CN109022025A - Full-cut fraction pyrolysis gasoline process for selective hydrogenation - Google Patents
Full-cut fraction pyrolysis gasoline process for selective hydrogenation Download PDFInfo
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- CN109022025A CN109022025A CN201811182796.1A CN201811182796A CN109022025A CN 109022025 A CN109022025 A CN 109022025A CN 201811182796 A CN201811182796 A CN 201811182796A CN 109022025 A CN109022025 A CN 109022025A
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- Prior art keywords
- catalyst
- palladium
- full
- carrier
- pyrolysis gasoline
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Links
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 55
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000008569 process Effects 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 90
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 39
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 65
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 46
- 239000003921 oil Substances 0.000 claims description 34
- 229910000859 α-Fe Inorganic materials 0.000 claims description 34
- 229910052759 nickel Inorganic materials 0.000 claims description 32
- 229910052746 lanthanum Inorganic materials 0.000 claims description 31
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 31
- 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 22
- 229920000620 organic polymer Polymers 0.000 claims description 20
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229920002125 Sokalan® Polymers 0.000 claims description 11
- 239000004584 polyacrylic acid Substances 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
- 239000000843 powder Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 229910001593 boehmite Inorganic materials 0.000 claims description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- -1 cyano palladium Chemical compound 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000011863 silicon-based powder Substances 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 4
- 238000002156 mixing Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000002816 nickel compounds Chemical class 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 230000001404 mediated effect Effects 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- PZKNFJIOIKQCPA-UHFFFAOYSA-N oxalic acid palladium Chemical compound [Pd].OC(=O)C(O)=O PZKNFJIOIKQCPA-UHFFFAOYSA-N 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 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
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229910052785 arsenic Inorganic materials 0.000 abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 14
- 239000011593 sulfur Substances 0.000 abstract description 13
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 abstract description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 37
- 239000011630 iodine Substances 0.000 description 37
- 229910052740 iodine Inorganic materials 0.000 description 37
- 150000001993 dienes Chemical class 0.000 description 35
- 230000000694 effects Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 150000002941 palladium compounds Chemical class 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 230000007774 longterm Effects 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
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
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- 230000000737 periodic effect Effects 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XMOKRCSXICGIDD-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O XMOKRCSXICGIDD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 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
- 239000000428 dust Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron 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
- XQBXQQNSKADUDV-UHFFFAOYSA-N lanthanum;nitric acid Chemical compound [La].O[N+]([O-])=O XQBXQQNSKADUDV-UHFFFAOYSA-N 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229940047670 sodium acrylate Drugs 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
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- C10G45/10—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 platinum group metals or compounds thereof
-
- 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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of full-cut fraction pyrolysis gasoline process for selective hydrogenation, using fixed bed reactors, catalyst is restored under hydrogen atmosphere, is adjusted to reaction process condition after process to be restored, into full-cut fraction pyrolysis gasoline feedstock oil, selective hydrogenation is carried out；Catalyst includes silicaalumina carrier and the metal active component palladium that is carried on carrier, and the content of palladium is 0.15-0.45wt% based on the total weight of the catalyst.Hydrogenation process conditions: reaction inlet temperature >=50 DEG C, reaction pressure 2.0-4.5MPa, 60~400:1 of hydrogen to oil volume ratio；Liquid volume air speed 2.5-5.0h‑1.Catalyst anticol mass-energy power is good, and anti-arsenic, sulfur resistive, water resistant ability are strong, and stability is good.
Description
Technical field
The present invention relates to a kind of full-cut fraction pyrolysis gasoline process for selective hydrogenation.
Background technique
Drippolene is the important by-product of steam cracking industrial production ethylene, propylene, including C5-C10 fraction.Drippolene
It forms very complicated, mainly there is benzene,toluene,xylene, monoolefine, diolefin, linear paraffin, cycloalkane and nitrogen, sulphur, oxygen, chlorine
With the organic compound of heavy metal etc., a component more than totally 200, wherein benzene,toluene,xylene (being referred to as BTX) about 50-90%, no
Saturated hydrocarbons 25-30%.It is the characteristics of according to a large amount of aromatic hydrocarbons are contained in drippolene, widely used, it both can be used as the tune of gasoline
And component, high-octane gasoline is produced, separation production aromatic hydrocarbons etc. can also be passed through.
Since drippolene complicated composition, thermal stability are poor, in general, first removing alkadienes and benzene through one-stage selective hydrogenation
Ethylene after Secondary hydrodesulfurization, is mainly used for Aromatics Extractive Project.Industrial catalyst for selective hydrogenation of cracked gasoline is mainly at present
Pd system or Ni series catalysts, midbarrel (C6~C8Hydrocarbon compound fraction) plus hydrogen or full fraction (C5Hydrocarbon~do is 204 DEG C
Hydrocarbon compound fraction) hydrogenation technique.Due to the difference of each ethylene unit cracking stock and cracking condition, each device drippolene is former
Material composition difference is larger, and especially (it is anti-that polymerization occurs for the unsaturation component such as alkadienes and styrene for the diene of drippolene, colloid
The high molecular polymer that should be generated) and As, content of beary metal there are larger differences；Some device raw pyrolysis gasoline dienes, glue
Matter is high, and the toxic contents such as colloid and As, heavy metal are higher in some device raw pyrolysis gasoline raw materials, and individual device slightly cracks vapour
The toxic contents such as oily diene, colloid and As, heavy metal are high.
Alkadienes and alkynes in drippolene are easy polymerization collagen at high temperature, are deposited on catalyst surface, Yi Zao
At catalyst inactivation, it is necessary to frequently activation and regeneration.Pyrolysis gasoline hydrogenation catalyst mainly has Pd/Al2O3And Ni/Al2O3
Two kinds of catalyst.The advantages that Pd series catalysts have initial temperature low, and hydrogenation activity is big, and adaptation air speed is high, long service life,
The catalyst mode for having industrial application includes Pd-Cr/Al2O3, Pd/Al2O3。
Usual pyrolysis gasoline hydrogenation catalyst is using the metal salt of active component or the solution dipping of organo-metallic compound
The carrier, it is then by processes such as dry, roastings that active component is oxide carried to carrier surface, logical hydrogen is needed before use
Pyrolysis gasoline hydrogenation reaction could be used for after gas reduction.Common carrying alumina body aperture is too small, when colloid, arsenic contain in raw material
When amount, sulfur content are exceeded, the easy coking and blocking in hole on catalyst influences catalyst activity and stabilized hydrogenation.
CN201010622227.1 is related to a kind of catalyst for selective hydrogenation of cracked gasoline, and it includes as carrier
Magnesia-titania-alumina composite oxide, and the Metal Palladium active component being carried on the composite oxide carrier
And Group IIA and/or IIIB race metal promoter metal, wherein metal palladium content is 0.25-0.35 weight %, and promoter metal content is
0.2-3 weight %, and the content based on oxidation aluminium magnesia in carrier is 0.1-3 weight % and the content of titanium oxide is 5-20
Weight %.The catalyst can be used for selective hydrogenation of cracked gasoline, and low temperature active is high, and selectivity is high, anti-As, S, O, N impurity energy
Power is strong, and charging capacity is greatly and activity stabilized under long-term operation.Moreover, it relates to the preparation of the catalyst and select
Application in hydrocracking gasoline.Finally, preparing composite oxides used using co-precipitation method the invention further relates to a kind of
The method of carrier.CN201310379189.5 discloses a kind of pyrolysis gasoline selective hydrogenation catalyst, including carrier and is carried on
Metal active constituent on carrier, the active component containing high molecular polymer water phase without the micro- of cosurfactant
It is prepared in lotion law system；The carrier be selected from aluminium oxide, titanium oxide, magnesia, zinc oxide, diatomite, molecular sieve,
At least one of kaolin, cordierite；The active component is main active component and helps active component, wherein main active group
It is divided into palladium, content is 0.01wt%~1.0wt% of carrier gross weight, and the high molecular polymer is water-soluble polyphosphazene polymer
Close object.The activity of the catalyst in the reaction is higher, and selectivity is more preferable, and appearance glue ability is more preferable, and preparation process is easy, catalyst
Particle shape can be controlled well.CN201110089806.9 is related to a kind of for drippolene or its fraction selective hydrogenation
Palladium-silver/alumina-silica titanium catalyst, which includes the aluminium oxide-titanium oxide compound as carrier, and negative
The active component Pd and Ag being loaded on the carrier, wherein the content of Pd is based on the total catalyst weight as 0.15-0.5 weight
% is measured, it is 0.8-4.5 weight % that the content of Ag, which is based on the total catalyst weight,.Compared with similar catalyst, present invention catalysis
Agent can be used for drippolene or its fraction plus hydrogen, low temperature hydrogenation selectivity is high, and anti-As impurity ability is strong, and charging capacity is big, and
It is activity stabilized.CN200610029962.5 is related to a kind of method for full-cut fraction pyrolysis gasoline selective hydrogenation, mainly solves
It exists in the prior art and is difficult to the full-cut fraction pyrolysis gasoline high to colloid and free water content and carries out the technology of selective hydrogenation ask
Topic.The present invention is by using with C5The drippolene and hydrogen of the hydrocarbon compound fraction of hydrocarbon~do for 204 DEG C are raw material, anti-
Answering temperature is 30~80 DEG C, and reaction pressure is 2.0~3.0MPa, and green oil air speed is 2.5~5.0 hours- 1, hydrogen/oil volume ratio
Under conditions of 60~120: 1, raw material is contacted with catalyst, is reacted, and diolefin and alkylene aromatic hydrocarbons group in raw material are made
Point it is converted to monoolefine and alkylaromatic hydrocarbon, wherein catalyst includes alumina support, activity component metal palladium or its oxide, extremely
Element or its oxide, at least one IVA or VA in the periodic table of elements of few a kind of IA in the periodic table of elements or IIA
Element or its oxide, carrier specific surface area be 40~160 meters2/ gram, total pore volume is 0.3~1.2 ml/g, and carrier has
There is the technical solution of compound pore size distribution, preferably solve the problems, such as this, can be used for the work of full-cut fraction pyrolysis gasoline selective hydrogenation
In industry production.The preparation method of catalyst of the present invention is identical as common lamella catalyst dipping technique: first with it is a kind of can be with dipping
Liquid that liquid dissolves each other presoaks carrier, then with salt solution impregnation containing palladium, and the carrier after dipping is washed, dry, in air
300~600 DEG C roast up to oxidative catalyst finished product.Finished catalyst only need to lead in the reactor hydrogen reducing and can make
With.The catalyst that the present invention uses has a composite pore structural, it is biggish can several apertures, and rich in abundant mesoporous.The present invention
Catalyst be used for full-cut fraction pyrolysis gasoline selective hydrogenation when have good low temperature active, selectivity and stability, and
And there is good anti-interference, resistance to high colloid and high-content free water performance.In 40 DEG C of inlet temperature, reaction pressure
2.7Mpa, hydrogen/oil volume are than 80: 1, and green oil air speed 3.8 hours-1Under the conditions of, be 150 milligrams/100 grams oil to gum level,
Free water content is the full fraction (C of 1000ppm5The hydrocarbon compound fraction of hydrocarbon~do for 204 DEG C) drippolene selected
Hydrogenation reaction, outlet diene average value are 0.0 gram of iodine/100 gram oil, and diolefin hydrogenation rate is 100%, achieve preferable technology
Effect.The preparation method of the invention carrier include aluminium oxide and modifying agent, peptizing agent, water are mixed in the desired amount, extruded moulding
Afterwards, first 1~24 hour dry at 50~120 DEG C, it is then roasted 1~10 hour at 800~1150 DEG C, obtains carrying alumina
Body.
The prior art changes support chemistry composition and type, and addition coagent mainly to promote catalyst performance
Energy.Since the impurity such as As, S, O, N and gum level are higher in drippolene, catalyst is set to be easy inactivation, it is therefore desirable to crack vapour
Oily catalyst has anticol matter, water resistant ability good, the strong characteristic of anti-arsenic, sulfur resistive ability.
Summary of the invention
One-stage selective hydrogenation of gasoline splitting method of the present invention, is particularly suitable for full-cut fraction pyrolysis gasoline selective hydrogenation.
The process uses load type palladium catalyst, and carrier is the silicaalumina carrier comprising nickel doped lanthanum ferrite, to difference
Arsenic content, different sulfur contents, water content, the drippolene adaptability to raw material of gum level are strong, and catalyst low-temperature activity is good.Activity
Higher, selectivity is more preferable, and appearance glue ability is more preferable, and anti-arsenic, inhibits coking ability strong at sulfur resistive, to different arsenic contents, different sulfur contents
Full-cut fraction pyrolysis gasoline it is adaptable.
A kind of full-cut fraction pyrolysis gasoline section selective hydrogenation method, using fixed bed reactors, to urging under hydrogen atmosphere
Agent is restored, and is adjusted to reaction process condition after process to be restored, into full-cut fraction pyrolysis gasoline feedstock oil, is selected
Selecting property hydrogenation reaction；Catalyst includes silicaalumina carrier and the metal active component palladium that is carried on carrier, and palladium contains
Total weight of the amount based on the catalyst is 0.15-0.45wt%, includes the oxygen of 0.1~12wt% in silicaalumina carrier
SiClx, the nickel doped lanthanum ferrite of 0.1~10wt%, the potassium of 0.05~6.8wt%, carrier is mesoporous to account for the 3~75% of total hole, macropore
Account for the 1.5~60% of total hole.Micropore, mesoporous, macropore uneven distribution in carrier；Hydrogenation process conditions: reaction inlet temperature >=
50 DEG C, reaction pressure 2.0-4.5MPa, hydrogen to oil volume ratio 60~400；Liquid volume air speed 2.5-5.0h-1。
Preferably, the hydrogenation process conditions: liquid volume air speed 3.0-4.5h-1, reaction pressure 2.5-4.0MPa, hydrogen oil
Volume ratio 60~300.
The above-mentioned preferred 0.20-0.3wt% of Palladium Content in Catalyst.Preferably, mesoporous to account for the 3~65% of total hole, macropore accounts for
The 3~45% of total hole.
The silicaalumina carrier the preparation method is as follows: boehmite and sesbania powder are added to kneader
In be uniformly mixed, inorganic acid solution and organic polymer is added, mediates uniformly, then adds nickel doped lanthanum ferrite, mixing is equal
It is even to obtain alumina precursor, it is spare；Silicon source is added in the acid solution of organic polymer and boehmite is uniformly mixed, obtains
Silicon source-boehmite-organic polymer mixture, the organic polymer of unit content is more quasi- than silicon source-in alumina precursor
The high 2 times or more of content of organic polymer in boehmite-organic polymer mixture (brief note silicon-aluminium-organic admixture),
Then by silicon source -- boehmite-organic polymer mixture is mixed with alumina precursor, adds potassium resource, through extrusion,
Molding, dry, roasting, obtain silicaalumina carrier.The silicon source is silica gel, sodium metasilicate or silicon powder.Silicon-aluminium-is organic
Aluminium oxide accounts for 1~35wt% of aluminium oxide in carrier in object mixture.
The preparation process of above-mentioned silicaalumina carrier, the organic polymer are polyvinyl alcohol, polyacrylic acid, gather
One or more of sodium acrylate, polyethylene glycol, polyacrylate.
Preferably, in above-mentioned silicaalumina carrier nickel doped lanthanum ferrite be 0.1~12wt%, more preferable 0.2~
8wt%, nickel accounts for 0.1~8wt% of cadmium ferrite in nickel doped lanthanum ferrite.
The preparation method of the nickel doped lanthanum ferrite: citric acid is dissolved in stirring and dissolving in deionized water, then by nitric acid
Lanthanum and ferric nitrate are added in citric acid, and Sodium Polyacrylate, polyacrylate or polyacrylic acid, polyacrylic acid is added in stirring and dissolving
The additional amount of sodium, polyacrylate or polyacrylic acid is the 0.1~10wt%, preferably 0.1~8.0wt% of nickel doped lanthanum ferrite.
Nickel compound containing is added, stirs, obtains finished product through drying, roasting, grinding.The nickel compound containing includes nickel nitrate, acetic acid
Nickel etc..
The preparation method of catalyst by active component palladium dipping, can spray to oxidation using the methods of dipping, spraying
On silicon-carrier, then catalyst is dried, roasts and obtains the catalyst.Such as it can prepare and urge according to the following steps
Agent: preparing palladium-containing solution oxide impregnation silicon-alumina support, dries 3~9 hours through 110~160 DEG C, 400~650 DEG C of roastings
It burns 4~9 hours, finally obtains catalyst prod.
In the preparation method of catalyst of the present invention, palladium compound used can be any one disclosed in prior art
Suitable for the palladium compound of palladium catalyst processed, such as palladium chloride, palladium nitrate, palladium sulfate, tetrachloro-palladium acid aluminium, four cyano palladium acid aluminium, four nitre
Base palladium acid sodium, acylate such as oxalic acid palladium of palladium etc..To prepare solvent used in palladium compound solution do not have it is any specifically limited,
As long as it can dissolve used palladium compound.Preferred solvent be for example water, dilute hydrochloric acid, dust technology, dilute sulfuric acid or
Their mixed liquor.
Nickel doped lanthanum ferrite is added in silicaalumina carrier, effectively improves anti-arsenic, sulfur resistive, water repelling property, improves alkynes
Hydrocarbon or diolefin hydrogenation selectivity.In the preparation process of silicaalumina carrier, unit content is organic in alumina precursor
Polymer 2 times or more higher than the content of organic polymer in silicon-aluminium-organic admixture, is not simply reaming, but is carried
Body micropore, mesoporous, macropore uneven distribution are different from simple reaming, can not only improve the pore structure of carrier, keep carrier micro-
Hole, mesoporous, macropore uneven distribution improve catalyst anticol mass-energy power, improve the stability and service life of catalyst, favorably
In device long-term operation；And carrier surface is promoted to produce more active sites load centres, it improves palladium catalyst and adds hydrogen
Activity.
Specific embodiment
The present invention is described in further detail by the following examples, but these embodiments are not considered as to limit of the invention
System.
Prepare primary raw material source used in catalyst: source chemicals used in the present invention are commercial product.
Embodiment 1
1, nickel doped lanthanum ferrite is prepared
Under stirring condition, 2.51mol lanthanum nitrate is dissolved in 120mL water, citric acid stirring and dissolving is added；It adds
Then 4.79mol ferric nitrate adds 190g Sodium Polyacrylate, add the aqueous solution of the nickel nitrate containing 42g, continue to stir
30min, drying, roasting, grinding obtain nickel doped lanthanum ferrite.
2, silicaalumina carrier is prepared
It is spare that citric acid is added in 4.5g nickel doped lanthanum ferrite.300g boehmite powder and 25.0g sesbania powder are added
Enter into kneader, nitric acid is added, adds 40.2g Sodium Polyacrylate nitric acid solution, and be uniformly mixed, nickel doping is then added
Cadmium ferrite is uniformly mixed, obtains alumina precursor.5g Sodium Polyacrylate is dissolved in nitric acid, adds 38g silicon powder and 50g
Boehmite powder, stirs evenly, and obtaining silicon powder-boehmite-Sodium Polyacrylate mixture, (brief note silicon-aluminium-is organic
Object mixture).Silicon-aluminium-the organic admixture for taking 1/8, adds above-mentioned alumina precursor and 2.5g potassium nitrate, and mixing is equal
It is even, it is clover shape by kneading-extruded moulding.8 hours dry at 120 DEG C, 650 DEG C roast 6 hours, obtain nickeliferous doping
The carrier 1 of the silica-alumina of cadmium ferrite.The mesoporous of carrier accounts for the 55.4% of total hole, and macropore accounts for the 28.6% of total hole.
3, catalyst is prepared
Palladium solution impregnating carrier 1 is configured, 6 hours dry at 140 DEG C, 560 DEG C roast 5 hours, obtain catalyst 1.It urges
1 palladium content of agent is 0.29wt%.
Embodiment 2
260g Sodium Polyacrylate, silicaalumina carrier is only added with embodiment 1 in the preparation of nickel doped lanthanum ferrite
Preparation with embodiment 1, in silicaalumina carrier include 4.4wt% silica, the nickel doped lanthanum ferrite of 5.7wt%,
The potassium of 1.6wt%, carrier is mesoporous to account for the 64.2% of total hole, and macropore accounts for the 25.6% of total hole.Unit content in alumina precursor
Sodium Polyacrylate it is 3 times higher than the content of Sodium Polyacrylate in silicon source-organic polymer mixture.The preparation method of catalyst 2
With embodiment 1, palladium amount is 0.35wt%.
Embodiment 3
220g polyacrylic acid is only added with embodiment 1 in the preparation of nickel doped lanthanum ferrite, silicaalumina carrier
Preparation includes the silica of 8.4wt% with embodiment 1, in silicaalumina carrier, the nickel doped lanthanum ferrite of 2.6wt%,
The potassium of 0.8wt%, carrier is mesoporous to account for the 54.6% of total hole, and macropore accounts for the 33.5% of total hole.Unit content in alumina precursor
Polyacrylic acid it is 3.3 times higher than the content of polyacrylic acid in silicon source-organic polymer mixture.The preparation method of catalyst 3 is same
Embodiment 1, palladium amount are 0.21wt%.
Embodiment 4
280g Sodium Polyacrylate, silicaalumina carrier is only added with embodiment 1 in the preparation of nickel doped lanthanum ferrite
Preparation with embodiment 1, in silicaalumina carrier include 8.4wt% silica, the nickel doped lanthanum ferrite of 2.6wt%,
The potassium of 3.5wt%, carrier is mesoporous to account for the 49.3% of total hole, and macropore accounts for the 39.4% of total hole.Unit content in alumina precursor
Polyacrylate it is 3.3 times higher than the content of polyacrylate in silicon source-organic polymer mixture.The preparation side of catalyst 3
For method with embodiment 1, palladium amount is 0.26wt%.
Comparative example 1
1, cadmium ferrite is prepared
Under stirring condition, 2.51mol lanthanum nitrate is dissolved in 120mL water, citric acid stirring and dissolving is added；It adds
Then 4.79mol ferric nitrate adds 190g Sodium Polyacrylate, stir 30min, drying, roasting, grinding obtain nickel doping iron
Sour lanthanum.
2, silicaalumina carrier is prepared
It is spare that citric acid is added in 4.5g nickel doped lanthanum ferrite.300g boehmite powder and 25.0g sesbania powder are added
Enter into kneader, nitric acid is added, adds 40.2g Sodium Polyacrylate nitric acid solution, and be uniformly mixed, nickel doping is then added
Cadmium ferrite is uniformly mixed, obtains alumina precursor.5g Sodium Polyacrylate is dissolved in nitric acid, adds 38g silicon powder and 50g
Boehmite powder, stirs evenly, and obtaining silicon powder-boehmite-Sodium Polyacrylate mixture, (brief note silicon-aluminium-is organic
Object mixture).Silicon-aluminium-the organic admixture for taking 1/8, adds above-mentioned alumina precursor and 2.5g potassium nitrate, and mixing is equal
It is even, it is clover shape by kneading-extruded moulding.8 hours dry at 120 DEG C, 650 DEG C roast 6 hours, obtain Fe-laden acid lanthanum
Silica-alumina carrier 1-1.
3, comparative catalyst 1 is prepared
Palladium solution impregnating carrier 1-1 is configured, 6 hours dry at 140 DEG C, 560 DEG C roast 5 hours, obtain catalyst 1.
1 palladium content of comparative catalyst is 0.29wt%.
Comparative example 2
1, nickel doped lanthanum ferrite is prepared
Under stirring condition, 2.51mol lanthanum nitrate is dissolved in 120mL water, citric acid stirring and dissolving is added；It adds
Then 4.79mol ferric nitrate adds 190g Sodium Polyacrylate, add the aqueous solution of the nickel nitrate containing 42g, continue to stir
30min, drying, roasting, grinding obtain nickel doped lanthanum ferrite.
2, silicaalumina carrier is prepared
It is spare that citric acid is added in 4.5g nickel doped lanthanum ferrite, 350g boehmite powder and 25.0g sesbania powder are added
Enter into kneader, nitric acid is added, adds 40.7g Sodium Polyacrylate nitric acid solution, and be uniformly mixed, it is micro- to add 4.8g silicon
Powder is mediated uniformly, nickel doped lanthanum ferrite and 2.5g potassium nitrate is then added, is uniformly mixed, and is three leaves by kneading-extruded moulding
Careless shape.8 hours dry at 120 DEG C, 650 DEG C roast 6 hours, obtain the load of the silica-alumina of nickeliferous doped lanthanum ferrite
Body 1-2.
3, comparative catalyst 2 is prepared
Palladium solution impregnating carrier 1-2 is configured, 6 hours dry at 140 DEG C, 560 DEG C roast 5 hours, obtain comparison catalysis
Agent 2.2 palladium content of comparative catalyst is 0.29wt%.
Catalyst 1-4 and comparative catalyst 1 and 2 are respectively charged into 100ml insulation bed reaction device, at 125 DEG C of temperature,
It is restored 8 hours under the conditions of the volume ratio 250:1 of hydrogen and catalyst, cools to 40 DEG C of laggard full-cut fraction pyrolysis gasoline (C5~C9)
Feedstock oil, diene content is 46.04g iodine/100g oil, iodine number 128.97g iodine/100g, glue in full-cut fraction pyrolysis gasoline feedstock oil
Matter content is 109mg/100ml oil, free water content is that 1123ppm sulfur content is 143ppm and arsenic content is 73ppb；React work
Skill condition are as follows: 55 DEG C of inlet temperature, hydrogen to oil volume ratio 260: 1, reaction pressure 3.0MPa, green oil air speed 3.5h-1；Operate 200h
The average diene of 1 hydrogenated products of catalyst is 1.21 grams of iodine/100 gram oil, iodine number 42.06g iodine/100g, diolefin hydrogenation rate
89.7%.The average diene of 2 hydrogenated products of catalyst is 1.49 grams of iodine/100 gram oil, iodine number 40.21g iodine/100g, diolefin hydrogenation
Rate 90.5%.The average diene of 3 hydrogenated products of catalyst is 1.73 grams of iodine/100 gram oil, and iodine number 41.25g iodine/100g, diene adds
Hydrogen rate 89.4%.The average diene of 4 hydrogenated products of catalyst is 1.71 grams of iodine/100 gram oil, iodine number 41.31g iodine/100g, diene
Hydrogenation rate 89.1%.The average diene of 1 hydrogenated products of comparative catalyst be 3.54 grams of iodine/100 gram oil, iodine number 47.89g iodine/
100g, diolefin hydrogenation rate 78.3%.；The anti-arsenic of comparative catalyst 1, sulfur resistive, water repelling property are poor, and diolefin hydrogenation is selectively low；Than urging
The average diene of 2 hydrogenated products of agent is 2.89 grams of iodine/100 gram oil, iodine number 44.22g iodine/100g, diolefin hydrogenation rate
80.1%.；2 anticol mass-energy power of comparative catalyst is poor, and activity is low.Catalyst 1-4 activity is higher, and selectivity is more preferable, and anticol matter resists
Outlet capacity is more preferable, and anti-arsenic, sulfur resistive ability are strong.
After catalyst 1-2 operates 600h, the average diene of 1 hydrogenated products of catalyst is 1.29 grams of iodine/100 gram oil, iodine number
42.75g iodine/100g, diolefin hydrogenation rate 89.5%.The average diene of 2 hydrogenated products of catalyst is 1.51 grams of iodine/100 gram oil, iodine
Value 40.75g iodine/100g, diolefin hydrogenation rate 90.3%.Contain nickel doped lanthanum ferrite in catalyst carrier, is conducive to inhibit diene
Polymerization reaction occurs for the unsaturation component such as hydrocarbon and styrene；Catalyst is insensitive to impurity such as water, colloids, catalyst anticol matter,
Water resistant ability is good, and anti-arsenic, sulfur resistive ability are strong, stable in catalytic performance.Catalyst carrier micropore, mesoporous, macropore uneven distribution, palladium
Good catalyst activity, stability is good, long service life, is conducive to device long-term operation.
Catalyst 1-2 is respectively charged into 100ml insulation bed reaction device, at 125 DEG C of temperature, the body of hydrogen and catalyst
Product cools to 40 DEG C of laggard feedstock oils, full-cut fraction pyrolysis gasoline (C than restoring 8 hours under the conditions of 250:15~C9) diene content is
42.14g iodine/100g oil, iodine number 135.42g iodine/100g, gum level are 213mg/100ml oil, sulfur content 51ppm, are dissociated
Water content is 936ppm and arsenic content is 110ppb；Reaction process condition are as follows: 60 DEG C of inlet temperature, hydrogen to oil volume ratio 280: 1, instead
Answer pressure 2.5MPa, green oil air speed 4.0h-1；The average diene for operating 1 hydrogenated products of 200h catalyst is 1.12 grams of iodine/100
Gram oil, iodine number 41.33g iodine/100g, diolefin hydrogenation rate 90.1%.The average diene of 2 hydrogenated products of catalyst be 1.21 grams of iodine/
100 grams of oil, iodine number 40.10g iodine/100g, diolefin hydrogenation rate 90.9%.Catalyst contains different sulfur contents, free water content, arsenic
Amount, the oil of gum level are adaptable.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (10)
1. a kind of full-cut fraction pyrolysis gasoline process for selective hydrogenation, which is characterized in that fixed bed reactors are used, under hydrogen atmosphere
Catalyst is restored, is adjusted to reaction process condition after process to be restored, into full-cut fraction pyrolysis gasoline feedstock oil, into
Row selective hydrogenation；Catalyst includes silicaalumina carrier and the metal active component palladium that is carried on carrier, palladium
Total weight of the content based on the catalyst be 0.15-0.45wt%, include 0.1~12wt% in silicaalumina carrier
Silica, the nickel doped lanthanum ferrite of 0.1~10wt%, the potassium of 0.05~6.8wt%, carrier is mesoporous to account for the 3~75% of total hole,
Macropore accounts for the 1.5~60% of total hole.Micropore, mesoporous, macropore uneven distribution in carrier；Hydrogenation process conditions: reaction entrance temperature
>=50 DEG C, reaction pressure 2.0-4.5MPa, 60~400:1 of hydrogen to oil volume ratio of degree；Liquid volume air speed 2.5-5.0h-1。
2. full-cut fraction pyrolysis gasoline process for selective hydrogenation according to claim 1, which is characterized in that the palladium is chlorination
One of palladium, palladium nitrate, palladium sulfate, tetrachloro-palladium acid aluminium, four cyano palladium acid aluminium, tetranitro palladium acid sodium, oxalic acid palladium, the content of palladium
For 0.20-0.3wt%.
3. full-cut fraction pyrolysis gasoline process for selective hydrogenation according to claim 1, which is characterized in that the hydrogenation technique
Condition: liquid volume air speed 3.0-4.5h-1, react inlet temperature >=55 DEG C, reaction pressure 2.5-4.0MPa, hydrogen to oil volume ratio 60
~300:1.
4. full-cut fraction pyrolysis gasoline process for selective hydrogenation according to claim 1, which is characterized in that the carrier is mesoporous
The 3~65% of total hole are accounted for, macropore accounts for the 3~45% of total hole.
5. full-cut fraction pyrolysis gasoline process for selective hydrogenation according to claim 1, which is characterized in that the silica-
Being uniformly mixed the preparation method is as follows: boehmite and sesbania powder are added in kneader for alumina support, is added inorganic
Acid solution and organic polymer are mediated uniformly, then add nickel doped lanthanum ferrite, are uniformly mixed and obtain alumina precursor,
It is spare；Silicon source is added in the acid solution of organic polymer and boehmite is uniformly mixed, obtaining silicon source-boehmite-has
Machine polymeric blends, the organic polymer of unit content is than silicon source-boehmite-organic polymer in alumina precursor
The high 2 times or more of the content of organic polymer in mixture, then by silicon source -- boehmite-organic polymer mixture and oxygen
Change the mixing of aluminium presoma, adds potassium resource, through extrusion, molding, drying, roasting, obtain silicaalumina carrier.
6. full-cut fraction pyrolysis gasoline process for selective hydrogenation according to claim 5, which is characterized in that the silica-
Nickel doped lanthanum ferrite is 0.1~12wt% in alumina support.
7. full-cut fraction pyrolysis gasoline process for selective hydrogenation according to claim 5, which is characterized in that the organic polymer
Object is one or more of polyvinyl alcohol, polyacrylic acid, Sodium Polyacrylate, polyethylene glycol, polyacrylate.
8. full-cut fraction pyrolysis gasoline process for selective hydrogenation according to claim 5, which is characterized in that the silicon source is silicon
Glue, sodium metasilicate or silicon powder, in silicon source-boehmite-organic polymer mixture aluminium oxide account for aluminium oxide in carrier 1~
35wt%.
9. described in any item full-cut fraction pyrolysis gasoline process for selective hydrogenation according to claim 1~8, which is characterized in that institute
It states the preparation method of nickel doped lanthanum ferrite: citric acid being dissolved in stirring and dissolving in deionized water, then by lanthanum nitrate and ferric nitrate
It is added in citric acid, stirring and dissolving, Sodium Polyacrylate, polyacrylate or polyacrylic acid, Sodium Polyacrylate, polyacrylic acid is added
The additional amount of ester or polyacrylic acid be nickel doped lanthanum ferrite 0.1~10wt%, add nickel compound containing, stir, through drying,
Roasting, grinding obtain finished product.
10. described in any item full-cut fraction pyrolysis gasoline process for selective hydrogenation according to claim 1~8, which is characterized in that institute
The preparation process for stating catalyst is as follows: it prepares palladium-containing solution and impregnates the alumina support containing macropore, through 110~160 DEG C of drying 3~
9 hours, 400~650 DEG C roasted 4~9 hours, finally obtained catalyst prod.
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| CN111375450A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Alumina carrier and preparation method and application thereof |
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| CN101035618A (en) * | 2004-09-07 | 2007-09-12 | Abb路慕斯全球股份有限公司 | Hydroprocessing catalyst with zeolite and high mesoporosity |
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| CN101035618A (en) * | 2004-09-07 | 2007-09-12 | Abb路慕斯全球股份有限公司 | Hydroprocessing catalyst with zeolite and high mesoporosity |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111375450A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Alumina carrier and preparation method and application thereof |
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Effective date of registration: 20200811 Address after: Chen Town Industrial Park 257447 Shandong city of Dongying province Lijin County Applicant after: Dongying Huahao Chemical Co., Ltd Address before: Room 302, Ladder C, Haojiang Building, 505 Haojiang Road, Shishi City, Quanzhou City, Fujian Province Applicant before: Shi Qingcai |
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Denomination of invention: Selective hydrogenation of pyrolysis gasoline Effective date of registration: 20200929 Granted publication date: 20200908 Pledgee: Hengfeng bank Limited by Share Ltd. Dongying branch Pledgor: Dongying Huahao Chemical Co., Ltd Registration number: Y2020370010042 |