CN109468144A - A kind of method of FCC gasoline light fraction dialkene removal - Google Patents
A kind of method of FCC gasoline light fraction dialkene removal Download PDFInfo
- Publication number
- CN109468144A CN109468144A CN201811286737.9A CN201811286737A CN109468144A CN 109468144 A CN109468144 A CN 109468144A CN 201811286737 A CN201811286737 A CN 201811286737A CN 109468144 A CN109468144 A CN 109468144A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- lanthanum
- light fraction
- nickel
- fcc 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 86
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 26
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011733 molybdenum Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000000470 constituent Substances 0.000 claims abstract description 7
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 5
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical group [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005520 cutting process Methods 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 66
- -1 lanthanum-magnesium aluminate Chemical class 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 239000003921 oil Substances 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- 239000004411 aluminium Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 10
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229920001661 Chitosan Polymers 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 claims description 5
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 5
- 239000001095 magnesium carbonate Substances 0.000 claims description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 239000011863 silicon-based powder Substances 0.000 claims description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 4
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 229960001633 lanthanum carbonate Drugs 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001223 polyethylene glycol 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
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims 1
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 abstract description 42
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 21
- 150000001336 alkenes Chemical class 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- 238000004939 coking Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 229910001593 boehmite Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 239000003223 protective agent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 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 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- RIAXXCZORHQTQD-UHFFFAOYSA-N lanthanum magnesium Chemical compound [Mg].[La] RIAXXCZORHQTQD-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 235000011160 magnesium carbonates Nutrition 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241000295146 Gallionellaceae Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 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
- 239000003513 alkali Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- SHFGJEQAOUMGJM-UHFFFAOYSA-N dialuminum dipotassium disodium dioxosilane iron(3+) oxocalcium oxomagnesium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Na+].[Na+].[Al+3].[Al+3].[K+].[K+].[Fe+3].[Fe+3].O=[Mg].O=[Ca].O=[Si]=O SHFGJEQAOUMGJM-UHFFFAOYSA-N 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 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
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel 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
- 238000005507 spraying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
- C10G45/06—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
- C10G45/08—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 in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- 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
- B01J23/74—Iron group metals
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Abstract
The present invention relates to a kind of methods of FCC gasoline light fraction dialkene removal, gasoline is first cut into light and heavy fractions, cutting temperature is 70 DEG C, gasoline light fraction enters reactor and carries out dialkene removal reaction, used catalyst is nickel molybdenum system hydrogenation catalyst, and catalyst includes silicaalumina carrier and the metal active constituent nickel, molybdenum, the strontium that are carried on carrier, reaction process condition are as follows: 120~210 DEG C of reaction temperature, 1.5~3.5MPa of reaction pressure, 1.0~25.0h of liquid volume air speed‑1, hydrogen to oil volume ratio is 4~300:1.FCC gasoline method for removing alkadiene of the invention, adaptable to different material oil, alkadienes removal efficiency is high, and catalyst is not easy to be poisoned, stable in catalytic performance.
Description
Technical field
The present invention relates to a kind of methods of FCC gasoline light fraction dialkene removal, split suitable for selective hydrogenation and removing catalysis
Change the alkadienes in (FCC) gasoline light fraction.
Background technique
Contain more alkadienes in the distillates such as catalytically cracked gasoline, coker gasoline, drippolene, in certain reaction
At a temperature of, alkadienes can also react in addition to polymerization itself with other hydro carbons, generate the cokings precursors such as colloid.Usually
It is removed using the method choice for adding hydrogen.US6,084,140 discloses height unsaturated hydrocarbons in a kind of pair of olefine fraction
The preparation method of selective hydrocatalyst.The catalyst is made of aluminium oxide and the Metal Palladium being supported on the aluminium oxide.Gold
The content for belonging to palladium is 0.02-3.0 weight %.The catalyst can effectively remove the height unsaturated hydrocarbons in olefine fraction.US6,
255,548 disclose a kind of preparation method to unsaturated hydro carbons such as alkynes and alkadienes selective hydrocatalyst.The catalysis
Agent is supported on carrier by least one group VIII metal and at least one promoter metal M and is made.The group VIII metal can be
One or more of nickel, palladium, platinum, rhodium, ruthenium, iridium.Selective hydrogenation is carried out using noble metal catalyst, it can be well by raw material
Alkadienes removing in oil.But for sulphur, the higher full fraction of nitrogen content or heavy distillat catalytically cracked gasoline, noble metal is easy to lose
It is living, it is restricted the use of this kind of catalyst.
Coking reaction can occur with hydro carbons other in catalytically cracked gasoline for alkadienes, and the burnt matter of generation is easy product knot and is urging
Agent bed causes reaction pressure drop to increase, until stop device.Therefore it needs to be removed using the method for selective hydrogenation.By
It is easy to polymerize in alkene, monoolefine is easy plus hydrogen is saturated, and to improve its selectivity and noble metal catalyst is used to carry out selective add
Hydrogen can remove the alkadienes in feedstock oil well.But it is evaporated entirely using sulphur, nitrogen content when noble metal catalyst are higher
Divide or heavy distillat catalytically cracked gasoline makes noble metal be easy to inactivate.Selectively added using non-noble metal hydrogenation catalyst for refining
Hydrogen can also remove the alkadienes in feedstock oil well.
CN1676580A discloses a kind of method for removing alkadiene by selective hydrogenation, and this method is included in hydrofining technology item
Under part, distillate is contacted with catalyst, the catalyst contain a kind of alumina support and load cobalt on this carrier and/
Or nickel, molybdenum and/or tungsten and alkaline components, the alkali metal are 1.3-6 with the atomic ratio of cobalt and/or nickel.Feedstock oil alkadienes
Value 1.8-1.9gI/100g, product oil alkadienes value 0.5-1.0gI/100g.CN1631529A discloses a kind of alkadienes selection
Property hydrogenation catalyst, which contains the cobalt and/or nickel, molybdenum and/or tungsten of a kind of alumina support and load on this carrier
And alkali metal, which is characterized in that the hole that the bore dia in the alumina support is 100-200 angstroms accounts for the 55-90% of total pore volume.
Feedstock oil alkadienes value 5.39gI/100g, product oil alkadienes value 0.4-1.6gI/100g.Above-mentioned alkadienes selective hydrogenation is urged
Agent can not preferably solve the pressure reacted in next step secondly olefin removal rate is lower due to the influence of its carrier compound
Drop.CN200710118860.5 is related to a kind of method of hydrogenation dialkene removal of catalytically cracked gasoline, to alkadienes value 2.56gI.
(100g)- 1Catalytically cracked gasoline distillate carry out hydrogenation dialkene removal, reaction temperature is 120-280 DEG C, and hydrogen partial pressure is
1.0-5.0 megapascal, liquid hourly space velocity (LHSV) are 1.0-20.0 hours- 1, hydrogen to oil volume ratio 10-400；Catalyst is with aluminium oxide and Y
Molecular sieve is complex carrier, loads 3.35% cobalt oxide, 10.03% molybdenum oxide, 0.86% magnesia, 1.01% nickel oxide, urges
Agent total weight is 100%；The atomic ratio of magnesium and cobalt and nickel is 6.8；The alkadienes average value for generating oil decreases below
0.2gI.(100g)- 1, dialkene removal selectively reaches 95.1%, and the octane number RON of feedstock oil reduces ≯ 1, and monoolefine reduces ≯
3v%, the liquid yield average value of gasoline are 99.6 mass %.CN200910082945.1 is related to a kind of catalytically cracked gasoline choosing
Selecting property hydrogenation catalyst and preparation method thereof.Catalyst of the present invention is by Al2O3-TiO2Composite oxide carrier and active metal oxygen
Compound composition, based on the weight percent to catalyst, the NiO content in reactive metal oxides is 10~20w%, MoO3
Content is 5~12w%；Wherein the weight ratio of carrier Al2O3-TiO2 oxide TiO2: Al2O3 is 0.01~1: 1.The present invention urges
Agent is in low temperature (100~200 DEG C), low pressure (1~3.0MPa), the condition of low hydrogen/gasoline ratio (hydrogen to oil volume ratio 5: 1~100: 1)
Under, catalytically cracked gasoline is handled, very high de- diolefin and removal of mercaptans activity, selectivity and stability are shown.
Gasoline selective alkadienes in hydrogenation and removing feedstock oil while, avoid or reduce olefinic polymerization, monoolefine
Hydrogen is added to be saturated, to improve the selectivity of hydrogenation reaction.Alkene saturation causes bed temperature rise to increase, and hydrogen consumption increases, CN1113829A
Disclose it is a kind of containing molybdenum, nickel, potassium metal component Hydrobon catalyst preparation method, being mainly characterized by will be preforming
Transition state of alumina carrier, molybdenum, nickel, potassium solution of the single-steeping containing ammonia, through drying, roast be made catalyst.Transient oxygen
Changing aluminium includes the preferred gama-alumina of η, γ, θ aluminium oxide.The catalyst metal components content be MoO310.0~24.0%,
NiO2.6~8.8%, K0.3~1.5%.The catalyst can be used for the hydrodesulfurization of light oil distillate or gas containing organic sulfur, special
Not Shi Yongyu naphtha and coking dry gas hydrodesulfurization.CN1302849A discloses a kind of Hydrogenation active protective agent and its preparation
Method contains gama-alumina and δ-aluminium oxide in protective agent used carrier simultaneously；Metal oxide containing group vib 3 in protective agent~
22% and group VIII metal 0.5~5m% of oxide, the 0~2m% of element of race containing IA, the 0~3m% of element of race containing VA, specific surface 100
~250m2/g.Hole holds 0.4~0.8ml/g.Group vib metal oxide is the oxide of Mo, W, group VIII gold in the protective agent
Belong to the oxide that oxide is Fe, Co, Ni, VA race element is P, As, Sb, Bi element.The catalyst adds suitable for mink cell focus
The protective agent that hydrogen handles catalyst uses.Using above-mentioned alkali metal containing component Hydrobon catalyst to gasoline fraction oil into
When row removing alkadiene by selective hydrogenation, since the activity and selectivity of catalyst is low, effect is poor.CN201210143124.6 is mentioned
For a kind of alkadienes selective hydrocatalyst, containing carrier, load on this carrier at least one selected from group VIII
Non-noble metal components, at least one metal component and at least one alkali gold selected from lithium, sodium, potassium and rubidium selected from group VIB
Belong to component, wherein on the basis of catalyst, the mass fraction of the group VIII metal component in terms of oxide is 1.5-8%, with oxygen
The mass fraction of the vib metals component of compound meter is 5.5-30 weight %, the quality of the alkaline components in terms of oxide
Score is 1-7%, and the carrier is the molding of alumina hydrate-containing.Catalyst provided by the invention is in gasoline fraction oil
Alkadienes hydrogenation activity with higher and selectivity, particularly suitable for the gasoline fraction oil containing alkadienes to add hydrogen de- two
Alkene is purpose hydrofinishing.A kind of distillate method for removing alkadiene by selective hydrogenation of CN200410029865.7, this method packet
It includes under the conditions of hydrofining technology, distillate is contacted with catalyst, the catalyst contains a kind of alumina support and negative
Carry cobalt on this carrier and/or nickel, molybdenum and/or tungsten and alkaline components, which is characterized in that the alkali metal and cobalt and/or
The atomic ratio of nickel is 1.3-6.Compared with the conventional method, the removing alkadiene by selective hydrogenation significant effect of the method provided by the present invention
It improves.CN201611113355.7 provides a kind of full fraction FCC gasoline dialkene removal/ultra-deep desulfurization compounding method,
The following steps are included: one, use full fraction FCC gasoline and hydrogen for raw material, contacted with dialkene removal catalyst, with removing evaporate entirely
Divide the alkadienes in FCC gasoline；Two, it is fractionated, forms heavy constituent and light component；Three, hydrodesulfurization is carried out to heavy constituent, obtained low
Sulphur heavy constituent；Light component is carried out to face hydrogen desulfurization absorption desulfurization, obtains low-sulfur light component；Four, low-sulfur heavy constituent and low-sulfur is light
Component mixing obtains the super low-sulfur oil that sulfur content is lower than 10ppmw.The present invention is by carrying out selectivity to full fraction FCC gasoline
Hydrogenation dialkene removal, and using hydrodesulfurization and face at the combined type of hydrogen absorption desulfurization combined technology progress ultra-deep desulfurization
Reason, the sulphur in full fraction FCC gasoline can be taken off to 10ppmw hereinafter, and loss of octane number lower than 2 units, liquid yield is big
In 99.8%.Above-mentioned catalytic component is more, and preparation process is complicated, part document diene hydrogenation selectivity and alkadienes removal efficiency
It is to be improved.
Therefore, it is necessary to develop a kind of dialkene removal activity it is high, selectivity good, the hydrogenation catalyst and work of stable in catalytic performance
Skill, and catalyst has good resistant to sulfur, water resistant, anticol matter, anti-coking, the performance for inhibiting olefinic polymerization.
Summary of the invention
The present invention provides a kind of method of FCC gasoline light fraction dialkene removal, using nickel, molybdenum series catalyst, catalyst
Carrier is a kind of silicaalumina carrier, includes nickel doped lanthanum ferrite in carrier, catalyst hydrogenation reactivity is high, selection
Property is good, and anticol matter, water resistant ability are good, and side reaction is few.Catalyst is particularly suitable for FCC gasoline selective hydrogenation and removing alkadienes.
A kind of method of FCC gasoline light fraction dialkene removal, using fixed bed reactors；Gasoline is first cut into weight and evaporates
Point, cutting temperature is 70 DEG C, and gasoline light fraction enters reactor and carries out dialkene removal reaction, and used catalyst is that nickel molybdenum system adds hydrogen
Catalyst, catalyst include silicaalumina carrier and the metal active constituent nickel, molybdenum, the strontium that are carried on carrier, with catalysis
It include following components: nickel oxide content 2-18wt% on the basis of the total weight of agent, the content of molybdenum oxide is 2-12wt%, oxidation
Content of strontium is 0.05~4.5%, and silicaalumina carrier content is 67-85wt%, includes in silicaalumina carrier
The silica of 0.1~15wt%, the lanthanum-magnesium aluminate of 0.5~15wt%, the aluminium oxide of 60~86.0wt%；Reaction process condition
Are as follows: 120~210 DEG C of reaction temperature, 1.5~3.5MPa of reaction pressure, 1.0~25.0h of liquid volume air speed-1, hydrogen to oil volume ratio
For 4~300:1.
Preferably, the fixed bed reactors are fixed bed adiabatic reactor either fixed bed isothermal reactors；Reaction
120~180 DEG C of device inlet temperature, 1.5~3MPa of reaction pressure, 2.0~20.0h of liquid volume air speed-1, hydrogen to oil volume ratio 4~
200:1。
It preferably, include following components: nickel oxide content 4-18wt%, molybdenum oxide on the basis of the total weight of catalyst
Content be 4-12wt%.
The silicaalumina carrier the preparation method is as follows: the silicon source of 55%-75% is taken to mix with sesbania powder
It is even, acid solution and expanding agent 1 is added, the additional amount of expanding agent 1, which accounts for, is added the 15~30% of quality of alumina, it mediates uniformly, then
Lanthanum-magnesium aluminate is added, is uniformly mixed and obtains the mixture (1) containing aluminium and lanthanum-magnesium aluminate；Silicon source is mixed with 25%~45% silicon source
Uniformly, add expanding agent 2, the additional amount of expanding agent 2 account for addition aluminium oxide and siliconoxide mass 0.1~8%, obtain
Silicon-aluminium mixture (2)；By containing aluminium and lanthanum-magnesium aluminate mixture (1) and silicon-aluminium mixture (2) be uniformly mixed, through extrusion, at
Type, drying, 400~650 DEG C of 3~12h of roasting, obtain silicaalumina carrier.The silicon source is silica gel, sodium metasilicate or silicon
One or both of micro mist, diatomite.Source of aluminium is one or more of aluminium oxide, boehmite, aluminum sulfate.Aluminium
Source can also be selected from one or more of montmorillonite, kaolin, perlite, rectorite.
The preparation process of above-mentioned silicaalumina carrier, the expanding agent 1 are polyvinyl alcohol, polyacrylic acid, polypropylene
One or more of sour sodium, polyethylene glycol, polyacrylate.The expanding agent 2 be methylcellulose, polymethylacrylic acid,
One or more of ammonium acrylate, glucose, chitosan etc..The binder is that the clay, Aluminum sol or silicon of silicon-aluminum containing are molten
Glue.It include the silica of 0.1~15wt%, the lanthanum-magnesium aluminate of 0.5~15wt%, the oxidation of 60~86.0wt% in control vector
Aluminium.
Deionized water is added in above-mentioned lanthanum-magnesium aluminate powder materials, obtains the aluminic acid of high dispersive through high-speed stirred or ultrasonic oscillation
Then magnesium lanthanum slurry adds in mixture (1).The clay, Aluminum sol, silicon that silicon-aluminum containing can be also introduced in lanthanum-magnesium aluminate slurry are molten
The one or more such as glue, dosage account for the 0.1~18% of lanthanum-magnesium aluminate slurry gross mass.In control vector comprising 0.1~
The silica of 15wt%, the lanthanum-magnesium aluminate of 0.5~15wt%, the aluminium oxide of 60~86.0wt%.
Prepare lanthanum-magnesium aluminate LaMgAl11O19Process it is as follows: basic magnesium carbonate, lanthanum carbonate and aluminium hydroxide are pressed
LaMgAl11O19Stoichiometric coefficient than being uniformly mixed, be added in deionized water, stir evenly, after spray-dried, logical
It under air conditions, is roasted 2~10 hours through 1200~1400 DEG C, is crushed, ball milling, obtain lanthanum-magnesium aluminate powder materials.Further
Ground introduces nickel in lanthanum-magnesium aluminate, prepares nickeliferous lanthanum-magnesium aluminate LaMgAl11O19Process it is as follows: basic magnesium carbonate, lanthanum carbonate and
Aluminium hydroxide presses LaMgAl11O19Stoichiometric coefficient than be uniformly mixed, be added deionized water in, stir evenly, add nitre
Sour nickel is uniformly mixed, and after spray-dried, under the conditions of blowing air, is roasted 2~10 hours through 1200~1400 DEG C, crushed,
Ball milling obtains lanthanum-magnesium aluminate powder materials.Nickel mass content is 0.1~12% in nickeliferous lanthanum-magnesium aluminate.Nickel is introduced in lanthanum-magnesium aluminate,
The interaction for improving carrier surface aluminium oxide and molybdenum, nickel isoreactivity component roasting process, makes nickel be not easy to assemble, molybdenum, nickel, strontium are most
It may uniformly be precipitated, be carried on carrier surface.
Solution containing active component can be impregnated, be sprayed to using the methods of dipping, spraying by the preparation method of catalyst
On silicaalumina carrier, then catalyst is dried, roasts and obtains the catalyst.Such as it can be by following
Step prepares catalyst: nickel nitrate, strontium nitrate, ammonium molybdate solution oxide impregnation silicon-alumina support is prepared, through 110~155 DEG C
Drying 3~12 hours, 420~650 DEG C roast 4~12 hours, obtain catalyst prod.
In the preparation method of catalyst of the present invention, the compound of nickel used and molybdenum can be prior art disclosed
A kind of what compound suitable for catalyst processed, such as nickel nitrate, nickel sulfate, nickel acetate, ammonium molybdate, molybdenum oxide.
Contain more alkadienes in the distillates such as catalytically cracked gasoline, coker gasoline, drippolene, in certain reaction
At a temperature of, alkadienes can also react in addition to polymerization itself with other hydro carbons, generate the cokings precursors such as colloid.In temperature
When higher, polymerization reaction easily occurs for alkene, alkadienes in raw material, and is further condensed green coke, and reacting system pressure increases, sternly
It is forced to stop when weight.
Nickel system selective hydrocatalyst of the invention, including silicaalumina carrier and the gold being carried on carrier
Belong to active component nickel, molybdenum, strontium, includes lanthanum-magnesium aluminate in silicaalumina carrier, effectively improve anti-arsenic, sulfur resistance, inhibit
Olefinic polymerization, the nickel molybdenum series catalyst of preparation, diolefin hydrogenation selectivity are high.The preparation process of silicaalumina carrier: oxidation
Aluminium is divided into two parts addition, mixes respectively with lanthanum-magnesium aluminate and silica, and different expanding agents, reaming are introduced in mixture
The content of agent is also different, and the expanding agent mass content in aluminium oxide and lanthanum-magnesium aluminate mixture (1) is higher than aluminium oxide and silica
Expanding agent mass content in mixture (2).Catalyst is able to suppress olefinic polymerization plastic, within certain reaction time, reduces
The production quantity of colloid improves catalyst anticol mass-energy power, reduces catalyst surface coking process, catalyst diene and alkynes add hydrogen
Selectivity is high.Be conducive to device long-term operation.
FCC gasoline method for removing alkadiene of the invention, to different sulfur contents, gum level, water content, olefin-content gasoline
Gasoline it is adaptable, alkadienes removal efficiency is high, and catalyst is not easy to be poisoned, stable in catalytic performance.
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, lanthanum-magnesium aluminate LaMgAl is prepared11O19Process it is as follows:
7.8 grams of basic magnesium carbonates, 25 grams of lanthanum carbonates and 70.5 grams of aluminium hydroxides are taken, are uniformly mixed, are added in deionized water
Form the suspension of high dispersive, it is spray-dried, 140 DEG C drying 5 hours, be placed in air atmosphere 1300 DEG C of roastings 4 hours,
Then lanthanum-magnesium aluminate powder is obtained within ball milling 18 hours.Lanthanum-magnesium aluminate powder adds water, and the aluminium of high dispersive is obtained after ultrasonic oscillation
Sour magnesium lanthanum slurry.
2, silicaalumina carrier is prepared
It takes the boehmite of 170g to be uniformly mixed with 30g sesbania powder, dust technology is added, adds 32g Sodium Polyacrylate
Nitric acid solution, and be uniformly mixed, lanthanum-magnesium aluminate slurry is then added, is uniformly mixed, obtains the mixture containing aluminium and lanthanum-magnesium aluminate
(1)；22g silicon powder is uniformly mixed with the boehmite of 71g, and 8.1g water soluble chitosan is added, adds silica solution, obtains
Silicon-aluminium mixture (2)；By containing aluminium and lanthanum-magnesium aluminate mixture (1) and silicon-aluminium mixture (2) mix and grind mixed, mediated, squeezed
Item obtains the silicaalumina carrier containing lanthanum-magnesium aluminate at trifolium-shaped, through 130 DEG C of dry 10h, 560 DEG C of roasting 5h.
3, catalyst is prepared
Nickel nitrate, strontium nitrate, ammonium molybdate solution impregnated carrier are configured, 6 hours dry at 140 DEG C, 560 DEG C of roastings 5 are small
When, obtain catalyst 1.The composition of catalyst is shown in Table 1.
Embodiment 2
The preparation of lanthanum-magnesium aluminate with embodiment 1, the preparation of silicaalumina carrier with embodiment 1, take 68% intend it is thin
Diaspore is uniformly mixed with sesbania powder, and the additional amount of 1 polyacids sodium of expanding agent, which accounts for, is added the 19% of quality of alumina, 2 first of expanding agent
The additional amount of base cellulose account for addition aluminium oxide and siliconoxide mass 4%.Include in silicaalumina carrier
The silica of 7.2wt%, the lanthanum-magnesium aluminate of 6.6wt%.
The preparation method is the same as that of Example 1 for catalyst, and the composition of catalyst is shown in Table 1.
Embodiment 3
The preparation of nickeliferous lanthanum-magnesium aluminate: taking 7.8 grams of basic magnesium carbonates, 25 grams of lanthanum carbonates and 70.5 grams of aluminium hydroxides, mixing
Uniformly, it is added in deionized water and forms the suspension of high dispersive, add 8 grams of nickel nitrates, spray-dried, 140 DEG C of dryings 5 are small
When, it is placed in air atmosphere and roasts 4 hours for 1300 DEG C, then obtain nickeliferous lanthanum-magnesium aluminate powder within ball milling 18 hours.Nickel-and aluminum-containing
Sour magnesium lanthanum powder adds water, and the nickeliferous lanthanum-magnesium aluminate slurry of high dispersive is obtained after ultrasonic oscillation.
Nickeliferous lanthanum-magnesium aluminate slurry is only added with embodiment 1 in the preparation of silicaalumina carrier, take 72% it is quasi-
Boehmite is uniformly mixed with sesbania powder, and the additional amount of 1 polyacrylate of expanding agent, which accounts for, is added the 21% of quality of alumina, reaming
The additional amount of 2 methylcellulose of agent account for addition aluminium oxide and siliconoxide mass 2.6%.It is wrapped in silicaalumina carrier
Silica containing 4.8wt%, the lanthanum-magnesium aluminate of 5.2wt%.
The preparation method is the same as that of Example 1 for catalyst 3, and the composition of catalyst is shown in Table 1.
Comparative example 1
Prepare silicaalumina carrier
It takes the boehmite of 170g to be uniformly mixed with 30g sesbania powder, dust technology is added, adds 32g Sodium Polyacrylate
Nitric acid solution, and be uniformly mixed, obtain (1) containing aluminium mixture；22g silicon powder is uniformly mixed with the boehmite of 71g, is added
8.1g water soluble chitosan, adds silica solution, obtains silicon-aluminium mixture (2)；Aluminium mixture (1) and silicon-aluminium mixture will be contained
(2) mixing grinds mixed, through kneading, extrusion at trifolium-shaped, obtains silica-alumina through 130 DEG C of dry 10h, 560 DEG C of roasting 5h
Carrier.
(2) comparative catalyst 1 is prepared
It configures nickel nitrate, strontium nitrate, ammonium molybdate solution and impregnates comparative example carrier 1, it is 6 hours, 560 DEG C dry at 140 DEG C
Roasting 5 hours, obtains comparative catalyst 1, the composition of comparative catalyst is shown in Table 1.
Comparative example 2
(1) comparative example silicaalumina carrier 2 is prepared
It is as follows to prepare silicaalumina carrier process with embodiment 1 for the preparation of lanthanum-magnesium aluminate:
It takes the boehmite of 241g to be uniformly mixed with 30g sesbania powder, dust technology is added, adds 32g Sodium Polyacrylate
Nitric acid solution and 8.1g water soluble chitosan, and be uniformly mixed, lanthanum-magnesium aluminate slurry and 16g silicon powder is then added, mixing is ground
It is mixed, through kneading, extrusion at trifolium-shaped, comparative example silica-alumina is obtained through 130 DEG C of dry 10h, 560 DEG C of roasting 5h and is carried
Body 2.
(2) comparative catalyst 2 is prepared
It configures nickel nitrate, strontium nitrate, ammonium molybdate solution and impregnates comparative example carrier 2, it is 6 hours, 560 DEG C dry at 140 DEG C
Roasting 5 hours, obtains comparative catalyst 2, the composition of comparative catalyst is shown in Table 1.
Catalyst 1-3 and comparative example Catalyst packing are subjected to evaluation catalyst reaction into fixed bed reactors respectively
Performance.Presulfurization, sulfide stress 2.5MPa, hydrogen to oil volume ratio 300, vulcanization oil volume sky are carried out to catalyst with sulfurized oil
Speed is 3.5h-1, vulcanization program is respectively in 240 DEG C, 280 DEG C of vulcanizing treatment 6h.After to vulcanizing treatment, it is switched to full fraction
FCC gasoline replacement Treatment 6h, gasoline are cut into light fraction and heavy distillat at 70 DEG C, are then adjusted to reaction process condition, into light
Distillate carries out dialkene removal reaction.55 μ g/g of FCC feedstock content of sulfur in gasoline, 34 μ g/g of mercaptan sulfur, arsenic content 25ppb, two
Alkene value 6.0gI2/ 100g oil, olefin(e) centent 32.6v%.Reaction process condition are as follows: 150 DEG C of temperature of reactor, volume space velocity 6.0h-1, hydrogen to oil volume ratio 150:1, reaction pressure 2.0MPa.Sampling analysis after reaction about 90h, reaction result are shown in Table 2.
1 embodiment of table/comparative example catalyst composition/wt%
2 embodiments of table/comparative example reaction 60h result
| Embodiment/comparative example | Alkadienes removal efficiency/% | Olefin(e) centent v% |
| Embodiment 1 | 100% | 31.1 |
| Embodiment 2 | 100% | 31.2 |
| Embodiment 3 | 100% | 31.4 |
| Comparative example 1 | 93.2 | 22.3 |
| Comparative example 2 | 90.1 | 25.6 |
The result of 3 embodiment of table reaction 600h
| Embodiment | Alkadienes removal efficiency/% | Olefin(e) centent v% |
| Embodiment 1 | 100% | 31.2 |
| Embodiment 2 | 100% | 31.1 |
Reaction result shows that olefin(e) centent decreases, alkadienes removal efficiency 100%, catalyst diolefin hydrogenation selectivity
Active high, anti-arsenic, sulfur resistance are good.Comparative example catalyst alkadienes removal efficiency is low, poor selectivity, and the possible plastic of catalyst is even
Coking and activity decline, 1 bed temperature rise ratio comparative example catalyst of comparative example catalyst 2 are significantly raised.
Stability test is carried out to catalyst, reaction operation 600h reaction result is shown in Table 3, and olefin(e) centent is declined slightly, and two
Olefin removal rate 100%, catalyst are not easy plastic even coking and deactivation, and anticol mass-energy power is strong, and stability is good.
Claims (10)
1. a kind of method of FCC gasoline light fraction dialkene removal, which is characterized in that use fixed bed reactors；Gasoline is first cut
For light and heavy fractions, cutting temperature is 70 DEG C, and gasoline light fraction enters reactor and carries out dialkene removal reaction, and used catalyst is nickel
Molybdenum system hydrogenation catalyst, catalyst include silicaalumina carrier and be carried on carrier metal active constituent nickel, molybdenum,
Strontium, includes following components: nickel oxide content 2-18wt% on the basis of the total weight of catalyst, and the content of molybdenum oxide is 2-
12wt%, oxidation content of strontium are 0.05~4.5%, and silicaalumina carrier content is 67-85wt%, silica-alumina
It include the silica of 0.1~15wt%, the lanthanum-magnesium aluminate of 0.5~15wt%, the aluminium oxide of 60~86.0wt% in carrier；Reaction
Process conditions are as follows: 120~210 DEG C of reaction temperature, 1.5~3.5MPa of reaction pressure, 1.0~25.0h of liquid volume air speed-1, hydrogen
Oil volume ratio is 4~300:1.
2. the method for FCC gasoline light fraction dialkene removal according to claim 1, which is characterized in that the fixed bed reaction
Device is fixed bed adiabatic reactor either fixed bed isothermal reactor.
3. the method for FCC gasoline light fraction dialkene removal according to claim 1, which is characterized in that the reaction process item
Part are as follows: 120~180 DEG C of reactor inlet temperature, 1.5~3MPa of reaction pressure, 2.0~20.0h of liquid volume air speed-1, hydrogen oil
4~200:1 of volume ratio.
4. the method for FCC gasoline light fraction dialkene removal according to claim 1, which is characterized in that in the lanthanum-magnesium aluminate
Comprising nickel, nickel mass content is 0.1~12% in nickeliferous lanthanum-magnesium aluminate.
5. the method for FCC gasoline light fraction dialkene removal according to claim 3, which is characterized in that the nickel molybdenum system adds hydrogen
The preparation method of catalyst includes the following steps: to prepare nickel nitrate, strontium nitrate, ammonium molybdate solution oxide impregnation silicon-carrying alumina
Body is dried 3~9 hours through 110~160 DEG C, and 400~650 DEG C roast 4~9 hours, finally obtain catalyst prod.
6. the method for FCC gasoline light fraction dialkene removal according to claim 1, which is characterized in that the lanthanum-magnesium aluminate
The preparation method is as follows: basic magnesium carbonate, lanthanum carbonate and aluminium hydroxide press LaMgAl11O19Stoichiometric coefficient than be uniformly mixed,
It is added in deionized water, stirs evenly, add nickel nitrate, be uniformly mixed, after spray-dried, under the conditions of blowing air, warp
1200~1400 DEG C roast 2~10 hours, are crushed, ball milling, obtain lanthanum-magnesium aluminate powder materials.
7. the method for FCC gasoline light fraction dialkene removal according to claim 1, which is characterized in that the silica-oxidation
Alumina supporter the preparation method is as follows: the silicon source of 55%-75% is taken to be uniformly mixed with sesbania powder, acid solution and expanding agent 1 is added, expands
The additional amount of hole agent 1, which accounts for, is added the 15~30% of quality of alumina, mediates uniformly, adds lanthanum-magnesium aluminate, is uniformly mixed and obtains
Mixture (1) containing aluminium and lanthanum-magnesium aluminate；Silicon source is uniformly mixed with 25%~45% silicon source, adds binder and expanding agent
2, the additional amount of expanding agent 2 account for addition aluminium oxide and siliconoxide mass 0.1~8%, obtain silicon-aluminium mixture (2)；It will contain
The mixture (1) and silicon-aluminium mixture (2) of aluminium and lanthanum-magnesium aluminate are uniformly mixed, through extrusion, molding, drying, 400~650 DEG C of roastings
3~12h is burnt, silicaalumina carrier is obtained.
8. the method for FCC gasoline light fraction dialkene removal according to claim 7, which is characterized in that the expanding agent 1 is poly-
One or more of vinyl alcohol, polyacrylic acid, Sodium Polyacrylate, polyethylene glycol, polyacrylate.
9. the method for FCC gasoline light fraction dialkene removal according to claim 7, which is characterized in that the expanding agent 2 is first
One or more of base cellulose, polymethylacrylic acid, ammonium acrylate, glucose, chitosan etc..
10. the method for FCC gasoline light fraction dialkene removal according to claim 7, which is characterized in that the silicon source is silicon
One or more of glue, sodium metasilicate or silicon powder, diatomite.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110184089A (en) * | 2019-05-10 | 2019-08-30 | 中海油惠州石化有限公司 | A kind of low-sulfur catalytic cracking gasoline processing method |
| CN111748375A (en) * | 2019-03-28 | 2020-10-09 | 中国石油化工股份有限公司 | Method and system for producing superposed raw material by hydrorefining mixed carbon four raw material |
| CN111748374A (en) * | 2019-03-28 | 2020-10-09 | 中国石油化工股份有限公司 | Method and system for hydrorefining mixed C-C raw material |
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| CN1179788C (en) * | 2000-09-29 | 2004-12-15 | 中国石油化工股份有限公司 | Unsaturated hydrocarbon selective hydrogenation catalyst, its preparation process and use thereof |
| CN1676580A (en) * | 2004-03-31 | 2005-10-05 | 中国石油化工股份有限公司 | Fractional oil selective hydro-de-diene method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1179788C (en) * | 2000-09-29 | 2004-12-15 | 中国石油化工股份有限公司 | Unsaturated hydrocarbon selective hydrogenation catalyst, its preparation process and use thereof |
| CN1676580A (en) * | 2004-03-31 | 2005-10-05 | 中国石油化工股份有限公司 | Fractional oil selective hydro-de-diene method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111748375A (en) * | 2019-03-28 | 2020-10-09 | 中国石油化工股份有限公司 | Method and system for producing superposed raw material by hydrorefining mixed carbon four raw material |
| CN111748374A (en) * | 2019-03-28 | 2020-10-09 | 中国石油化工股份有限公司 | Method and system for hydrorefining mixed C-C raw material |
| CN111748375B (en) * | 2019-03-28 | 2021-12-17 | 中国石油化工股份有限公司 | Method and system for producing superposed raw material by hydrorefining mixed carbon four raw material |
| CN111748374B (en) * | 2019-03-28 | 2021-12-17 | 中国石油化工股份有限公司 | Method and system for hydrorefining mixed C-C raw material |
| CN110184089A (en) * | 2019-05-10 | 2019-08-30 | 中海油惠州石化有限公司 | A kind of low-sulfur catalytic cracking gasoline processing method |
| CN110184089B (en) * | 2019-05-10 | 2022-01-25 | 中海油惠州石化有限公司 | Low-sulfur catalytic cracking gasoline treatment method |
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