CN109364930B - Selective hydrogenation catalyst for pyrolysis gasoline and preparation method thereof - Google Patents
Selective hydrogenation catalyst for pyrolysis gasoline and preparation method thereof Download PDFInfo
- Publication number
- CN109364930B CN109364930B CN201811183092.6A CN201811183092A CN109364930B CN 109364930 B CN109364930 B CN 109364930B CN 201811183092 A CN201811183092 A CN 201811183092A CN 109364930 B CN109364930 B CN 109364930B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- nickel
- alumina
- pyrolysis gasoline
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 45
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 64
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 39
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 39
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 30
- 239000011148 porous material Substances 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 26
- 229920000620 organic polymer Polymers 0.000 claims description 23
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 21
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 9
- 239000004584 polyacrylic acid Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 238000004898 kneading Methods 0.000 claims description 8
- 229920000058 polyacrylate Polymers 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 239000000084 colloidal system Substances 0.000 abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052785 arsenic Inorganic materials 0.000 abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 abstract description 9
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000395 magnesium oxide Substances 0.000 abstract description 2
- 238000007654 immersion Methods 0.000 abstract 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract 1
- 150000001993 dienes Chemical class 0.000 description 24
- 239000003921 oil Substances 0.000 description 22
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 14
- 229910052794 bromium Inorganic materials 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 229910052740 iodine Inorganic materials 0.000 description 7
- 239000011630 iodine Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 150000002941 palladium compounds Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 241000219793 Trifolium Species 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- -1 alkyl aromatic hydrocarbon Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910002094 inorganic tetrachloropalladate Inorganic materials 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
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- PZKNFJIOIKQCPA-UHFFFAOYSA-N oxalic acid palladium Chemical compound [Pd].OC(=O)C(O)=O PZKNFJIOIKQCPA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a selective hydrogenation catalyst for pyrolysis gasoline and a preparation method thereof, wherein the catalyst comprises a silicon oxide-alumina carrier and a metal active component palladium loaded on the carrier, the content of the palladium is 0.15-0.45 wt% based on the total weight of the catalyst, the silicon oxide-alumina carrier comprises silicon oxide, nickel-doped lanthanum ferrite and magnesium oxide, mesoporous pores of the carrier account for 3-75% of total pores, and macroporous pores account for 1.5-60% of the total pores. The catalyst is prepared by adopting an immersion method, and has good colloid resistance, strong arsenic resistance, strong sulfur resistance and strong water resistance.
Description
Technical Field
The invention relates to a catalyst for one-stage selective hydrogenation of pyrolysis gasoline and a preparation method thereof.
Background
The pyrolysis gasoline is an important byproduct of ethylene and propylene produced by steam cracking industry and comprises C5-C10 fractions. The pyrolysis gasoline has complex composition, mainly comprises benzene, toluene, xylene, monoolefin, diolefin, straight-chain alkane, cycloparaffin, nitrogen, sulfur, oxygen, chlorine and heavy metal organic compounds, and the like, and has more than 200 components, wherein the benzene, the toluene and the xylene (generally called BTX) are about 50-90%, and the unsaturated hydrocarbon is 25-30%. According to the characteristic that pyrolysis gasoline contains a large amount of aromatic hydrocarbon, the application of the pyrolysis gasoline is wide, and the pyrolysis gasoline can be used as a blending component of gasoline to produce gasoline with high octane number, and can also be used for producing aromatic hydrocarbon and the like through separation.
Because the pyrolysis gasoline has complex composition and poor thermal stability, usually, the diolefin and the styrene are removed by first-stage selective hydrogenation, and the pyrolysis gasoline is mainly used for extracting the aromatic hydrocarbon after second-stage hydrodesulfurization. At present, the catalyst for selective hydrogenation of pyrolysis gasoline in industry is mainly Pd-series or Ni-series catalyst, and middle distillate (C)6～C8Hydrocarbon compound fraction) hydrogenation or whole fraction (C)5Hydrocarbon-hydrocarbon compound fraction having a dry point of 204 deg.c). Due to the difference between the pyrolysis raw materials and the pyrolysis conditions of all ethylene units, the composition of the pyrolysis gasoline raw materials of all the ethylene units has larger difference, and particularly, the contents of diene, colloid (high molecular polymer generated by polymerization reaction of unsaturated components such As diene, styrene and the like) As well As As and heavy metal of the pyrolysis gasoline have larger difference; some crude pyrolysis gasoline has high diene and colloid content, while some crude pyrolysis gasoline has high colloid content, high As content, high heavy metal content and other toxic materials, and some crude pyrolysis gasoline has high diene, colloid content, high As content, high heavy metal content and other toxic materials.
The dialkene and alkyne in the pyrolysis gasoline are easily polymerized into the gasoline at high temperatureColloid, deposited on the surface of the catalyst, is easy to cause the deactivation of the catalyst, and must be activated and regenerated frequently. The first-stage hydrogenation catalyst for pyrolysis gasoline mainly comprises Pd/Al2O3And Ni/Al2O3Two catalysts. The Pd catalyst has the advantages of low initial temperature, high hydrogenation activity, high adaptive airspeed, long service life and the like, and the existing catalyst for industrial application comprises Pd-Cr/Al2O3，Pd/Al2O3。
Generally, the pyrolysis gasoline hydrogenation catalyst adopts a solution of metal salt or organic metal compound of an active component to impregnate the carrier, then the active component oxide is loaded on the surface of the carrier through the working procedures of drying, roasting and the like, and the catalyst can be used for the pyrolysis gasoline hydrogenation reaction after being reduced by introducing hydrogen before use. The pore diameter of the common alumina carrier is too small, and when the content of colloid, arsenic and sulfur in the raw material exceeds the standard, pores on the catalyst are easy to coke and block, so that the activity and the hydrogenation stability of the catalyst are influenced.
CN201310379189.5 discloses a pyrolysis gasoline selective hydrogenation catalyst, which comprises a carrier and a metal active component loaded on the carrier, wherein the active component is prepared in a microemulsion method system containing a high molecular polymer water phase and no auxiliary surfactant; the carrier is selected from at least one of alumina, titanium oxide, magnesia, zinc oxide, diatomite, molecular sieve, kaolin and cordierite; the active component comprises a main active component and an auxiliary active component, wherein the main active component is palladium, the content of the palladium is 0.01-1.0 wt% of the total weight of the carrier, and the high molecular polymer is a water-soluble high molecular polymer. The catalyst has higher activity, better selectivity and better gel-holding capacity in the reaction, the preparation process is simple and convenient, and the particle shape of the catalyst can be well controlled. CN201110089806.9 relates to a palladium-silver/alumina-titania catalyst for selective hydrogenation of pyrolysis gasoline or fractions thereof, comprising an alumina-titania composite as a carrier, and active components Pd and Ag supported on the carrier, wherein the content of Pd is 0.15-0.5 wt% based on the total weight of the catalyst, and the content of Ag is 0.8-4.5 wt% based on the total weight of the catalyst. In the same class asCompared with the catalyst, the catalyst can be used for hydrogenation of pyrolysis gasoline or fractions thereof, and has the advantages of high low-temperature hydrogenation selectivity, strong As impurity resistance, large gel capacity and stable activity. CN200610029962.5 relates to a method for selective hydrogenation of full-range pyrolysis gasoline, which mainly solves the technical problem that the full-range pyrolysis gasoline with high content of colloid and free water is difficult to be selectively hydrogenated in the prior art. The invention adopts C5Cracking gasoline of hydrocarbon compound fraction with a hydrocarbon-dry point of 204 ℃ and hydrogen are used as raw materials, the reaction temperature is 30-80 ℃, the reaction pressure is 2.0-3.0 MPa, and the space velocity of fresh oil is 2.5-5.0 hours－1Under the condition that the volume ratio of hydrogen to oil is 60-120: 1, the raw material is contacted with a catalyst for reaction to convert diolefin and olefin-based aromatic hydrocarbon components in the raw material into mono-olefin and alkyl aromatic hydrocarbon, wherein the catalyst comprises an alumina carrier, an active component of metallic palladium or an oxide thereof, at least one element selected from IA or IIA in a periodic table of elements or an oxide thereof, and at least one element selected from IVA or VA in the periodic table of elements or an oxide thereof, the specific surface area of the carrier is 40-160 m2The catalyst has the advantages that the catalyst can be used for the selective hydrogenation of full fraction pyrolysis gasoline, the total pore volume is 0.3-1.2 ml/g, and the carrier has the technical scheme of composite pore distribution, so that the problem is solved well, and the catalyst can be used for the industrial production of the selective hydrogenation of the full fraction pyrolysis gasoline. The preparation method of the catalyst is the same as the impregnation technology of the common shell layer catalyst: the method comprises the steps of pre-soaking a carrier in a liquid capable of being mutually soluble with an impregnation solution, then impregnating the carrier in a salt solution containing palladium, washing, drying and roasting the impregnated carrier in air at 300-600 ℃ to obtain the finished product of the oxidative catalyst. The finished catalyst can be used only by introducing hydrogen into a reactor for reduction. The catalyst adopted by the invention has a composite pore structure, a larger pore diameter and rich mesopores. The catalyst of the invention has good low-temperature activity, selectivity and stability when being used for selective hydrogenation of full-fraction pyrolysis gasoline, and has good anti-interference performance, high colloid resistance and high free water content. At the inlet temperature of 40 ℃, the reaction pressure of 2.7Mpa, the hydrogen/oil volume ratio of 80: 1 and the fresh oil airspeed of 3.8 hours-1Under the conditions of 150 mg of colloid per 100g of oil and free water content1000ppm of a total fraction (C)5Hydrocarbon-to-dry point 204 deg.c) pyrolysis gasoline, the average value of the diene at the outlet is 0.0 g iodine/100 g oil, and the diene hydrogenation rate is 100%, so as to obtain good technological effect. The preparation method of the carrier comprises the steps of mixing alumina, a modifier, a peptizing agent and water according to required amounts, extruding and forming, drying at 50-120 ℃ for 1-24 hours, and then roasting at 800-1150 ℃ for 1-10 hours to obtain the alumina carrier.
The prior art mainly changes the chemical composition and type of a carrier and adds a promoter to improve the performance of a catalyst. As the contents of impurities such As As, S, O, N and the like and colloid in the pyrolysis gasoline are high, the catalyst is easy to inactivate, so that the pyrolysis gasoline catalyst is required to have the characteristics of good colloid resistance and water resistance, and strong arsenic resistance and sulfur resistance.
Disclosure of Invention
The invention aims to provide a first-stage selective hydrogenation catalyst for pyrolysis gasoline, which has higher activity and better selectivity in reaction and has strong colloid resistance, arsenic resistance and sulfur resistance. The carrier of the catalyst is a silicon oxide-aluminum oxide carrier, the carrier contains nickel-doped lanthanum ferrite, and the catalyst is particularly suitable for pyrolysis gasoline C6-C8And (4) selectively hydrogenating the distillate.
The invention provides a pyrolysis gasoline first-stage selective hydrogenation catalyst which comprises a silicon oxide-aluminum oxide carrier and a metal active component palladium loaded on the carrier, wherein the content of the palladium is 0.15-0.45 wt% based on the total weight of the catalyst, the silicon oxide-aluminum oxide carrier contains 0.1-12 wt% of silicon oxide, 0.1-10 wt% of nickel-doped lanthanum ferrite and 0.05-7.8 wt% of magnesium, the carrier accounts for 3-75% of the total pores, and the macropores account for 1.5-60% of the total pores. The micropores, mesopores and macropores in the carrier are not uniformly distributed.
The palladium content in the above catalyst is preferably 0.20 to 0.35% by weight. Preferably, the mesopores account for 3-65% of the total pores, and the macropores account for 3-45% of the total pores.
The preparation method of the silica-alumina carrier comprises the following steps: adding pseudo-boehmite and sesbania powder into a kneading machine, uniformly mixing, adding an inorganic acid solution and an organic polymer, uniformly kneading, then adding nickel-doped lanthanum ferrite, and uniformly mixing to obtain an alumina precursor for later use; adding a silicon source and pseudo-boehmite into acid liquor of an organic polymer, and uniformly mixing to obtain a silicon source-pseudo-boehmite-organic polymer mixture, wherein the content of the organic polymer in the unit content of an alumina precursor is more than 2 times higher than that of the organic polymer in the silicon source-pseudo-boehmite-organic polymer mixture (abbreviated as silicon-aluminum-organic matter mixture), then mixing the silicon source-pseudo-boehmite-organic polymer mixture with the alumina precursor, adding a magnesium source, extruding, forming, drying and roasting to obtain the silica-alumina carrier. The silicon source is silica gel, sodium silicate or silica micropowder. The alumina in the silicon-aluminum-organic matter mixture accounts for 1-35 wt% of the alumina in the carrier.
In the preparation process of the silicon oxide-alumina carrier, the organic polymer is one or more of polyvinyl alcohol, polyacrylic acid, sodium polyacrylate, polyethylene glycol and polyacrylate.
Preferably, the nickel-doped lanthanum ferrite in the silica-alumina carrier is 0.1-12 wt%, more preferably 0.2-8 wt%, and the nickel in the nickel-doped lanthanum ferrite accounts for 0.1-8 wt% of the lanthanum ferrite.
The preparation method of the nickel-doped lanthanum ferrite comprises the following steps: dissolving citric acid in deionized water, stirring and dissolving, then adding lanthanum nitrate and ferric nitrate into the citric acid, stirring and dissolving, and adding sodium polyacrylate, polyacrylate or polyacrylic acid, wherein the adding amount of the sodium polyacrylate, the polyacrylate or the polyacrylic acid is 0.1-10 wt% of the nickel-doped lanthanum ferrite, and preferably 0.1-8.0 wt%. Adding nickel-containing compound, stirring, drying, roasting and grinding to obtain the finished product. The nickel-containing compound includes nickel nitrate, nickel acetate, and the like.
The preparation method of the catalyst can adopt the methods of dipping, spraying and the like, dipping and spraying the active component palladium on the silicon oxide-alumina carrier, and then drying and roasting the catalyst to obtain the catalyst. The catalyst can be prepared, for example, by the following steps: preparing a palladium-containing solution to dip a silicon oxide-alumina carrier, drying the carrier for 3 to 9 hours at the temperature of 110 to 160 ℃, and roasting the carrier for 4 to 9 hours at the temperature of 400 to 650 ℃ to finally obtain a catalyst product.
In the preparation method of the catalyst of the present invention, the palladium compound used may be any one of the palladium compounds disclosed in the prior art as being suitable for preparing a palladium catalyst, such as palladium chloride, palladium nitrate, palladium sulfate, aluminum tetrachloropalladate, aluminum tetracyanopalladate, sodium tetranitropalladate, salts of organic acids of palladium such as palladium oxalate, etc. The solvent used for preparing the palladium compound solution is not particularly limited as long as it can dissolve the palladium compound used. Preferred solvents are, for example, water, dilute hydrochloric acid, dilute nitric acid, dilute sulfuric acid, or a mixture thereof.
The nickel-doped lanthanum ferrite is added into the silicon oxide-alumina carrier, so that the arsenic resistance, the sulfur resistance and the water resistance are effectively improved, and the alkyne or diene hydrogenation selectivity is improved. In the preparation process of the silicon oxide-aluminum oxide carrier, the content of organic polymers with unit content in the aluminum oxide precursor is more than 2 times higher than that of organic polymers in a silicon-aluminum-organic matter mixture, and the organic polymers are not simply expanded, but the micropores, mesopores and macropores of the carrier are not uniformly distributed, so that the pore structure of the carrier can be improved, the micropores, mesopores and macropores of the carrier are not uniformly distributed, the colloid resistance of the catalyst is improved, the stability and the service life of the catalyst are improved, and the long-period operation of the device is facilitated; and the surface of the carrier is promoted to generate more active site loading centers, and the hydrogenation activity of the palladium catalyst is improved.
Detailed Description
The present invention is described in further detail below by way of examples, which should not be construed as limiting the invention thereto.
The main raw material sources for preparing the catalyst are as follows: the raw material reagents used in the invention are all commercial products.
Example 1
1. Preparation of nickel-doped lanthanum ferrite
Dissolving 2.51mol of lanthanum nitrate in 120mL of water under the condition of stirring, adding citric acid, and stirring for dissolving; then adding 4.79mol of ferric nitrate, then adding 190g of sodium polyacrylate, then adding the water solution containing 42g of nickel nitrate, continuously stirring for 30min, and obtaining the nickel-doped lanthanum ferrite through drying, roasting and grinding.
2. Preparation of silica-alumina Carrier
4.5g of nickel-doped lanthanum ferrite is added with citric acid for standby. Adding 300g of pseudo-boehmite powder and 25.0g of sesbania powder into a kneader, adding nitric acid, adding 40.2g of sodium polyacrylate nitric acid solution, uniformly mixing, adding nickel-doped lanthanum ferrite, and uniformly mixing to obtain an alumina precursor. 5g of sodium polyacrylate is dissolved in nitric acid, 38g of silica powder and 50g of pseudo-boehmite powder are added and stirred uniformly to obtain a silica powder-pseudo-boehmite-sodium polyacrylate mixture (abbreviated as silica-alumina-organic matter mixture). 1/8 silicon-aluminum-organic matter mixture is taken, the alumina precursor and 4.2g magnesium nitrate are added, the mixture is evenly kneaded, and the mixture is kneaded and extruded to form clover shape. Drying at 120 ℃ for 8 hours, and roasting at 650 ℃ for 6 hours to obtain the nickel-doped lanthanum ferrite-containing silica-alumina carrier 1. The mesopores of the carrier account for 55.4 percent of the total pores, and the macropores account for 28.6 percent of the total pores.
3. Preparation of the catalyst
The carrier 1 is impregnated with a palladium solution, dried at 140 ℃ for 6 hours and calcined at 560 ℃ for 5 hours to obtain the catalyst 1. The palladium content of catalyst 1 was 0.29 wt%.
Example 2
The nickel-doped lanthanum ferrite is prepared as in example 1, except that 260g of sodium polyacrylate is added, and the silica-alumina carrier is prepared as in example 1, wherein the silica-alumina carrier contains 4.4 wt% of silica, 5.7 wt% of nickel-doped lanthanum ferrite and 1.2 wt% of magnesium, the mesopores of the carrier account for 63.8% of the total pores, and the macropores account for 25.9% of the total pores. The unit content of sodium polyacrylate in the alumina precursor is 3 times higher than that of sodium polyacrylate in the silicon source-organic polymer mixture. Catalyst 2 was prepared in the same manner as in example 1, except that the amount of palladium was 0.35% by weight.
Example 3
The nickel-doped lanthanum ferrite is prepared as in example 1, except that 220g of polyacrylic acid is added, and the silica-alumina carrier is prepared as in example 1, wherein the silica-alumina carrier contains 8.4 wt% of silica, 2.6 wt% of nickel-doped lanthanum ferrite and 2.1 wt% of magnesium, mesoporous pores of the carrier account for 54.9% of total pores, and macroporous pores account for 33.1% of total pores. The unit content of polyacrylic acid in the alumina precursor is 3.3 times higher than that of polyacrylic acid in the silicon source-organic polymer mixture. Catalyst 3 was prepared in the same manner as in example 1, except that the amount of palladium was 0.21% by weight.
Example 4
The nickel-doped lanthanum ferrite was prepared as in example 1 except that 280g of sodium polyacrylate was added, and the silica-alumina carrier was prepared as in example 1, wherein the silica-alumina carrier contained 8.4 wt% of silica, 2.6 wt% of nickel-doped lanthanum ferrite, and 2.8 wt% of magnesium, the mesopores of the carrier accounted for 50.1% of the total pores, and the macropores accounted for 39.7% of the total pores. The polyacrylate content per unit content in the alumina precursor was 3.3 times higher than the polyacrylate content in the silicon source-organic polymer mixture. Catalyst 3 was prepared in the same manner as in example 1, except that the amount of palladium was 0.26% by weight.
Comparative example 1
1. Preparation of lanthanum ferrite
Dissolving 2.51mol of lanthanum nitrate in 120mL of water under the condition of stirring, adding citric acid, and stirring for dissolving; then adding 4.79mol of ferric nitrate, then adding 190g of sodium polyacrylate, stirring for 30min, drying, roasting and grinding to obtain the nickel-doped lanthanum ferrite.
2. Preparation of silica-alumina Carrier
5g of sodium polyacrylate is dissolved in nitric acid, 38g of silica powder and 50g of pseudo-boehmite powder are added and uniformly stirred to obtain a silica powder-pseudo-boehmite-sodium polyacrylate mixture (abbreviated as a silica-alumina-organic matter mixture), 1/8 is taken for later use, and 4.5g of lanthanum ferrite is added with citric acid for later use. Adding 300g of pseudo-boehmite powder and 25.0g of sesbania powder into a kneader, adding nitric acid, adding 40.2g of sodium polyacrylate nitric acid solution, uniformly mixing, adding the silicon micropowder-sodium polyacrylate mixture, uniformly kneading, adding lanthanum ferrite and 4.2g of magnesium nitrate, uniformly mixing, and kneading and extruding to form the clover shape. Drying at 130 deg.C for 7 hr, and calcining at 620 deg.C for 7 hr to obtain the carrier 1-1 of silicon oxide-aluminium oxide containing lanthanum ferrite.
3. Preparation of comparative catalyst 1
Preparing a palladium solution to impregnate a carrier 1-1, drying at 140 ℃ for 6 hours, and roasting at 560 ℃ for 5 hours to obtain the catalyst 1. The palladium content of comparative catalyst 1 was 0.29 wt%.
Comparative example 2
1. Preparation of nickel-doped lanthanum ferrite
Dissolving 2.51mol of lanthanum nitrate in 120mL of water under the condition of stirring, adding citric acid, and stirring for dissolving; then adding 4.79mol of ferric nitrate, then adding 190g of sodium polyacrylate, then adding the water solution containing 42g of nickel nitrate, continuously stirring for 30min, and obtaining the nickel-doped lanthanum ferrite through drying, roasting and grinding.
2. Preparation of silica-alumina Carrier
Adding citric acid into 4.5g of nickel-doped lanthanum ferrite for later use, adding 350g of pseudo-boehmite powder and 25.0g of sesbania powder into a kneader, adding nitric acid, adding 40.7g of sodium polyacrylate nitric acid solution, uniformly mixing, adding 4.8g of silicon micropowder, uniformly kneading, adding nickel-doped lanthanum ferrite and 4.2g of magnesium nitrate, uniformly mixing, and kneading and extruding to form the clover shape. Drying at 130 deg.C for 7 hr, and calcining at 620 deg.C for 7 hr to obtain the carrier 1-2 containing nickel-doped lanthanum ferrite silica-alumina.
3. Preparation of comparative catalyst 2
A palladium solution was prepared to impregnate the support 1-2, dried at 140 ℃ for 6 hours and calcined at 560 ℃ for 5 hours to give comparative catalyst 2. The palladium content of comparative catalyst 2 was 0.29 wt%.
Catalysts 1-4 and comparative catalysts 1 and 2 were each charged to a 100ml adiabatic bed reactor at a temperature of 130 ℃, a hydrogen to catalyst volume ratio of 220: reducing for 7 hours under the condition of 1, cooling to 40 ℃, and then adding the raw oil and the pyrolysis gasoline C6-C8A fraction having a diene content of 19.51g iodine/100 g oil, a bromine number of 26.76g bromine/100 g oil, a gum content of 41mg/100ml oil, a free water content of 1123ppm, a sulphur content of 156ppm and an arsenic content of 151 ppb; the reaction process conditions are as follows: the inlet temperature is 45 ℃, the volume ratio of hydrogen to oil is 300: 1, the reaction pressure is 3.5MPa, and the space velocity of fresh oil is 3.5h-1(ii) a The average diene of the hydrogenation product of the catalyst 1 in 220h running is 0.38 g of iodine/100 g of oil, the bromine number is 15.68 g of bromine/100 g, and the diene hydrogenation rate is 98.7%. Catalyst 2 the average diene content of the hydrogenation product was 0.33 gIodine/100 g of oil, bromine number of 14.56 g of bromine/100 g of oil, and diene hydrogenation rate of 98.8 percent; the average diene of the hydrogenation product of the catalyst 3 is 0.42 g of iodine/100 g of oil, the bromine number is 16.54 g of bromine/100 g, and the hydrogenation rate of the diene is 98.2 percent. The average diene of the hydrogenated product of the catalyst 4 is 0.40 g of iodine/100 g of oil, the bromine number is 15.29 g of bromine/100 g of oil, and the hydrogenation rate of the diene is 98.3 percent. The catalyst has higher activity, better selectivity, better colloid resistance and water resistance, and strong arsenic resistance and sulfur resistance.
After the catalyst 1-2 is operated for 500 hours, the average diene of the hydrogenation product of the catalyst 1 is 0.40 g of iodine/100 g of oil, the bromine number is 20.25 g of bromine/100 g of oil, and the diene hydrogenation rate is 98.5 percent; the average diene of the hydrogenation product of the catalyst 2 is 0.45 g of iodine/100 g of oil, the bromine number is 20.48 g of bromine/100 g of oil, and the hydrogenation rate of the diene is 98.7 percent. The catalyst carrier contains nickel-doped lanthanum ferrite, which is beneficial to inhibiting polymerization reaction of unsaturated components such as alkadiene, styrene and the like; the catalyst is not sensitive to impurities such as water, colloid and the like, and has good colloid resistance and water resistance, strong arsenic resistance and sulfur resistance and stable catalytic performance. The catalyst carrier has unevenly distributed micropores, mesopores and macropores, and the palladium catalyst has good activity, good stability and long service life and is beneficial to long-period operation of the device.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (7)
1. The selective hydrogenation catalyst for the pyrolysis gasoline is characterized by comprising a silicon oxide-aluminum oxide carrier and a metal active component palladium loaded on the carrier, wherein the content of the palladium is 0.15-0.45 wt% based on the total weight of the catalyst, the silicon oxide-aluminum oxide carrier contains 0.1-12 wt% of silicon oxide, 0.1-10 wt% of nickel-doped lanthanum ferrite and 0.05-7.8 wt% of magnesium, and nickel in the nickel-doped lanthanum ferrite accounts for 0.1-8 wt% of the lanthanum ferrite; the mesopores of the carrier account for 3-75% of the total pores, the macropores account for 1.5-60% of the total pores, and micropores, mesopores and macropores in the carrier are not uniformly distributed; the preparation method of the silica-alumina carrier comprises the following steps: adding pseudo-boehmite and sesbania powder into a kneading machine, uniformly mixing, adding an inorganic acid solution and an organic polymer, uniformly kneading, then adding nickel-doped lanthanum ferrite, and uniformly mixing to obtain an alumina precursor for later use; adding a silicon source and pseudo-boehmite into acid liquor of an organic polymer, and uniformly mixing to obtain a silicon source-pseudo-boehmite-organic polymer mixture, wherein the content of the organic polymer in the unit content of an alumina precursor is more than 2 times higher than that of the organic polymer in the silicon source-pseudo-boehmite-organic polymer mixture, then mixing the silicon source-pseudo-boehmite-organic polymer mixture with the alumina precursor, adding a magnesium source, extruding, forming, drying and roasting to obtain a silica-alumina carrier; the organic polymer is one or more of sodium polyacrylate, polyacrylic acid or polyacrylate; the preparation method of the catalyst comprises the following steps: the active component palladium is dipped and sprayed on a silicon oxide-alumina carrier, and then the catalyst is dried and roasted to obtain the catalyst.
2. The selective hydrogenation catalyst for pyrolysis gasoline of claim 1 wherein the catalyst palladium content is 0.20-0.35 wt%.
3. The selective hydrogenation catalyst for pyrolysis gasoline according to claim 1, wherein the carrier mesopores account for 3-65% of the total pores, and macropores account for 3-45% of the total pores.
4. The selective hydrogenation catalyst for pyrolysis gasoline according to claim 1, wherein the silicon source is silica gel, sodium silicate or silica micropowder, and the alumina in the silicon source-pseudo-boehmite-organic polymer mixture accounts for 1-35 wt% of the alumina in the carrier.
5. The selective hydrogenation catalyst for pyrolysis gasoline of claim 1, wherein the nickel-doped lanthanum ferrite in the silica-alumina carrier is 0.2-8 wt%.
6. The selective hydrogenation catalyst for pyrolysis gasoline according to any one of claims 1 to 5, wherein the preparation method of the nickel-doped lanthanum ferrite comprises the following steps: dissolving citric acid in deionized water, stirring and dissolving, then adding lanthanum nitrate and ferric nitrate into the citric acid, stirring and dissolving, adding sodium polyacrylate, polyacrylate or polyacrylic acid, wherein the adding amount of the sodium polyacrylate, the polyacrylate or the polyacrylic acid is 0.1-10 wt% of that of the nickel-doped lanthanum ferrite, then adding a nickel-containing compound, stirring, drying, roasting and grinding to obtain a finished product.
7. The selective hydrogenation catalyst for pyrolysis gasoline according to claim 6, wherein the catalyst is prepared by the following steps: preparing a palladium-containing solution to dip a silicon oxide-alumina carrier, drying the carrier for 3 to 9 hours at the temperature of 110 to 160 ℃, and roasting the carrier for 4 to 9 hours at the temperature of 400 to 650 ℃ to finally obtain a catalyst product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811183092.6A CN109364930B (en) | 2018-10-11 | 2018-10-11 | Selective hydrogenation catalyst for pyrolysis gasoline and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811183092.6A CN109364930B (en) | 2018-10-11 | 2018-10-11 | Selective hydrogenation catalyst for pyrolysis gasoline and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109364930A CN109364930A (en) | 2019-02-22 |
| CN109364930B true CN109364930B (en) | 2021-07-20 |
Family
ID=65403578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811183092.6A Active CN109364930B (en) | 2018-10-11 | 2018-10-11 | Selective hydrogenation catalyst for pyrolysis gasoline and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109364930B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1798716A (en) * | 2003-06-04 | 2006-07-05 | 约翰森·马瑟公开有限公司 | Selective hydrogenation process and catalyst therefor |
| CN1830560A (en) * | 2005-03-11 | 2006-09-13 | 石油大学(北京) | Macropore hydrogenation catalyst and its preparation method |
| CN101121899A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Selectivity hydrogenation method for whole fraction crack petroleum |
| CN101260320A (en) * | 2008-04-17 | 2008-09-10 | 中国石油天然气集团公司 | Selectivity hydrodeolefin catalyst used for continuously reforming gasoline and preparation method thereof |
| CN103418378A (en) * | 2013-08-01 | 2013-12-04 | 济南开发区星火科学技术研究院 | Catalytic agent for cracking C-4 fraction selective hydrogenating palladium base |
| FR2993795A1 (en) * | 2012-07-25 | 2014-01-31 | IFP Energies Nouvelles | Preparing supported catalyst based on metal particles, comprises providing aqueous solution of metal precursor, heating porous support, contacting aqueous solution with porous support by dry impregnation, and drying the product |
| CN107159279A (en) * | 2017-06-02 | 2017-09-15 | 钦州学院 | A kind of one-stage selective hydrogenation of gasoline splitting catalyst and preparation method thereof |
| CN107754818A (en) * | 2017-11-24 | 2018-03-06 | 福州大学 | A kind of hydrocracking catalyst for suspension bed and preparation method |
-
2018
- 2018-10-11 CN CN201811183092.6A patent/CN109364930B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1798716A (en) * | 2003-06-04 | 2006-07-05 | 约翰森·马瑟公开有限公司 | Selective hydrogenation process and catalyst therefor |
| CN1830560A (en) * | 2005-03-11 | 2006-09-13 | 石油大学(北京) | Macropore hydrogenation catalyst and its preparation method |
| CN101121899A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Selectivity hydrogenation method for whole fraction crack petroleum |
| CN101260320A (en) * | 2008-04-17 | 2008-09-10 | 中国石油天然气集团公司 | Selectivity hydrodeolefin catalyst used for continuously reforming gasoline and preparation method thereof |
| FR2993795A1 (en) * | 2012-07-25 | 2014-01-31 | IFP Energies Nouvelles | Preparing supported catalyst based on metal particles, comprises providing aqueous solution of metal precursor, heating porous support, contacting aqueous solution with porous support by dry impregnation, and drying the product |
| CN103418378A (en) * | 2013-08-01 | 2013-12-04 | 济南开发区星火科学技术研究院 | Catalytic agent for cracking C-4 fraction selective hydrogenating palladium base |
| CN107159279A (en) * | 2017-06-02 | 2017-09-15 | 钦州学院 | A kind of one-stage selective hydrogenation of gasoline splitting catalyst and preparation method thereof |
| CN107754818A (en) * | 2017-11-24 | 2018-03-06 | 福州大学 | A kind of hydrocracking catalyst for suspension bed and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109364930A (en) | 2019-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2008508089A (en) | Selective hydrogenation catalyst for crude gas feed streams. | |
| CN108927173B (en) | Alkyne selective hydrogenation catalyst and preparation method and application thereof | |
| CN109364929B (en) | Method for selective hydrogenation of pyrolysis gasoline | |
| CN109289868B (en) | Pyrolysis gasoline selective hydrogenation catalyst and preparation method thereof | |
| CN109364945B (en) | Method for selective hydrogenation of full-fraction pyrolysis gasoline | |
| CN109022025B (en) | Selective hydrogenation method for full-fraction pyrolysis gasoline | |
| CN109364930B (en) | Selective hydrogenation catalyst for pyrolysis gasoline and preparation method thereof | |
| CN109022026B (en) | Pyrolysis gasoline one-stage selective hydrogenation method | |
| CN109364934B (en) | Nickel series selective hydrogenation catalyst and preparation method thereof | |
| CN109433218B (en) | Unsaturated hydrocarbon selective hydrogenation catalyst and preparation method thereof | |
| CN109355093B (en) | Pyrolysis gasoline full-fraction selective hydrogenation method | |
| CN103418379B (en) | Remove the Catalysts and its preparation method of alkadienes in carbon four | |
| CN109355095B (en) | Pyrolysis gasoline C6-C8Distillate oil selective hydrogenation method | |
| CN109355094B (en) | Pyrolysis gasoline one-stage selective hydrogenation method | |
| WO2023134779A1 (en) | Hydrogenation catalyst and preparation method therefor, and method for preparing isohexanediol and methyl isobutyl carbinol | |
| CN112439433B (en) | Catalyst with hydrogenation and dimerization functions and preparation method and application thereof | |
| CN109321270B (en) | Selective hydrogenation method for unsaturated hydrocarbons in middle distillate of pyrolysis gasoline | |
| CN112675871B (en) | Preparation method of hydrogenation catalyst before deethanization before carbon dioxide fraction | |
| CN112844405B (en) | Catalyst for selective hydrogenation of light hydrocarbon cracking carbon-enriched fraction | |
| CN112939717B (en) | Alkyne removing method for selective hydrogenation process of light hydrocarbon cracking carbon-dioxide fraction | |
| CN112939718B (en) | Alkyne removing method for pre-depropanization and pre-hydrogenation process | |
| CN112675872B (en) | Hydrogenation catalyst before deethanization before carbon dioxide fraction | |
| WO2020052144A1 (en) | Method for pre-hydrogenation of catalytically cracked gasoline | |
| CN112939723B (en) | Alkyne removing method for carbon three-fraction selective hydrogenation process | |
| CN112844408B (en) | Preparation method of hydrogenation catalyst before front depropanization of carbon two fractions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210630 Address after: 257000 No.12 Hesheng Road, Dongji Town, Kenli District, Dongying City, Shandong Province Applicant after: DONGYING TIANXI CHEMICAL Co.,Ltd. Address before: 362100 No.39 tangzao, Yiban village, Tuling Town, Quangang District, Quanzhou City, Fujian Province Applicant before: Chen Xinzhong |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: The invention relates to a catalyst for selective hydrogenation of cracked gasoline and a preparation method thereof Effective date of registration: 20211229 Granted publication date: 20210720 Pledgee: Shandong Tianlai Energy Saving Technology Co.,Ltd. Pledgor: DONGYING TIANXI CHEMICAL Co.,Ltd. Registration number: Y2021980016738 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20190222 Assignee: Shandong Tianlai Energy Saving Technology Co.,Ltd. Assignor: DONGYING TIANXI CHEMICAL Co.,Ltd. Contract record no.: X2022980019417 Denomination of invention: A catalyst for selective hydrogenation of cracked gasoline and its preparation method Granted publication date: 20210720 License type: Common License Record date: 20221024 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20221021 Granted publication date: 20210720 Pledgee: Shandong Tianlai Energy Saving Technology Co.,Ltd. Pledgor: DONGYING TIANXI CHEMICAL Co.,Ltd. Registration number: Y2021980016738 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Shandong Tianlai Energy Saving Technology Co.,Ltd. Assignor: DONGYING TIANXI CHEMICAL Co.,Ltd. Contract record no.: X2022980019417 Date of cancellation: 20230317 |
|
| EC01 | Cancellation of recordation of patent licensing contract |