000177) Invention Title: Hydrophobically modified polyamine scale inhibitors The following statement is a full description of this invention, including the best method of performing it known to me/us: 5845c(5604718_1) HYDROPHOBICALLY MODIFIED POLYAMINE SCALE INHIBITORS Background of the Invention Field of the Invention [0001] This invention relates to polyamines and methods of using them for treating scale in various industrial process streams. Preferred embodiments relate to hydrophobically modified Si-containing polyamines that have been found to be particularly useful for treating aluminosilicate scale in difficult-to-treat industrial process streams, such as in the Bayer alumina process, nuclear waste streams and kraft paper mill effluent streams. Description of the Related Art [0002] The formation of scale is a problem in a number of industrial process streams. Scale is a solid material that generally forms on the surfaces of equipment that are exposed to aqueous process streams. Scale typically contains inorganic materials having relatively low aqueous solubility, including for example various hydrated sodium aluminosilicate materials such as amorphous aluminosilicates (e.g., aluminosilicate hydrogel), zeolites, sodalites and canerinites. The removal of scale by mechanical methods, e.g., by scraping, is often undesirable because such procedures may involve considerable expense in terms of process downtime, and may be impractical where the scale forms on surfaces of the process equipment that are difficult to access. [0003] A number of chemical treatments have been developed to remove scale and/or inhibit the formation of scale in various industrial process streams. Such chemical treatments are generally applied by intermixing the treatment chemical with the process stream, thus allowing treatment of surfaces that are difficult to access and reducing or eliminating downtime. A number of Si-containing polymers have been developed in recent years and applied to the treatment of scale. See, e.g., U.S. Patent No. 6,814,873; U.S. Patent Publication Nos. 2005/0010008, 2004/0162406, 2006/0124553, 2004/0162406, 2004/0011744, and 2005/0274926; and WO 2004 009606. The foregoing patent publications are hereby incorporated by reference in their entireties, and particularly for the purpose of describing various types of scale, as well as particular Si-containing polymers and their use as anti-scalants in certain industrial process streams: [0004] The Si-containing polymers and methods of using them described above represent a significant advance in the art, but have not completely solved the problem of scale -1- 2 formation in industrial process streams. Difficult-to-treat industrial process streams are particularly vexing. For example, there is a long-felt need for chemical treatments and methods of reducing and/or inhibiting scale in process streams that contain a relatively high level of sulphate, finely dispersed iron oxide (e.g., "red mud"), finely dispersed 5 sodalite, and/or combined nitrate/nitrite. 100051 A variety of Si-containing polymers have been developed for other pruposes, but without any particular motivation to apply such non-analogous art to the treatment of scale. See, e.g., U.S. Patent Nos. 3,560,543; 5,354,829; 6,262,216; 6,410,675; 6,429,275; 6,486,287; and 6,743,882; U.S. Patent Publication No. 10 2006/0159975; Canadian CA 2,193,155; Yan et al, Prepr. Pap. Am. Chem. Soc., Div. Fuel Chem. 2004, 49(2), 599-600; and Macromol. Symp. 2004, 210, 329. Summary of the Invention [00061 Novel Si-containing polymers and methods have now been developed is for the treatment of scale in industrial process streams. Surprisingly, it has been found that relatively hydrophobic Si-containing polymers may provide substantially higher performance than otherwise comparable polymers of lesser hydrophobicity. 10006a] According to a first aspect of the present invention there is provided a method for reducing or eliminating scale in an industrial process, comprising adding a 20 composition comprising a polymeric reaction product of at least a polyamine, a first nitrogen-reactive compound, and a second nitrogen-reactive compound, the polymeric reaction product having a weight average molecular weight of at least about 500, wherein: the first nitrogen-reactive compound comprises a -Si(OR ) 3 group and a nitrogen-reactive group, wherein R = H, optionally substituted CI-C 20 alkyl, optionally 25 substituted C 6
-C
12 aryl, optionally substituted C 7
-C
2 0 aralkyl, optionally substituted C 2 C 20 alkenyl, Group I metal ion, Group II metal ion, or NR' 4 , each R' being independently selected from H, optionally substituted CI-C 2 0 alkyl, optionally substituted C 6
-C
12 aryl, optionally substituted C-C 2 0 aralkyl, and optionally substituted C 2
-C
20 alkenyl; the second nitrogen-reactive compound comprises a nitrogen-reactive group 30 and does not contain a Si(OR )3 group; and at least one of the polyamine and the second nitrogen-reactive compound comprises an optionally substituted hydrocarbyl radical comprising from about 2 to about 40 carbons, to the process. [00071 An embodiment provides polymer comprising a recurring unit of the 35 formula (I) and a recurring unit of the formula (II): 2a T- - tE-N A A2 Si(OR") 3 U (I) (II) wherein: 5 T and E are each independently a first optionally substituted hydrocarbyl radical comprising from about 2 to about 40 carbons; Q is H or a second optionally substituted hydrocarbyl radical comprising from about I to about 20 carbons; AI and A 2 are each independently a direct bond or an organic 1o connecting group comprising from about 1 to about 20 carbons; R" = H, optionally substituted C,-C 20 alkyl, optionally substituted C 6
-CI
2 aryl, optionally substituted C 7 -C20 aralkyl, optionally substituted C 2
-C
2 0 alkenyl, Group I metal ion, Group H metal ion, or NR 1 4 , where each R' is independently selected from H, optionally substituted C 1
-C
2 0 alkyl, optionally substituted C 6
-CI
2 aryl, optionally substituted C 7
-C
2 o aralkyl, and optionally substituted C 2
-C
20 alkenyl; and the polymer has a weight average molecular weight of at least about 500; with a first proviso that when A 2 -Q is H, at least one of T and E comprises 4 or more carbon atoms; with a second proviso that when A 2 -Q is not H, at least one of T and E comprises 2 or more carbon atoms; with a third proviso that Q does not contain a Si(OR )3 group; with a fourth proviso that A2 is not unsubstituted -C(=O)-alkyl; and with a fifth proviso that when Q is OH or NH 2 , A' and A2 are not both alkylene. [0008] Another embodiment provides a composition comprising a polymeric reaction product of at least a polyamine, a first nitrogen-reactive compound, and a second nitrogen-reactive compound, the polymeric reaction product having a weight average molecular weight of at least about 500, wherein: the first nitrogen-reactive compound comprises a -Si(OR") 3 group and a nitrogen-reactive group, where R H, optionally substituted C-C 2 0 alkyl, optionally substituted C 6
-CI
2 aryl, optionally substituted C 7
-C
20 aralkyl, optionally substituted
C
2
-C
2 0 alkenyl, Group I metal ion, Group RI metal ion, or NR 4 , each R1 being independently selected from H, optionally substituted C-C 2 0 alkyl, optionally substituted C 6
-C
2 aryl, optionally substituted C 7
-C
2 0 aralkyl, and optionally substituted C 2
-C
20 alkenyl; the second nitrogen-reactive compound comprises a nitrogen-reactive group and does not contain a Si(OR )3 group; and at least one of the polyamine and the second nitrogen-reactive compound comprises an optionally substituted hydrocarbyl radical comprising from about 2 to about 40 carbons. [0009] Another embodiment provides a method for reducing or eliminating scale in an industrial process, comprising adding a polymer or composition as described herein to the process. -3- [0010] Another embodiment provides a method for treating scale in a difficult-to treat process stream, comprising intermixing a polymer with a process stream in an amount effective to reduce or eliminate aluminosilicate scale in the process stream, wherein the process stream comprises at least one selected from a sulfate level of at least about 1 g/L, a finely dispersed iron oxide level of at least about 20 mg/L, a finely dispersed sodalite level of at least about 20 mg/L, and a combined nitrate/nitrite concentration of at least about 0.5 molar; and wherein the polymer comprises a recurring unit of the formula (I) and a recurring unit of the formula (II): T-N+ 4E-N A'
A
2 I I Si(OR") 3 Q (1) (II) wherein: T and E are each independently a first optionally substituted hydrocarbyl radical comprising from about 2 to about 40 carbons; Q is H or a second optionally substituted hydrocarbyl radical comprising from about 1 to about 20 carbons; A' and A 2 are each independently a direct bond or an organic connecting group comprising from about 1 to about 20 carbons; and R = H, optionally substituted C-C 2 o alkyl, optionally substituted C 6
-C,
2 aryl, optionally substituted C 7 -C20 aralkyl, optionally substituted C 2
-C
2 o alkenyl, Group I metal ion, Group II metal ion, or NR' 4 , where each R' is independently selected from H, optionally substituted C-C 2 o alkyl, optionally substituted C 6 -Cn 2 aryl, optionally substituted C7-C 2 0 aralkyl, and optionally substituted C 2
-C
2 0 alkenyl. [0011] These and other embodiments are described in greater detail below. Detailed Description of the Preferred Embodiments [0012] Terms such as "treatment" and "treating", in the context of describing methods for the treatment of scale, are broad terms that are used herein in their ordinary sense as understood by those skilled in the art, and thus include methods that result in the inhibition -4and/or prevention of scale formation, as well as reduction, removal and/or elimination of existing scale. [0013] The term "scale" is a broad term that is used herein in its ordinary sense as understood by those skilled in the art, and thus includes various primarily or completely inorganic deposits formed on the surfaces of equipment exposed to industrial process streams. Examples of scale include hydrated sodium aluminosilicate materials such as amorphous aluminosilicates (e.g., aluminosilicate hydrogel), zeolites, sodalites and canerinites. [0014] Terms used herein to describe chemical materials, such as "anti-scalant", "scale inhibitor", "scale reducing additive", etc., are broad terms that are used herein in their ordinary sense as understood by those skilled in the art and thus include chemical materials (such as polymers) that are useful for treating scale. [0015] The term "polymer" is a broad term that is used herein in its ordinary sense as understood by those skilled in the art, and thus includes copolymers. Reference herein to the molecular weight of a polymer is understood to be a reference to weight average molecular weight as measured by size exclusion chromatography (light scattering detection). In various embodiments, Si-containing polymers (including, for example, the polymer P1 described herein) can have a molecular weight of at least about 500, at least about 1,000, at least about 2,000, or at least about 5,000. In some embodiments, higher or lower molecular weights are preferred. Although some polymers may be referred to herein as being "hydrophobically modified", it will be understood that this term is used for the sake of convenience, and that such polymers are not limited to those produced by hydrophobic modification of a pre-existing polymer. [0016] The terms "hydrocarbon" and "hydrocarbyl" are broad terms that are used herein in their ordinary sense as understood by those skilled in the art, and thus include organic compounds or radicals consisting exclusively of the elements carbon and hydrogen. These moieties include alkyl, alkylene, alkenyl, alkynyl, and aryl moieties. These moieties also include alkyl, alkenyl, alkynyl, and aryl moieties substituted with other aliphatic or cyclic hydrocarbon groups, such as alkaryl, alkenaryl and alkynaryl. Unless otherwise indicated, these moieties preferably comprise I to 40 carbon atoms. Hydrocarbyl radicals may be substituted with various groups that do not consist exclusively of the elements carbon and hydrogen, and thus a substituted hydrocarbyl radical may contain one or more heteroatoms such as oxygen and/or nitrogen. -5- [0017] The term "substituted", whether preceded by the term "optionally" or not, is a broad term that is used herein in its ordinary sense as understood by those skilled in the art. "Substituted" thus includes replacement of one or more hydrogen radicals in a given structure with one or more substituent groups, which may be any permissible organic substituents of the given structure. Examples of substituents that may be permissible for a given structure include hydroxy; C 1
.
1 o alkyl; C 1
.
10 alkenyl; allyl; halogen; C.
1 0 haloalkyl; C 1 . 1 o alkoxy; hydroxy CI1 0 alkyl; carboxy; C 1
.
1 0 carboalkoxy (also referred to as alkoxycarbonyl);
C
1
.
1 0 carboxyalkoxy; C 1
.
1 0 carboxamido (also referred to as alkylaminocarbonyl); cyano; formyl; C 1
.
1 0 acyl; nitro; amino; Cio 10 alkylamino; C 1 .i 0 dialkylamino; anilino; mercapto; C 1 lo alkylthio; sulfoxide; sulfone; Ci.
1 o acylamino; amidino; phenyl; benzyl; heteroaryl; heterocycle; phenoxy; benzoyl; benzoyl substituted with amino, hydroxy, methoxy, methyl or halo; benzyloxy and heteroaryloxy. When the group that is substituted contains an alkyl segment, two hydrogen atoms on the same carbon atom may be replaced by a single substituent double bonded to the carbon atom, e.g,, oxo (=0). [0018] Various compositions are described herein, including polymers and polymeric reaction products, along with various methods for using such compositions. It will be understood by those skilled in the art that the various compositions described herein may be used in any of the described methods, and that the described methods may employ any of the described compositions. Thus, it will be understood that the inventions described herein are not limited to the descriptions of the particular embodiments. Compositions and Methods of Making Them [00191 An embodiment provides a polymer comprising a recurring unit of the formula (I) and a recurring unit of the formula (II): 4-T-N44 E-N A'
A
2 I I Si(OR") 3 Q (I) (II) wherein: T and E are each independently a first optionally substituted hydrocarbyl radical comprising from about 2 to about 40 carbons; -6- Q is 1 or a second optionally substituted hydrocarbyl radical comprising from about I to about 20 carbons; A' and A 2 are each independently a direct bond or an organic connecting group comprising from about I to about 20 carbons; and R = H, optionally substituted Ci-C 20 alkyl, optionally substituted C 6
-C,
2 aryl, optionally substituted C 7
-C
20 aralkyl, optionally substituted C 2
-C
20 alkenyl, Group I metal ion, Group H metal ion, or NR' 4 , where each R' is independently selected from H, optionally substituted C-C 20 alkyl, optionally substituted C 6 -C1 2 aryl, optionally substituted C7-C 20 aralkyl, and optionally substituted C 2
-C
20 alkenyl. [0020] The term "polymer P1" may be used herein to refer to polymers comprising a recurring unit of the formula (1) and a recurring unit of the formula (II). In an embodiment, the polymer P1 comprises recurring units of the formula (I) in which R" is a Group I metal ion (e.g., Na), a Group (H) metal ion (e.g., K) and/or NR' 4 (e.g., ammonium). In various embodiments, the polymer P1 may be further described as being subject to one or more of the following provisos: a first proviso that when A2-Q is H, at least one of T and E comprises 4 or more carbon atoms; a second proviso that when A -Q is not H, at least one of T and E comprises 2 or more carbon atom; a third proviso that Q does not contain a Si(OR") 3 group; a fourth proviso that A2 is not unsubstituted -C(=O)-alkyl; and/or a fifth proviso that when Q is OH or NH 2 , A' and A 2 are not both alkylene. It will be understood that the polymer P1 may comprise other recurring units as well. For example, in an embodiment, a polymer comprising a recurring unit of the formula (1) and a recurring unit of the formula ([1) further comprises a recurring unit of the formula -((CH 2 )n-NH)-, wherein n is an integer in the range of about 2 to about 10. The amounts of recurring unit in the polymer P1 may vary over a broad range. For example, in an embodiment, the polymer P1 comprises at least about 0.1 mole percent, preferably at least about I mole percent of recurring units of the formula (I) and at least about 0.1 mole percent, preferably at least about 1 mole percent of recurring units of the formula (II), based on total moles of recurring units in the polymer P1. [0021] As indicated above, the recurring units of the formulae (1) and (II) in the polymer P1 include A' and A 2 , which are each independently a direct bond or an organic connecting group comprising from about 1 to about 20 carbons. Examples of suitable organic connecting groups include those in which A] and A2 are each independently represented by A-A 4
-A
5
-A
6 -, where: AS = a direct bond, NR' or 0, where R' is H or C1.
3 alkyl; -7-
A
4 = a direct bond, C=O, optionally substituted CI-Co alkylene, or optionally substituted C 6
-C
12 aryl; As = a direct bond, 0, NR"', amide, urethane or urea, where R.' is H or C,.
3 alkyl; and A = a direct bond, 0, optionally substituted C 1
-C
2 0 alkyl, optionally substituted C 2
-C
20 alkenyl or optionally substituted C 7
-C
20 aralkyl. [0022] Examples of organic connecting groups A' and A 2 include -CH(OH)-CH 2 -,
-CH
2 -CH(OH)-, -CH(OH)-CH 2 -0-, -CH 2 -CH(OH)-O-, -CH 2
-CH(OH)-CH
2 -0-, -C(=0)
CH(CO
2 M)-, -C(=O)-CH(CH 2
CO
2 M)- and -C(=0)-CH 2
-CH(CO
2 M)-, where M is H, a metal cation such as Na, an ammonium cation such as tetraalkylammonium or NH 4 , or an organic group such as optionally substituted C,-C 20 alkyl, optionally substituted C 6 -C1 2 aryl, optionally substituted C 7
-C
2 0 aralkyl, or optionally substituted C 2
-C
2 o alkenyl. In a preferred embodiment, at least one of the organic connecting groups A' and A 2 is -CH 2
-CH(OH)-CH
2 0-. [0023] Those skilled in the art will appreciate that hydrophobicity may be incorporated in various ways into the polymer P1. In an embodiment, at least one of the first and second hydrocarbyl radicals T, E and Q is optionally substituted C-C 20 alkyl, optionally substituted C 6
-C,
2 aryl, optionally substituted C 7
-C
20 aralkyl, or optionally substituted C 2
-C
20 alkenyl. For example, in some embodiments, at least one of the first hydrocarbyl radicals T and E is selected from -(CH 2
)
2 - and a hydroxypropylene, e.,g., -CH 2
-CH(OH)-CH
2 -. Q is preferably selected from propyl, butyl, pentyl, hexyl, 2-ethylhexyl, octyl, decyl, C 7
-C
2 0 alkylphenyl (e.g., cresyl, nonylphenyl), cetyl, octenyl, and octadecyl. In some embodiments, Q is selected from butyl, 2-ethylhexyl, phenyl, cresyl, nonylphenyl, cetyl, octenyl, and octadecyl. When A -Q is H, T and E are preferably each independently selected from optionally substituted C 2
-C
8 alkylene, isophorone and hydroxypropylene. [0024] Another embodiment provides a composition comprising a polymeric reaction product of at least a polyamine, a first nitrogen-reactive compound, and a second nitrogen-reactive compound, the polymeric reaction product having a weight average molecular weight of at least about 500, wherein: the first nitrogen-reactive compound comprises a -Si(OR") 3 group and a nitrogen-reactive group, where R = H, optionally substituted C-C 20 alkyl, optionally substituted C 6
-C
12 aryl, optionally substituted C 7
-C
2 o aralkyl, optionally substituted
C
2
-C
20 alkenyl, Group I metal ion, Group H metal ion, or NR' 4 , each R' being -8independently selected from H, optionally substituted Ci-C 20 alkyl, optionally substituted C 6
-CI
2 aryl, optionally substituted C 7
-C
20 aralkyl, and optionally substituted C 2
-C
20 alkenyl; the second nitrogen-reactive compound comprises a nitrogen-reactive group and does not contain a Si(OR )3 group; and at least one of the polyamine and the second nitrogen-reactive compound comprises an optionally substituted hydrocarbyl radical comprising from about 2 to about 40 carbons. [0025] The term "PRP1" may be used herein to refer to such a polymeric reaction product. Various polyamines may be used to make PRPL. For example, in an embodiment, the polyamine comprises a recurring unit of the formula -(CH 2 )r-NR"")-, where r is an integer in the range of I to about 20 and R"" is H, optionally substituted C 1
-C
20 alkyl, optionally substituted C 6
-C
12 aryl, optionally substituted C 7
-C
2 o aralkyl, or optionally substituted C 2 -C2o alkenyl. In another embodiment, the polyamine comprises a (NR 4 2
)-J
(NR 42) moiety, wherein J is an optionally substituted hydrocarbyl fragment comprising from about 2 to about 40 carbons; and each R 4 is independently H, optionally substituted Ci.
8 alkyl, or optionally substituted C6.10 aryl. Preferably, the hydrocarbyl fragment J is optionally substituted C 3
-C
2 o alkyl, optionally substituted C 3
-C
2 0 alkenyl group or optionally substituted
C
3
-C
20 aryl. Preferably, the polyamine is a C 6
-C
20 aliphatic diamine. Examples of suitable polyamines include polyethyleneimine, triethylenetetramine, 1,2-diaminoethane, 1,3 diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,5-diaminohexane, 1,8 diaminooctane, diaminoisophorone, aminoaniline, and aminomethylbenzylamine. [00261 Various Si-containing nitrogen-reactive compounds may be used to make PRP1. Suitable Si-containing nitrogen-reactive compounds comprise a nitrogen-reactive group, e.g., containing suitably configured halide, sulfate, epoxide, isocyanates, anhydride, carboxylic acid, and/or acid chloride functionalities. Examples of suitable nitrogen-reactive groups include alkyl halide (e.g., chloropropyl, bromoethyl, chloromethyl, and bromoundecyl) epoxy (e.g., glycidoxypropyl, 1,2-epoxyamyl, 1,2-epoxydecyl or 3,4-epoxycyclohexylethyl), isocyanate (e.g., isocyanatopropyl or isocyanatomethyl that react to form a urea linkage), anhydride (e.g., malonic anhydride, succinic anhydride) and combinations of such groups, e.g., a combination of a hydroxyl group and a halide, such as 3-chloro-2-hydroxypropyl. Triethoxysilylpropylsuccinic anhydride, glycidoxypropyl trimethoxysilane and chloropropyl trimethoxysilane are examples a nitrogen-reactive compounds that comprise a -Si(OR )3 -9group and a nitrogen-reactive group. A variety of such compounds are known to those skilled in the art, see, e.g., U.S. Patent No. 6,814,873, which is hereby incorporated by reference and particularly for the purpose of describing such compounds and methods of incorporating them into polymers. [0027] Various nitrogen-reactive compounds that comprise a nitrogen-reactive group and that do not contain a Si(OR )3 group may be used to make PRP1. Suitable nitrogen-reactive compounds include those containing one or more of the nitrogen-reactive groups mentioned above. Non-limiting examples of nitrogen-reactive compounds that comprise a nitrogen-reactive group and that do not contain a Si(OR )3 group include C,-C 2 0 alkyl halides (e.g., chlorides, bromides, and iodides of alkyls such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl), alkenyl halides such as allyl chloride, aralkyl halides such as benzyl chloride, alkyl sulfates such as dimethyl sulfate, compounds containing at least one epoxide group (e.g., glycidyl alcohols, phenols, and amines), and compounds containing an anhydride group e.g., alkenyl malonic anydrides and/or alkenyl succinic anhydrides. Examples of preferred second nitrogen-reactive compounds include dimethylsulfate, chlorooctane, chlorohexane, benzyl chloride, epichlorohydrin, glycidyl 4-nonylphenylether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, C1 2 -C1 4 alkyl glycidyl ether, cresyl glycidyl ether, octenylsuccinic anhydride and octadecenylsuccinic anhydride. In some embodiments, the second nitrogen-reactive compound (comprising a nitrogen-reactive group and not containing a Si(OR") 3 group) comprises at least two nitrogen-reactive functionalities, which may be the same or different from one another. [0028] A composition that comprises PRPI may comprise the polymer Pl. For example, in an embodiment, PRP1 comprises a recurring unit of the formula (I) and a recurring unit of the formula (H), wherein T, E, Q, A', A2 and R" have the same meanings as set forth above. It will be understood that the first, second, third, fourth and fifth provisos described above with respect to the polymer P1, each alone or together in any combination, may apply in the context of a PRP1 that comprises the polymer P1. [0029] The polymers and compositions described herein can be made in various ways. For example, PRP1 and the polymer P1 may be prepared by reacting together under suitable conditions, in any order, a polyamine, a first nitrogen-reactive compound, and a second nitrogen-reactive compound, as those materials are described above. It will be understood that each of the polyamine, the first nitrogen-reactive compound, and the second nitrogen-reactive compound may comprise a mixture of particular compounds. Those skilled -10in the art can identify suitable reaction conditions and prepare a wide variety of polymers and compositions (e.g., PRPI and the polymer Pl), using routine experimentation informed by the guidance provided herein. [0030] In a first embodiment of a method of making PRPI and the polymer P1, a backbone polyamine (e.g., polyethylencimine), typically having a relatively higher molecular weight (as compared to the polyfunctional amine monomer described below), is functionalized by reacting with the first nitrogen-reactive compound (to thereby incorporate Si(OR") 3 groups), and the second nitrogen-reactive compound (to thereby incorporate or increase hydrophobicity). In many cases, the overall length of the backbone polyamine is not increased, although the molecular weight of the polyamine is increased by the attachment of the Si-containing group and the non-Si-containing hydrophobic group. Molecular weight may also be increased by crosslinking. In many cases the reaction is not a polymerization per se, but is instead a polymer functionalization (with possible crosslinking). The product of such a reaction (which may be PRPI or P1) may be referred to herein as a silanized hydrophobically modified polyamine. Examples 1-6 below illustrate methods for making polymers in accordance with this first embodiment. [0031] In a second embodiment of a method of making PRPI and the polymer P1, a relatively low molecular weight polyamine monomer or oligomer (e.g., a polyfunctional amine monomer such a triethylenetetramine) is reacted with the first nitrogen-reactive compound and the second nitrogen-reactive compound. In this second embodiment, at least one of the first nitrogen-reactive compound and the second nitrogen-reactive compound comprises at least two nitrogen-reactive functionalities, and the overall formation of the resulting polymer may be considered to involve a condensation polymerization between the polyamine and the first/and or second nitrogen-reactive compound(s), along with possible crosslinking. Examples 7-15 below illustrate methods for making polymers in accordance with this second embodiment. Methods of Treating Scale [0032] The polymers and compositions described herein (e.g., PRPI and the polymer P1, including all of the embodiments described herein) are useful for treating scale (e.g., aluminosilicate scale) in various industrial process streams, e.g., Bayer process streams, boiler water, nuclear waste process streams, a papermaking process streams. Methods for treating scale may be carried out by intermixing the polymer with the process stream in an -11amount effective to reduce or eliminate scale. In preferred embodiments, such methods unexpectedly provide significant improvements in scale reduction. An embodiment provides a method for reducing or eliminating scale in an industrial process, comprising adding a polymer and/or composition as described herein to the process, preferably in an amount effective to reduce or eliminate scale. Typically the amount of polymer and/or composition that is effective to reduce or eliminate scale (e.g., aluminosilicate scale) in the process stream is in the range of about 1 ppm to about 500 ppm, by weight based on the process stream, although in some cases smaller or larger amounts may be effective. Those skilled in the art can identify effective amounts of polymer and/or composition for a particular process steam, using routine experimentation informed by the guidance provided herein. [0033] In preferred embodiments, the polymers and/or compositions are particularly useful for treating aluminosilicate scale in difficult-to-treat industrial process streams, such as in the Bayer alumina process, nuclear waste streams and kraft paper mill effluent streams. An embodiment provides a method for treating scale in a difficult-to-treat process stream, comprising intermixing a polymer with a process stream in an amount effective to reduce or eliminate aluminosilicate scale in the process stream. Those skilled in the art are familiar with difficult-to-treat process streams, which may have any or more, in any combination, of the following characteristics: a sulfate level of at least about 1 g/L, a finely dispersed iron oxide level of at least about 20 mg/L, a finely dispersed sodalite level of at least about 20 mg/L, and/or a combined nitrate/nitrite concentration of at least about 0.5 molar. EXAMPLES [0034] Test Procedure A: A difficult-to-treat liquor is prepared and used to test the polymers described in the Examples below. The difficult-to-treat liquor is made by adding 12 ml of a sodium silicate solution (27.7 g/L of a sodium silicate solution which is 28.9% SiO 2 ) to 108 ml of a sodium aluminate solution that contains sodium aluminate, excess sodium hydroxide, sodium carbonate, and sodium sulfate. After mixing, the solution contains 0.8 g/L SiO 2 , 45 g/L A1 2 0 3 , 150 g/L NaOH, 60 g/L Na 2
CO
3 , and 20 g/L Na 2
SO
4 . Aliquots of this solution are placed into 125 ml polyethylene bottles. A polymer described in the Examples below is also added to the bottle (generally the polymer is added in the form of a solution containing 0.1-10% of active reagent); blank (control) samples are also prepared without the polymer. The sealed bottles are heated with agitation at 100"C for 18 + 2 hours. -12- At the end of the 18 hours, the bottles are opened and the solution is filtered. With no polymer additive to the system (blank tests), considerable aluminosilicate is formed and is recovered on the filter paper. The total aluminosilicate precipitated in the blank tests is typically about 200 mg. In the Examples below, the amount of aluminosilicate precipitated is a measure of antiscalant activity and is expressed as a percentage of the aluminosilicate that formed in the corresponding blank experiments that were part of the same set of tests. Results obtained using comparative polymers are indicated by a "" in the Tables below. [0035] This difficult-to-treat liquor contains relatively high levels of sulfate and carbonate and is considered more difficult to treat than the liquor described in U.S. Patent No. 6,814,873, and thus represents a particularly difficult-to-treat Bayer liquor. Only about 150 mg of precipitate is formed in the blank tests with the liquor described in U.S. Patent No. 6,814,873, whereas a larger amount (typically about 200 mg) of precipitate forms in the blank tests with the difficult-to-treat liquor used to test the polymers described in the Examples below. [0036] Test Procedure B: This procedure is conducted in the same manner as Test Procedure A except that 150 mg/L of "red mud" solids are added to the test liquor. These red mud solids are obtaining by washing, drying and grinding actual red mud waste obtained from a Bayer alumina plant. [0037] Test Procedure C: This procedure is conducted in the same manner as Test Procedure A except that 50 mg/L of sodalite solids are added to the test liquor and the test is run for only four hours instead of 18. The sodalite solids are made by reacting kaolin with sodium hydroxide. EXAMPLE 1 [0038] Product A (comparative) is made as follows: 10.00 g of polyethyleneimine (Lupasol WF from BASF) is mixed with about 2.19 g of glycidoxypropyl trimethoxysilane (4 mole % based on the PEI recurring unit weight). The mixture is heated at 750 C for 16 hours to give a polymeric reaction product. Aqueous NaOH solution (20 g/L) is then added to hydrolyze the methoxysilane groups to -Si-ONa groups to make a 10% solution of the sodium salt. [0039] Product B1 (hydrophobically modified) is made in a similar fashion as follows: 10.00 g of polyethyleneimine (Lupasol WF from BASF) is mixed with 2.19 g glycidoxypropyltrimethoxysilane (4 mole % based on the PEI recurring unit weight) and 0.71 -13g chlorooctane (2 mole % based on the PEI recurring unit weight). The mixture is heated at 750 C for 16 hours to give a polymeric reaction product. Aqueous NaO-l solution (20 g/L) is then added to make a 10% solution of the sodium salt. [0040] Product B2 (hydrophobically modified) is made as follows: 8.66 g of polyethyleneimine (Lupasol WF from BASF) is mixed with 1.90 g glycidoxypropyltrimethoxysilane (4 mole % based on the PEI recurring unit weight) and 1.34 benzyl chloride (5.26 mole % based on the PEI recurring unit weight). The mixture is heated at 75* C for 16 hours to give a polymeric reaction product. Aqueous NaOH solution (20 g/L) is then added to make a 10% solution of the sodium salt. [0041] Tests comparing Products A, B1 and B2 (Table 1) in accordance with Test Procedure A show that the relatively more hydrophobic Products B 1 and B2 give significantly better reduction in the amount of sodalite precipitated. TABLE 1: % Sodalite Precipitated No. Product Dose 5 ppm 3 ppm IA* A 19 35 1B BI 0.4 4.1 IC* A 12 ID B2 2.0 EXAMPLE 2 [0042] Product C (hydrophobically modified) is made as follows: 10.00 g of polyethyleneimine (Lupasol WF made by BASF) is mixed with 2.19 g glycidoxypropyltrimethoxysilane (4 mole % based on the PEI recurring unit weight) and 0.64 g glycidyl 4-nonylphenylether (1 mole % based on the PEI recurring unit weight). The mixture is heated at 750 C for 16 hours to give a polymeric reaction product. Aqueous NaOH solution (20 g/L) is then added to make a 10% solution of the sodium salt. [0043] Tests comparing Products A and C (Table 2) in accordance with Test Procedure A show that the relatively more hydrophobic Product C gives significantly better reduction in the amount of sodalite precipitated. TABLE 2: % Sodalite Precipitated -14- No. Product Dose 5 ppm 3 ppm 2A* A 12 32 2B C 0 4.9 EXAMPLE 3 [00441 Product D (comparative) is made as follows: 5.00 g of polyethyleneimine (Lupasol PR 8515 from BASF) is mixed with about 1.1 g of glycidoxypropyl trimethoxysilane (4 mole % based on the PEI recurring unit weight). The mixture is kept at room temperature for 16 hours, then heated at 750 C for 4 hours to give a polymeric reaction product. Aqueous NaOH solution (20 g/L) is then added to hydrolyze the methoxysilane groups to -Si-ONa groups to make a 10% solution of the sodium salt. [0045] Product E (hydrophobically modified) is made as follows: 5.00 g of polyethyleneimine (Lupasol PR 8515 from BASF) is mixed with 1.10 g glycidoxypropyltrimethoxysilane (4 mole % based on the PEI recurring unit weight) and 0.64 g glycidyl 4-nonylphenylether (1 mole % based on the PEI recurring unit weight). The mixture is kept at room temperature for 16 hours, then heated at 75" C for 4 hours to give a polymeric reaction product. Aqueous NaOH solution (20 g/L) is then added to make a 10% solution of the sodium salt. [0046] Products F and G are made in a similar fashion to Product E, except that 1.61 g glycidyl 4-nonylphenylether (5 mole % based on the PEI recurring unit weight) is used to make Product F, and 3.21 g glycidyl 4-nonylphenylether (10 mole % based on the PEI recurring unit weight) is used to make product G, instead of the amount of glycidyl 4 nonylphenylether used to make Product E. [0047] Tests comparing Products D, E, F and G (Table 3) in accordance with Test Procedum A show that the relatively more hydrophobic Products E, F and G give significantly better reduction in the amount of sodalite precipitated. TABLE 3: % Sodalite Precipitated No. Product Dose 20 ppm 10 pm 5 ppm 3 ppm 3A* D 96 100 3B E 0.1 1.3 20 54 3C F 0 0.2 1.1 9.3 -15- 3D G 0 0 25 24 EXAMPLE 4 [0048] Product H (comparative) is made as follows: 5.00 g of polyethyleneimine (Lupasol PR 8515 from BASF) is mixed with about 0.92 g of chloropropyl trimethoxysilane (4 mole % based on the PEI recurring unit weight). The mixture is kept at room temperature for 16 hours, then heated at 750 C for 4 hours to give a polymeric reaction product. Aqueous NaOH solution (20 g/L) is then added to hydrolyze the methoxysilane groups to -Si-ONa groups to make a 10% solution of the sodium salt. [0049] Product I (hydrophobically modified) is made as follows: 5.00 g of polyethyleneimine (Lupasol PR 8515 from BASF) is mixed with 0.92 g of chloropropyl trimethoxysilane (4 mole % based on the PEI recurring unit weight) and 1.46 g dimethylsulfate (10 mole % based on the PEI recurring unit weight). The mixture is kept at room temperature for 16 hours, then heated at 750 C for 4 hours to give a polymeric reaction product. Aqueous NaOH solution (20 g/L) is then added to make a 10% solution of the sodium salt. [0050] Tests comparing Products H and I (Table 4) in accordance with Test Procedure A show that the relatively more hydrophobic Product I gives significantly better reduction in the amount of sodalite precipitated. TABLE 4: % Sodalite Precipitated No. Product Dose 100 ppm 300 ppm 4A* H 80 7.9 4B I 4.3 0 EXAMPLE 5 [0051] Product J (comparative) is made as follows: 5.00 g of polyethyleneimine (Lupasol PR 8515 from BASF) is mixed with about 1.65 g of glycidoxypropyl trimethoxysilane (6 mole % based on the PEI recurring unit weight). The mixture is kept at room temperature for 16 hours, then heated at 750 C for 4 hours to give a polymeric reaction product. Aqueous NaOH solution (20 g/L) is then added to hydrolyze the methoxysilane groups to -Si-ONa groups to make a 10% solution of the sodium salt. -16- [0052] Products K-R (hydrophobically modified) are made as follows: 5.00 g of polyethyleneimine (Lupasol PR 8515 from BASF) is mixed with about 1.65 g of glycidoxypropyl trimethoxysilane (6 mole % based on the PEI recurring unit weight) and the amount of a second nitrogen-reactive compound (5 mole % based on the PEI recurring unit weight) shown in Table 5. The mixtures are kept at room temperature for 16 hours, then heated at 750 C for 4 hours to give polymeric reaction products. Aqueous NaOH solution (20 g/L) is then added to hydrolyze the methoxysilane groups to -Si-ONa groups to make a 10% solution of the sodium salt. [0053] Tests comparing Products J-R (Table 5) in accordance with Test Procedure A show that the relatively more hydrophobic Products K-R give significantly better reduction in the amount of sodalite precipitated. TABLE 5: % Sodalite Precipitated No. Product Second Nitrogen-Reactive Compound Dose (5 ppm) 5A* J None 100 5B K 4-nonylphenyl glycidyl ether 0.5 5C L butyl glycidyl ether 83 5D M 2-ethylhexyl glycidyl ether 1.1 5E N phenyl glycidyl ether 70 5F 0 C 12
-C
14 alkylglycidyl ether 8.4 5G P cresyl glycidyl ether 23 5H Q octenylsuccinic anhydride 6.5 51 R octadecenylsuccinic anhydride 86 EXAMPLE 6 [0054] Product S (comparative) is made as follows: 10.00 g of polyethyleneimine (Lupasol WF from BASF) is mixed with about 1.1 g of glycidoxypropyl trimethoxysilane (2 mole % based on the PEI recurring unit weight). The mixture is heated at 75* C for 5 hours to give a polymeric reaction product. Aqueous NaOH solution (20 g/L) is then added to hydrolyze the methoxysilane groups to -Si-ONa groups to make a 10% solution of the sodium salt. [0055] Product T (hydrophobically modified) is made as follows: 10.00 g of polyethyleneimine (Lupasol WF from BASF) is mixed with 1.10 g glycidoxypropyltrimethoxysilane (2 mole % based on the PEI recurring unit weight) and -17- 0.064 g glycidyl 4-nonylphenylether (0.1 mole % based on the PEI recurring unit weight). The mixture is heated at 750 C for 5 hours to give a polymeric reaction product. Aqueous NaOH solution (20 g/L) is then added to make a 10% solution of the sodium salt. [0056] Products U and V are made in a similar fashion to Product T, except that 0.128 g glycidyl 4-nonylphenylether (0.2 mole % based on the PEI recurring unit weight) is used to make Product U, and 0.32 g glycidyl 4-nonylphenylether (0.5 mole % based on the PEI recurring unit weight) is used to make product V, instead of the amount of glycidyl 4 nonylphenylether used to make Product T. [0057] Tests comparing Products S, T, U and V (Table 6) in accordance with Test Procedure A show that the relatively more hydrophobic Products E, F and G give significantly better reduction in the amount of sodalite precipitated, and that products containing relatively low levels of nonylphenyl (NP) provide improved performance. TABLE 6: % Sodalite Precipitated No. Product Dose (% NP) 10 ppm 5 ppm 3 ppm 6A* S (0) 5.0 22.6 43.5 6B T (0.1) 0.2 15.0 26.8 6C U (0.2) 0 12.7 25.4 6D V (0.5) 0 6.6 20.7 EXAMPLES 7-15 [0058] 20.0 g of triethylenetetramine (TETA) is dissolved in a mixture of 50 ml of deionized water and 2.0 g of 50% sodium hydroxide. While stirring, 7.8 g of glycidyloxypropyltrimethoxysilane is added dropwise and the resulting mixture stirred for one hour. Then 10.1 gm of epichlorohydrin (Epi) is added dropwise. The temperature is held below 30*C by cooling in an ice bath. After completion of an exotherm, 14.6 gm of 50% sodium hydroxide is added dropwise, with cooling to hold the temperature below 30C to give a polymeric reaction product (Example 7). [0059] The polymer products of Examples 8-15 are prepared in a similar manner, except: In Examples 8-11 and 13, about a third (on molar basis) of the triethylenetetramine is replaced with 1,8-diaminooctane (Example 8), diaminoisophorone (Example 9), 1,2 diaminoethane (Example 10), 1,3-diaminopropane (Example 11) or 1,6-diaminohexane (Example 13); in Example 12, 20.0 gm of triethylenetetramine is first reacted with 0.2 mole -18- (based on TETA and Epi) of glycidylnonylphenol (GNP) for 5 hrs at 80*C before being reacted with the epichlorohydrin, sodium hydroxide and glycidyloxypropyltrimethoxysilane; and in Examples 14 and 15, the TETA is replaced with N,N'-bis(3 aminopropyl)ethylenediamine (BAPED) and N,N'-bis(3-aminopropyl)-1,3-propanediamine (BAPPD), respectively. The compositions of the resulting polymers are shown in Table 7A. The "mole %" values are expressed as percentages of total polymer backbone monomer (sum of all amines and epichlorohydrin). TABLE 7A: Polymer compositions Oflimeric Moes Molet Moe. Mole.% Mole Totalpolymer Moles Moles M Eua le anine Diamine Ta rmilne To amine Diamin Diamin Mole E.JEL badcbonemoles GNP smlane silane 7 TETA None 1 55.56 0.00 0.80 44.44 1.80 0.24 13.33 8 TETA 1.8-4amnooctane 0.7 33.33 0.60 28.57 0.80 3810 2.10 0.24 11.43 9 TETA diamni' me 0.7 33.33 0.60 2857 0.80 38.10 210 0.24 11.43 10 TETA 1.2-diamboethane 0.7 33.33 0.60 28.57 080 38.10 2.10 0.24 11.43 11 TETA 13-diamin e 0.7 33.33 0.60 28.57 0.80 38.10 2.10 0.24 11.43 12 TETA nune 1 58.56 080 0.80 44.44 1.80 0.20 0.24 13.33 13 TETA 164aminoOexame 0.7 3333 0.60 2857 0.80 38.10 2.10 024 11.43 14 BAPED none 1 55.56 0.00 0.80 44.44 1.80 0.24 13.33 15 BAPPD none 1 55.56 0.00 0.80 44.44 1.80 0.24 13.33 TETA - tIthylenetetramine BAPED-NX.-Bsp-amInOPrll etlenedimne 8APPiD-N,N-Bis(3--p andiamilne EpiEpcao Exarpe 12 was prepared with 0 2 moles GMP [0060] The polymers of Examples 7-15 comprise a recurring unit of the formula (I) and a recurring unit of the formula (II) in which E is -CH 2
CH(OH)CH
2 -, A' is
CH
2
CH(OH)CH
2 -0-CH 2
CH
2
CH
2 -, R" is Na, and in which A2, T and Q are shown in Table 7B below. TABLE 7B: Polymer compositions Ex. A 2 T Q 7 none -(CH 2
)
2 - H 8 none -(CH 2
)
8 - + -(CH 2
)
2 - H 9 none Isophorone 5-(1,3,3- H trimethylcyclohexylmethyl) + (CH 2
)
2 10 none -(CH 2
)
2 - H 11 none -(CH 2
)
3 - + -(CH 2
)
2 - H 12 -CH 2
CH(OH)CH
2 -0- -(CH 2
)
2 - nonylphenyl 13 none -(CH 2
)
6 - + -(CH 2
)
2 - H 14 none -(CH 2
)
3 - + -(CH 2
)
2 - H 15 none -(CH 2
)
3 - H -19- EXAMPLES 16A-N [0061] Tests comparing the polymer products of Examples 7-15 in accordance with Test Procedure A show (Table 8) that the relatively more hydrophobic of Examples 7-15 generally give better reduction in the amount of sodalite precipitated. For these tests, the blank contains no polymer. TABLE 8: % Sodalite Precipitated Ex. Product Dose 10ppm 20ppm ppm 300ppm 16A Example 7 98 96 96 87 16B Example 8 31 2 4 16C Example 9 80 46 31 16D Example 7 98 98 16E Example 10 98 97 92 16F Example 11 99 100 97 16G Example 8 8 1 16H Example 9 58 5 161 Example 12 66 60 16J Example 7 99 98 16K Example 8 11 1 16L Example 13 91 52 16M Example 14 24 1 16N Example 15 2 0 EXAMPLES 17-30 [0062] A difficult-to-treat synthetic liquor (representative of a high level nuclear waste stream) is prepared by dissolving the appropriate salts in water to provide the composition shown in Table 9. TABLE 9 Liquor component Molarity OH 1.60 Al 0.50 Si 0.0156 N0 3 1.94 N0 2 1.37 C0 3 0.31 C204 0.00345 -20- PO3 0.016 K 0.0090 Cl 0.010
SO
4 0.028 [0063] A series of hydrophobically modified polyethylenei mines are prepared in a manner similar to that described for Product B1 in Example I above, except that butyl chloride (Hydrophobe type: B), hexyl chloride (Hydrophobe type: H), or 4-nonylphenyl glycidyl ether (Hydrophobe type: GNP) are used in place of chlorooctane. Tests are conducted comparing the performance of the resulting polymer products to one another, using the difficult-to-treat synthetic liquor described in Table 9, in accordance with the test method described above. The results shown in Table 10 illustrate the utility of these polymer products for reducing the amount of sodalite precipitated in this difficult-to-treat synthetic liquor. In Table 10, the Scale % is reported as a percentage of the blank in which no scale inhibitor was used. TABLE 10 Example Silane PEI MW Hydrophobe Dose Scale % vs content type and mole mg/L Blank mole % % 17 4 25 k B (5%) 300 9 18 4 25 k B (11%) 300 10 19 4 25 k B (18%) 300 10 20 4 25 k B (25%) 300 14 21 4 25 k H (5%) 300 7 22 4 25 k H (11%) 300 9 23 4 25 k H (18%) 300 11 24 4 25 k H (25%) 300 12 25* 4 1.2k None 300 99 26 4 1.2 k GNP (2%) 300 100 27 4 1.2 k GNP (5%) 300 80 28 4 1.2 k GNP (10%) 300 4 29 4 1.2 k GNP (15%) 300 2 30 4 25k GNP(8%) 300 25 EXAMPLES 31-34 [0064] Polymer #1 is made in the same manner as Product C in Example 2, except that twice as much glycidyl 4-nonylphenyl ether (2 mole % based on the PEI unit weight) is used. -21- [0065] Polymer #2 is made in the same manner as Product C in Example 2, except that glycidyl 2-ethylhexyl ether (2 mole % based on the PEI unit weight) is used instead of glycidyl 4-nonylphenyl ether. [0066] Polymer #3 is made in the same manner as Product C in Example 2, except that glycidyl octyl/decyl ether (2 mole % based on the PEI unit weight) is used instead of glycidyl 4-nonylphenyl ether. [0067] Tests comparing Products #1, #2 and #3 with Product A are conducted in accordance with Test Procedures A and C (Table 11). The results show that the relatively more hydrophobic polymers of Examples 31-33 provide significantly better reductions in scale than the less hydrophobic Product A for both of the difficult-to-treat liquors. TABLE 11: % Sodalite Precipitated No. Product Test Procedure A B (5 ppm dose) (5 ppm dose) 31* A 20 46 32 Polymer #1 0 3.8 33 Polymer #2 0 0.1 34 Polymer #3 0.6 11.6 EXAMPLES 35-52 [0068] The products shown in Tables 12 and 13 below are made with the same PEI and in the same manner as Product F in Example 3, except the nonylphenyl group is replaced with octyl/decyl (10 mole % vs. PE) or 2-ethylhexyl (5 mole % vs. PEI), and the mole % of glycidoxypropyltrimethoxysilane vs. the PEI is varied as shown. The results of tests conducted on these polymers in accordance with Test Procedures A, B and C show that the relatively more hydrophobic polymers generally provide significantly better reductions in scale than the control polymers for all three of the difficult-to-treat liquors. -22- Table 8 % sodalite formed vs. blank (no reagent added) Test Procedure A Test Procedure C
----------------------------------------
Hydrophobic group (silane) 4 ppm 10 2pm 5 Ppm 10 ppm Product D none (4% silane) 100 Product #4 10% octyl/decyl (4% silane) 0 4.7 3.3 Product #5 10% octyl/decyl (5% silane) 0 3.1 1.7 Product #6 10% octyl/decyl (6% silane) 0 2.0 1.8 Product #7 10% octyl/decyl (8% silane) 0 2.3 0.4 Product F 5% nonylphenyl (4% silane) 0 8.2 0.2 Product K 5% nonylphenyl (6% silane) 1.8 8.0 0.7 Product #8 5% 2-ethylhexyl (4% silane) 2.3 10.7 3.5 Product M 5% 2-ethylhexyl (6% silane) 0.6 4.2 0.9 Product #9 5% 2-ethylhexyl (8% silane) 4.0 5.9 1.1 -23- Table 9 % sodalite formed vs. blank (no reagent added) Test Procedure A Test Procedure B --------------- --------- - --------- ------- Hydrophobic group (silane) 4 ppm 10 ppm 5 ppm 10 ppm Product D none (4% silane) 100 Product #4 10% octyl/decyl (4% silane) 0 4.7 (7.2) Product #5 10% octyl/decyl (5% silane) 0 6.4 1.2 Product #6 10% octyl/decyl (6% silane) 0 5.7 0 Product #7 10% octyl/decyl (8% silane) 0 0 0 Product K 5% nonylphenyl (6% silane) 1.8 0 0 Product M 5% 2-ethylhexyl (6% silane) 0.6 1.3 0 Product #9 5% 2-ethylhexyl (8% silane) 4.0 5.9 1.1 EXAMPLES 53-104 [0069] Polymer products are made and tested as described in Examples 1-52 above, except that potassium salts of the polymers are made by hydrolyzing with potassium hydroxide in place of sodium hydroxide. Similar results are achieved. EXAMPLES 105-156 [0070] Polymer products are made and tested as described in Examples 1-52 above, except that potassium salts of the polymers are made by hydrolyzing with ammonium hydroxide in place of sodium hydroxide. Similar results are achieved. [00711 It will be appreciated by those skilled in the art that various modifications and changes can be made without departing from the scope of the embodiments disclosed herein. Such modifications and changes are intended to fall within the scope of the embodiments disclosed herein, as defined by the appended claims. -24-
Claims (19)
1. A method for reducing or eliminating scale in an industrial process, comprising adding a composition comprising a polymeric reaction product of at least a polyamine, a first nitrogen-reactive compound, and a second nitrogen-reactive compound, 5 the polymeric reaction product having a weight average molecular weight of at least about 500, wherein: the first nitrogen-reactive compound comprises a -Si(OR ) 3 group and a nitrogen-reactive group, wherein R = H, optionally substituted CI-C 20 alkyl, optionally substituted C 6 -C 12 aryl, optionally substituted C 7 -C 2 0 aralkyl, optionally substituted C 2 10 C 20 alkenyl, Group I metal ion, Group II metal ion, or NR1 4 , each R' being independently selected from H, optionally substituted Ci-C 20 alkyl, optionally substituted C 6 -C 12 aryl, optionally substituted C 7 -C 2 0 aralkyl, and optionally substituted C 2 -C 20 alkenyl; the second nitrogen-reactive compound comprises a nitrogen-reactive group and does not contain a Si(OR )3 group; and is at least one of the polyamine and the second nitrogen-reactive compound comprises an optionally substituted hydrocarbyl radical comprising from about 2 to about 40 carbons, to the process.
2. The method according to claim I wherein the polyamine comprises a recurring unit of the formula -((CH 2 )r-NR."")-, where r is an integer in the range of 1 to 20 about 20 and R"" is H, optionally substituted CI-C 2 0 alkyl, optionally substituted C 6 -C 1 2 aryl, optionally substituted C7-C 2 0 aralkyl, or optionally substituted C 2 -C 2 0 alkenyl.
3. The method of claim I or claim 2, wherein the polymeric reaction product comprises a recurring unit of the formula (I) and a recurring unit of the formula (II): T-N- tE-N Al A2 | 1 Si(OR") 3 Q 25() (II) wherein T and E are each independently a first optionally substituted hydrocarbyl radical comprising from about 2 to about 40 carbons; Q = a second optionally substituted hydrocarbyl radical comprising from about I to 30 about 20 carbons; A] and A2 are each independently a direct bond or an organic connecting group comprising from about I to about 20 carbons; and 26 R" = H, optionally substituted C 1 -C 2 0 alkyl, optionally substituted C 6 -CI 2 aryl, optionally substituted C 7 -C 20 aralkyl, optionally substituted C 2 -C 2 0 alkenyl, Group I metal ion, Group II metal ion, or NR' 4 , where each R' is independently selected from H, optionally substituted C,-C 2 0 alkyl, optionally substituted C 6 -CI 2 aryl, optionally 5 substituted C 7 -C 2 0 aralkyl, and optionally substituted C 2 -C 2 0 alkenyl.
4. The method of claim 3, wherein the polymeric reaction product further comprises a -((CH 2 )n-NH)- recurring unit, wherein n is an integar in the range of about 2 to about 10.
5. The method of claim 3 or 4, wherein the organic connecting groups A' and A2 10 are each independently represented by -A 3 4 -A-A 6 -, where: A3 = a direct bond, NR' or 0, where R' is H or C,. 3 alkyl; A = a direct bond, C=0, optionally substituted Ci-CIO alkylene, or optionally substituted C 6 -CI 2 aryl; A5 = a direct bond, 0, NR"', amide, urethane or urea, where R"' is H or CI. 3 is alkyl; and 6 A = a direct bond, 0, optionally substituted C 1 -C 20 alkyl, optionally substituted C 2 -C 20 alkenyl or optionally substituted C 7 -C 2 0 aralkyl.
6. The method of any one of claims 3 to 5, wherein at least one of the organic connecting groups Al and A2 is selected from -CH(OH)-CH 2 -, -CH 2 -CH(OH)-, 20 CH(OH)-CH 2 -0-, -CH 2 -CH(OH)-O-, -CH 2 -CH(OH)-CH 2 -0-, -C(=0)-CH(CO 2 M)-, C(=O)-CH(CH 2 CO 2 M)- and -C(=0)-CH 2 -CH(CO 2 M)-, where M is selected from H, a metal cation, an ammonium cation, optionally substituted Ci-C 20 alkyl, optionally substituted C 6 -C 12 aryl, optionally substituted C
7 -C 2 0 aralkyl, and optionally substituted C 2 -C 2 0 alkenyl. 25 7. The method of claim 6, wherein at least one of the organic connecting groups Al and A 2 is -CH 2 -CH(OH)-CH 2 -0-.
8. The method of any one of claims 3 to 7, wherein at least one of the first and second hydrocarbyl radicals T, E and Q is optionally substituted Ci-C 20 alkyl, optionally substituted C 6 -C, 2 aryl, optionally substituted C 7 -C 2 0 aralkyl, or optionally substituted C 2 30 C 2 0 alkenyl.
9. The method of any one of claims 3 to 8, wherein at least one of the first hydrocarbyl radicals T and E is selected from -(CH 2 ) 2 - and -CH 2 -CH(OH)-CH 2 -.
10. The method of any one of claims 3 to 9, wherein the polymeric reaction product comprises at least about I mole percent of recurring units for the formula (I) and 27 at least about 1 mole percent of recurring units of the formula (II), based on total moles of recurring units in the polymer.
11. The method of any one of claims 3 to 10, wherein Q is selected from butyl, 2 ethylhexyl, phenyl, cresyl, nonylphenyl, cetyl, octenyl, and octadecyl. 5
12. The method of claim 11, wherein at least one of the organic connecting groups AI and A2 is -CH 2 -CH(OH)-CH 2 -0-.
13. The method of any one of claims 1 to 12, wherein R" = Group I metal ion, Group II metal ion, or NR1 4 .
14. The method of claim 1, wherein: 10 the polyamine comprises a (NR 4 2 )-J-(NR 4 2 ) moiety; J is an optionally substituted hydrocarbyl fragment comprising from about 2 to about 40 carbons; and each R 4 is independently H, optionally substituted C 1 . 8 alkyl, or optionally substituted C 6 - 10 aryl. is
15. The method of claim 14, wherein the second nitrogen-reactive compound comprises at least two nitrogen-reactive moieties.
16. The method of claim 1, wherein: the polyamine is selected from polyethyleneimine, thriethylenetetramine, 1,2 diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane; 1,5-diaminopentane, 1,5 20 diaminohexane, 1,8-diaminooctane and diaminoisophorone; the first nitrogen-reactive compound is selected from glycidoxypropyl trimethoxysilane and chloropropyl trimethoxysilane; and the second nitrogen-reactive compound is selected from dimethylsulfate, chlorooctane, chlorohexane, benzyl chloride, epichlorohydrin, glycidyl 4 25 nonylphenylether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, C 12 -Ci 4 alkyl glycidyl ether, cresyl glycidyl ether, octenylsuccinic anhydride and octadecenylsuccinic anhydride.
17. The method of any one of claims I to 16, wherein the process stream comprises at least one selected from a sulphate 30 level of at least about 1 g/L, a finely dispersed iron oxide level of at least about 20 mg/L, a finely dispersed sodalite level of at least about 20 mg/L, and a combined nitrate/nitrite concentration of at least about 0.5 molar.
18. The method of any one of claims 1 to 17, wherein the process stream is a Bayer process stream. 28
19. The method of any one of claims I to 18, wherein the amount of polymer that is effective to reduce or eliminate aluminosilicate scale in the process stream is in the range of about 1 ppm to about 500 ppm, by weight based on the process stream. s Dated 6 November 2012 Cytec Technology Corp Patent Attorneys for the Applicant/Nominated Person SPRUSON & FERGUSON
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| AU2011226768A AU2011226768B2 (en) | 2006-10-13 | 2011-09-20 | Hydrophobically modified polyamine scale inhibitors |
| AU2012241116A AU2012241116B2 (en) | 2006-10-13 | 2012-10-15 | Hydrophobically modified polyamine scale inhibitors |
| AU2013201421A AU2013201421B2 (en) | 2006-10-13 | 2013-03-12 | Hydrophobically modified polyamine scale inhibitors |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5415782A (en) * | 1993-11-22 | 1995-05-16 | Nalco Chemical Company | Method for the alteration of siliceous materials from bayer process liquors |
| WO1996033953A1 (en) * | 1995-04-26 | 1996-10-31 | Albright & Wilson Uk Limited | Stain corrosion and scale inhibitors |
| EP0990671A1 (en) * | 1998-09-30 | 2000-04-05 | Dow Corning Toray Silicone Company, Ltd. | Gas barrier composition and molded resin |
| US20060124553A1 (en) * | 2002-07-22 | 2006-06-15 | Taylor Matthew L | Method of preventing or reducing aluminosilicate scale in high level nuclear wastes |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6541088B1 (en) * | 2000-03-03 | 2003-04-01 | Eg Technology Partners, L.P. | Alkylenimine/organic barrier coatings having bis-silane additives |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5415782A (en) * | 1993-11-22 | 1995-05-16 | Nalco Chemical Company | Method for the alteration of siliceous materials from bayer process liquors |
| WO1996033953A1 (en) * | 1995-04-26 | 1996-10-31 | Albright & Wilson Uk Limited | Stain corrosion and scale inhibitors |
| EP0990671A1 (en) * | 1998-09-30 | 2000-04-05 | Dow Corning Toray Silicone Company, Ltd. | Gas barrier composition and molded resin |
| US20060124553A1 (en) * | 2002-07-22 | 2006-06-15 | Taylor Matthew L | Method of preventing or reducing aluminosilicate scale in high level nuclear wastes |
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| AU2012241116B2 (en) | 2013-06-13 |
| AU2013201421A1 (en) | 2013-04-04 |
| AU2013201421B2 (en) | 2014-04-10 |
| AU2011226768A1 (en) | 2011-10-13 |
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