CN102167985B - Inferior gasoline hydro-upgrading method - Google Patents
Inferior gasoline hydro-upgrading method Download PDFInfo
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- CN102167985B CN102167985B CN201010114303.8A CN201010114303A CN102167985B CN 102167985 B CN102167985 B CN 102167985B CN 201010114303 A CN201010114303 A CN 201010114303A CN 102167985 B CN102167985 B CN 102167985B
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- 238000000034 method Methods 0.000 title claims abstract description 81
- 239000003054 catalyst Substances 0.000 claims abstract description 99
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 66
- 150000001336 alkenes Chemical class 0.000 claims abstract description 46
- 230000008569 process Effects 0.000 claims abstract description 39
- 238000002715 modification method Methods 0.000 claims abstract description 14
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000002808 molecular sieve Substances 0.000 claims description 58
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 58
- 238000005984 hydrogenation reaction Methods 0.000 claims description 32
- 238000006477 desulfuration reaction Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 230000023556 desulfurization Effects 0.000 claims description 24
- 238000000746 purification Methods 0.000 claims description 19
- 238000010335 hydrothermal treatment Methods 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 17
- 239000011777 magnesium Substances 0.000 claims description 17
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 14
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011591 potassium Substances 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 229910052810 boron oxide Inorganic materials 0.000 claims description 11
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 11
- 238000004898 kneading Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 9
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 238000005899 aromatization reaction Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 5
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 4
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 238000004230 steam cracking Methods 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 20
- 239000007788 liquid Substances 0.000 abstract description 19
- 230000004048 modification Effects 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000005864 Sulphur Substances 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 11
- 238000005070 sampling Methods 0.000 description 10
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- 229910017313 Mo—Co Inorganic materials 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910004349 Ti-Al Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910004692 Ti—Al Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000004821 distillation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003269 fluorescent indicator Substances 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract
The invention provides a modification method for selective hydrodesulfurization, olefin reduction and octane number recovery of inferior gasoline. The method adopts a process flow of connecting two agents and two devices in series. The first reactor is filled with a selective hydrodesulfurization catalyst, and the second reactor is filled with an octane number recovery catalyst. The poor gasoline is directly hydrogenated and modified without being prefractionated into light and heavy fractions. The sulfur content of the gasoline product after two-stage modification is less than 30 mu g/g, the olefin is reduced by 17-20 percent compared with the raw material, the best effect can be achieved without loss of octane number basically, and the total liquid yield is more than 98.5 wt%. The invention can obtain better hydro-upgrading effect especially for full-fraction catalytic cracking gasoline with higher sulfur and olefin contents, can greatly reduce the olefin and sulfur contents, basically does not lose octane number and keeps higher product liquid yield.
Description
Technical field
The present invention relates to a kind of method of inferior patrol hydro-upgrading, relate in particular to a kind of refining of petroleum field for the hydrogenation modification method of for example catalytic cracking (FCC) gasoline, particularly sulphur and the higher FCC gasoline inferior of olefin(e) centent.The method by inferior patrol by selective hydrodesulfurization, octane value recovering two-stage hydrogenation upgrading after producing country IV normal benzene.
Background technology
The topsoil causing for controlling motor vehicle exhaust, countries in the world have all formulated that to take low-sulfur, low olefin-content be the clean gasoline standard of sign.From the existing technical process of China's oil processing industry and development trend thereof, within the quite a long time from now on, China's motor spirit blend component be take catalytically cracked gasoline as main, and the less present situation of high-octane number component (reformed gasoline and gasoline alkylate) is difficult to obtain the change of essence.Therefore, for meeting the clean gasoline standard-required of increasingly stringent, the upgrading of catalytically cracked gasoline just becomes one of gordian technique of China's clean fuel for vehicle production, but how to solve the loss of octane number causing because of olefin saturated, and the coordination between octane value hold facility and process operation economy is catalytic gasoline hydrogenation desulfurization and the difficult point that reduces alkene.
US 5,362, and 376 have introduced a kind of gasoline hydrodesulfurizationmethod and two sections of combination procesies of octane value recovering.By catalytically cracked gasoline be cut at a certain temperature gently, last running, last running is first by a kind of conventional Hydrobon catalyst Ni-Mo/Al
2o
3or Co-Mo/Al
2o
3carry out hydrogenating desulfurization, product is processed through NiO/HZSM-5 catalyzer again, low-octane alkane shape slective cracking or isomery are turned to high-octane alkane, thereby recover the loss of octane number causing because of olefin saturated in first paragraph hydrodesulfurization process, together with being finally in harmonious proportion with the lighting end of prefractionation again.
US 5,413, and 698 have introduced two sections of combination procesies of another kind of catalyzed gasoline hydrogenation desulfurization/octane value recovering.First catalytic gasoline last running carry out desulfurization by a kind of conventional hydrogenating desulfurization Mo-Co or Mo-Ni catalyzer, product is again through the mesopore HZSM-5/ macropore H-Beta catalyst selectivity cracking containing nickel oxide, by low-octane macromole alkane cracking, be high-octane small molecules alkane, by low-octane normal alkane isomerization, be high-octane highly-branched chain isomerous alkane, thus the loss of octane number that recovery causes because of olefins hydrogenation in hydrodesulfurization process.
The patent EP0537372 of Uop Inc. has reported and has adopted two-step approach to carry out the method for FCC gasoline hydrogenation modifying.The first step of the method is that the high unsaturates (for example diolefine) that utilizes clay to remove in FCC gasoline forms stable FCC gasoline; Second step adopts SAPO-11 zeolite to carry out isomerization reaction as gasoline isomerization catalyst.Compare with stock oil, in product, isomerization product content significantly increases, and isoparaffin and normal paraffin ratio bring up to 3.97 by 1.09 of stock oil, and product gasoline yield is 100wt%, and anti-knock index and stock oil approach.The double diffusion technique that it adopts, first first paragraph removes the high unsaturated hydrocarbons in gasoline, avoid it in treating processes, to generate colloid, affect the steady running of catalyzer, but the catalyst desulfurizing ability that the method adopts a little less than, and to be only applicable to olefin(e) centent be that the FCC gasoline hydrogenation modifying of about 20v% is processed.
Because forming with external FCC gasoline, China FCC gasoline differs greatly, the olefin(e) centent (40～55v%) of China FCC gasoline, far above foreign level (20～30v%), therefore causes the external generally gasoline hydrogenation modifying technology of application to be difficult to be applicable to the upgrading of domestic gasoline.Although the gasoline hydrogenation modifying method that above-mentioned patented technology provides also can realize desulfurization and fall the object of alkene, but mainly for external FCC gasoline component exploitation, be unsuitable for domestic FCC gasoline component to process, be especially unsuitable for the modifying process of the FCC gasoline inferior that alkene and sulphur content are higher.
CN200410060574.4 discloses a kind of inferior patrol hydrogenation modifying process.FCC gasoline stocks is cut into light, last running at 60～90 ℃, wherein last running is carried out upgrading by desulfurization and two sections of upgrading combination procesies of aromizing, upgraded products is mixed to get the finished product with lighting end or through the pretreated lighting end of mercaptan removal again, sulphur≤150 μ g/g, alkene≤20v%, aromatic hydrocarbons≤40v%, RON improves 1～3 unit.
Above-mentioned patented technology emphasized by catalytically cracked gasoline be cut into gently, last running, then last running is carried out to modifying process, then is in harmonious proportion with lighting end.Although gasoline cutting is conducive to hydro-upgrading, makes troubles to technological operation, has increased running cost.
CN03133992.1 provides a kind of full cut FCC gasoline hydrodesulfurizationmethod to fall the processing method of alkene.Under the condition that hydrogen exists and temperature raises gradually, full cut FCC gasoline contacts with three kinds of catalyzer, forms three reaction zones.The first reaction zone temperature is lower, uses Hydrobon catalyst, mainly removes the diolefin in gasoline; Second reaction zone temperature is higher, uses catalyst for selectively hydrodesulfurizing, mainly removes organic sulfide and part alkene wherein; The 3rd reaction zone temperature is higher, uses gasoline reforming catalyst, comprises the upgrading reaction of aromizing, isomerization and benzene alkylation reaction, improves the octane value of gasoline, improves quality product.
CN200410020933.3 has related to a kind for the treatment of process of inferior patrol deep hydrogenation.The full distillation gasoline of FCC, through two reactors, is first taken off at a lower temperature to diene and processes, then enter the reactor that modifying catalyst and Hydrobon catalyst are housed, under comparatively high temps, carry out aromatization modification and hydrogenating desulfurization and process.
CN200410074058.7 relates to the hydrogenation modifying process that a kind of catalytically cracked gasoline is controlled olefin(e) centent, be characterised in that its adopt four kinds there is hydrofining desulfurization, fall alkene and hydroisomerizing, aromatization function catalyzer, be seated in three reactors.
Above technology is all catalytic gasoline of whole fraction to be carried out to the method for upgrading, and shortcoming is all to adopt at least two reactors, loads three to four kinds of catalyzer, and technique is comparatively complicated; And the temperature of aromatization is higher, and higher temperature of reaction easily causes the cracking of gasoline in hydro-upgrading process, thereby has influence on the yield of product gasoline.
CN101508912A provides a kind of deep desulfuration-recovery octane value hydrogenation modification method of inferior patrol, is characterised in that and adopts two kinds of different catalysts of two-stage reaction filling, and one section mainly removes unstable diolefine and the difficult sulfide removing in gasoline; Second segment adopts hydro-thermal, the modified HZSM-5 zeolite of mineral acid-organic acid comprehensive treating process and the catalyzer that Ti-Al mixture is carrier, realizes further desulfurization, falls alkene and recovers octane value.In the present invention, one section of catalyzer is used Al-Ti-Mg complex carrier, and because magnesian physical strength is poor, so the physical strength of catalyzer is poor, is unsuitable for large-scale industrial application.
CN101440306A discloses a kind of hydrogenation modification method of catalytically cracked gasoline, and the method adopts two-stage method to process FCC gasoline stocks, makes the catalyzer contact different from two kinds of FCC gasoline that hydrogenation reaction occur, and forms two-stage reaction district.First paragraph is used removing alkadiene by selective hydrogenation catalyzer, mainly removes the unstable diolefin in oil product; Second segment adopts isomery/aromizing ZSM-5/SAPO-11 composite zeolite catalyst based, mainly realizes desulfurization, falls alkene and improves the object of product octane value.But the method only adopts one-step desulfurization, so desulfurization degree is lower.
Therefore, for catalytic gasoline hydrogenation modifying, process, first to select to have the catalyzer of selection hydrogenating desulfurization, olefin saturated and octane value recovering that can modulation, the catalyzer especially with hydrogenating desulfurization function and the octane value recovering function of highly selective, it is less important operates under simple suitable selective hydrodesulfurization, octane value recovering combination process, realizes deep desulfuration, significantly falls alkene, keeps octane value and improves the hydro-upgrading target of liquid yield.
Summary of the invention
The object of the present invention is to provide a kind of hydro-upgrading method for ungraded gasoline, the method does not need inferior patrol to cut, directly carry out selective hydrodesulfurization, octane value recovering two-stage hydrogenation modifying process, not only flow process simple, invest low and catalyst stability good, be particularly useful for the hydro-upgrading of the full cut FCC gasoline that alkene and sulphur content are higher.
Hydro-upgrading method for ungraded gasoline of the present invention comprises: inferior patrol passes through successively two insulation fix bed reactors under hydrogen atmosphere, first enter the reactor that catalyst for selectively hydrodesulfurizing is housed, catalyzer is that the aluminum oxide of take containing boron oxide is carrier, active ingredient is cobalt and molybdenum, take total catalyst weight as 100wt%, cobalt oxide content 2～4wt%, molybdenum oxide content 14～18wt%; Auxiliary agent is magnesium, potassium and phosphorus, and the content in catalyzer is respectively: magnesium oxide 4～6wt%, potassium oxide 2～5wt%, phosphorus oxide 2～4wt%; In carrier, boron oxide accounts for 10～15wt%, and aluminum oxide accounts for 85～90wt%, specific surface area of catalyst 180～230m
2/ g, pore volume 0.4～0.5ml/g; Material after hydrogenating desulfurization enters the reactor that octane value recovering catalyst is housed, mainly carry out the processes such as hydroisomerizing, aromatization and cyclisation of alkene, catalyzer is comprised of active ingredient molybdenum, nickel and carrier, take total catalyst weight as 100wt%, wherein containing molybdenum oxide 3～10wt%, nickel oxide 1～5wt%, 20～80wt% modified HZSM-5 molecular sieve and 10～80wt% binding agent, wherein modified HZSM-5 molecular sieve obtains by following method: HZSM-5 molecular sieve is carried out to alkaline purification, ammonium exchange and hydrothermal treatment consists, make modified HZSM-5 molecular sieve; Alkaline purification is that the HZSM-5 molecular sieve of HZSM-5 molecular sieve or process hydrothermal treatment consists is placed in to alkaline solution by liquid-solid ratio 5～15ml/g, by pH regulator to 9～14, at 60～90 ℃, stir 2～6h, then product is filtered, washed, at 110～130 ℃ of dry, 450～520 ℃ of roasting 2～6h.
The reaction conditions that inferior patrol enters the reactor that catalyst for selectively hydrodesulfurizing is housed is: hydrogen dividing potential drop is 1.0～2.5MPa, and temperature of reaction is 180～260 ℃, and volume space velocity is 2.0～4.0h
-1, hydrogen to oil volume ratio is 200～400.
The reaction conditions that material after hydrogenating desulfurization enters the reactor that octane value recovering catalyst is housed is: hydrogen dividing potential drop is 1.0～2.5MPa, and temperature of reaction is 290～400 ℃, and volume space velocity is 0.5～4.0h
-1, hydrogen to oil volume ratio is 200～400.
In first reactor, mainly carry out selective hydrodesulfurization reaction, and be accompanied by the saturated of a small amount of alkene; In second reactor, mainly carry out hydrogenation of olefins isomery/face hydrogen aromatization, deep desulfuration, significantly fall five kinds of reactions such as alkene and mercaptan removal, guaranteeing deep desulfuration, significantly fall octane value under the prerequisite of alkene and remain on higher level.Reactor insulation fix bed reactor preferably in the present invention.
Inferior patrol comprises one or more the mixture in catalytically cracked gasoline, coker gasoline, catalytic cracking gasoline, pressure gasoline and steam cracking gasoline, preferably catalytically cracked gasoline.
Catalytically cracked gasoline can be the last running FCC gasoline after cutting, full cut FCC gasoline.
The present invention also provides a kind of catalyzer that is applicable to selective hydrogenation desulfurization process condition, uses this catalyzer can obtain excellent especially selection hydrogenating desulfurization effect.
Select Hydrobon catalyst can adopt the following preparation method that the present invention recommends to obtain:
Aluminum oxide and boron oxide are mixed, add sesbania powder and nitric acid to mediate, extruded moulding, 100～120 ℃ are dry, and 500～600 ℃ of roasting 4～6h make composite oxide carrier; Then this composite oxide carrier is flooded to magnesium, potassium and phosphorus, 20～30 ℃ of ageing 6～8h, 100～120 ℃ are dry, and 500～600 ℃ of roasting 4～6h obtain addition agent modified composite oxide carrier; Finally active ingredient cobalt and molybdenum are immersed on this carrier, 20～30 ℃ of ageing 6～8h, 100～120 ℃ are dry, and 500～600 ℃ of roasting 4～6h obtain catalyst for selectively hydrodesulfurizing.Composite oxide carrier is preferably 63～76wt% of catalyzer.
Oxygen-freeization magnesium when catalyst for selectively hydrodesulfurizing is characterized in the moulding of catalyst for selectively hydrodesulfurizing carrier in the present invention, magnesium is to load in support of the catalyst as auxiliary agent, so both can avoid causing catalyzer physical strength to decline because containing a large amount of magnesium oxide, can improve the desulfuration selectivity of catalyzer again, and support of the catalyst employing kneading method of the present invention preparation, can adapt to the requirement that large-scale industrialization is produced.The introducing of auxiliary agent potassium and phosphorus has reduced acid amount and the strength of acid of catalyzer, catalyzer strong acidic site is disappeared, reduced olefin saturated rate in selection hydrodesulfurization process, improved selectivity of catalyst, reduced the loss of octane value, in carrier, add the strong acid center that can reduce support of the catalyst after boron, make catalyzer there is lower olefin saturated active, improved the anti-coking performance of catalyzer.Material alkene loss after this catalyst treatment is little, and octane value does not lose substantially, is more suitable for processing the full cut FCC of the poor quality gasoline that olefin(e) centent is high, more active than selecting other type catalyst to have the active and lower olefin saturated of better selective desulfurization.
Binding agent in octane value recovering catalyst of the present invention is general binding agent, generally refers to pseudo-boehmite, Al
2o
3, SiO
2, one or more in diatomite.
The preparation method of the octane value recovering catalyst that the present invention recommends is: first modified HZSM-5 molecular sieve is mixed with binding agent, through kneading, extruded moulding, dry, 480～650 ℃ of roasting 3～7h, make support of the catalyst, then adopt pickling process that active metal component Ni, Mo are loaded in support of the catalyst, after drying, 450～520 ℃ of roasting 3～5h, make catalyzer.
Modified HZSM-5 molecular sieve of the present invention obtains by HZSM-5 molecular sieve being carried out to alkaline purification, ammonium exchange and hydrothermal treatment consists; Alkaline purification is that HZSM-5 molecular sieve is placed in to alkaline solution by liquid-solid ratio 5～15ml/g, by pH regulator to 9～14, at 60～90 ℃, stirs 2～6h, then product is filtered, washed, at 110～130 ℃, be dried, 450～520 ℃ of roasting 2～6h, the alkali of employing is selected from NaOH, KOH, Na
2cO
3or K
2cO
3, preferred NaOH; Hydrothermal treatment consists, ammonium give-and-take conditions are all same as the prior art, and the present invention does not have particular requirement.
In the present invention, the exchange of alkaline purification when HZSM-5 molecular sieve is carried out to modification and ammonium is very necessary, if be only the acidity that hydrothermal treatment consists just can only modulation molecular sieve and can not optimize the pore structure of molecular sieve; If only there is alkaline purification there is no ammonium exchange, molecular sieve is Na type, acidity a little less than; If only there is the exchange of alkaline purification and ammonium there is no hydrothermal treatment consists, pore structure that can only modulation molecular sieve and the acidity of molecular sieve can not optimized.The exchange of alkaline purification and ammonium can be that before hydrothermal treatment consists, to carry out can be also to carry out after hydrothermal treatment consists, preferably before hydrothermal treatment consists, carries out, and can more effectively optimize like this acidity and the pore structure of molecular sieve, thereby improve the reactivity worth of catalyzer.
Because the HZSM-5 molecular sieve that uses modification carries out alkaline purification after HZSM-5 molecular sieve is first carried out carrying out hydrothermal treatment consists again or first carrying out hydrothermal treatment consists after alkaline purification and ammonium exchange and ammonium exchange obtains again, therefore there is acidity and the pore structure of complex optimum.
Octane value recovering catalyst of the present invention has higher hydrogenating desulfurization, olefin saturated, hydroisomerization, aromatization activity and mercaptan removal ability, shows good combined reaction performance.This is mainly because HZSM-5 molecular sieve is carried out to alkaline purification and hydrothermal treatment consists, makes the acidity of HZSM-5 molecular sieve suitable, has formed more mesopore, and catalyst deactivation rate is reduced.In support of the catalyst, contain more modified HZSM-5 molecular sieve simultaneously, improved aromizing shape selectivity and the octane value hold facility of catalyzer.
Inferior patrol hydrogenation modifying process of the present invention adopts conventional fixed-bed reactor, adopts two doses, the technical process of two devices series connection, is applicable to the hydro-upgrading of inferior patrol, is particularly useful for the full cut FCC gasoline that sulphur and olefin(e) centent are higher.
Hydrogenating materials does not need to carry out pre-treatment, directly full feedstock is carried out to hydro-upgrading.In product after upgrading, content of sulfur in gasoline < 30 μ g/g, compare with raw material, and upgraded products alkene reduces by 17～20 percentage points, and octane value does not lose substantially, and total liquid is received and is greater than 98.5wt%.
Inferior patrol hydrogenation modifying process of the present invention has the following advantages:
1, processing simulation full scale plant of the present invention, adopts insulation fix bed reactor, is conducive to the popularization to full scale plant.
2, catalyst for selectively hydrodesulfurizing provided by the invention has desulfurization and slightly falls the effect of alkene.
3, octane value recovering catalyst provided by the invention has and significantly falls alkene, deep desulfuration, octane value recovering and mercaptan removal multi-functional, there is good low temperature active, octane value recovering process can be carried out under lower temperature of reaction, has reached and has not only kept octane value but also make the economically viable effect of operating process.
4, selective hydrodesulfurization provided by the invention and octane value recovering process are carried out respectively in two reactors, have avoided influencing each other of two processes, and the sulphur content in hydrogenated products can meet state IV requirement.
5, adopt technique of the present invention not need to set up separately de-diene device, technological operation is simple.
6, the content of sulfur in gasoline after the invention provides method upgrading and olefin(e) centent can reach state IV gasoline standard (sulphur < 50 μ g/g, alkene < 25v%) requirement, octane value does not lose substantially, total liquid is received and is greater than 98.5wt%, has deep desulfuration, alkene, the effective feature of octane value recovering fall in appropriateness.
Embodiment
Raw material sources and Standard of analytical methods:
HZSM-5 molecular sieve (SiO
2/ Al
2o
3mol ratio=34): Hua Heng chemical plant, Shanghai;
Pseudo-boehmite is (containing γ-Al of 76wt%
2o
3crystal water with 24wt%): German Sasol company;
Sesbania powder: China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute;
SB powder: pseudo-boehmite, moisture 26wt%, specific surface area 230m after roasting
2/ g, pore volume 0.51mL/g, German Condea company produces.
Research octane number (RON) (RON): GB/T5487;
Gasoline forms: GB-T11132-2002 liquid petroleum product hydro carbons assay method (fluorescent indicator adsorption method);
Sulphur content: adopt WK-2B Microcoulomb instrument to measure;
Boiling range: adopt petroleum products test method SYB-2110-60 to measure;
Liquid yield: product liquid quality/charging quality * 100%;
Catalyzer agent active component content measuring method: XRF;
The preparation of catalyst for selectively hydrodesulfurizing 1～4:
The preparation of catalyzer 1:
SB powder, boron oxide and sesbania powder are mixed, add nitric acid and water kneading and compacting, 120 ℃ dry, and 520 ℃ of roasting 4h make composite oxide carrier.
Prepare suitable magnesium nitrate, saltpetre and Secondary ammonium phosphate mixed impregnant liquor, dipping composite oxide carrier, ageing 6h under room temperature, 120 ℃ of dry 3h, 530 ℃ of roasting 4h obtain the support of the catalyst of modifying containing auxiliary agent magnesium, potassium and phosphorus.
At the temperature of 70 ℃, prepare Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and the ammonium molybdate mixed solution of suitable concentration, and add ammoniacal liquor to make it whole dissolvings, be then immersed in the support of the catalyst of modifying containing auxiliary agent magnesium, potassium and phosphorus, room temperature ageing 8h, 120 ℃ of dry 4h, 550 ℃ of roasting 5h, make catalyst for selectively hydrodesulfurizing 1.
The preparation of catalyzer 2:
SB powder, boron oxide and sesbania powder are mixed, add nitric acid and water kneading and compacting, 120 ℃ dry, and 520 ℃ of roasting 4h make composite oxide carrier.
Prepare suitable magnesium nitrate, saltpetre and Secondary ammonium phosphate mixed impregnant liquor, dipping composite oxide carrier, ageing 5h under room temperature, 120 ℃ of dry 3h, 540 ℃ of roasting 4h obtain the support of the catalyst of modifying containing auxiliary agent magnesium, potassium and phosphorus.
At the temperature of 75 ℃, prepare Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and the ammonium molybdate mixed solution of suitable concentration, and add ammoniacal liquor to make it whole dissolvings, be then immersed in the support of the catalyst of modifying containing auxiliary agent magnesium, potassium and phosphorus, room temperature ageing 7h, 120 ℃ of dry 4h, 540 ℃ of roasting 5h, make catalyst for selectively hydrodesulfurizing 2.
The preparation of catalyzer 3:
SB powder, boron oxide and sesbania powder are mixed, add nitric acid and water kneading and compacting, 120 ℃ dry, and 520 ℃ of roasting 4h make composite oxide carrier.
Prepare suitable magnesium nitrate, saltpetre and Secondary ammonium phosphate mixed impregnant liquor, dipping composite oxide carrier, ageing 7h under room temperature, 120 ℃ of dry 4h, 560 ℃ of roasting 4h obtain the support of the catalyst of modifying containing auxiliary agent magnesium, potassium and phosphorus.
At the temperature of 80 ℃, prepare Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and the ammonium molybdate mixed solution of suitable concentration, and add ammoniacal liquor to make it whole dissolvings, be then immersed in the support of the catalyst of modifying containing auxiliary agent magnesium, potassium and phosphorus, room temperature ageing 8h, 120 ℃ of dry 4h, 540 ℃ of roasting 6h, make catalyst for selectively hydrodesulfurizing 3.
The preparation of catalyzer 4:
SB powder, boron oxide and sesbania powder are mixed, add nitric acid and water kneading and compacting, 120 ℃ dry, and 520 ℃ of roasting 5h make composite oxide carrier.
Prepare suitable magnesium nitrate, saltpetre and Secondary ammonium phosphate mixed impregnant liquor, dipping composite oxide carrier, ageing 7h under room temperature, 120 ℃ of dry 4h, 550 ℃ of roasting 4h obtain the support of the catalyst of modifying containing auxiliary agent magnesium, potassium and phosphorus.
At the temperature of 75 ℃, prepare Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and the ammonium molybdate mixed solution of suitable concentration, and add ammoniacal liquor to make it whole dissolvings, be then immersed in the support of the catalyst of modifying containing auxiliary agent magnesium, potassium and phosphorus, room temperature ageing 8h, 120 ℃ of dry 4h, 550 ℃ of roasting 4h, make catalyst for selectively hydrodesulfurizing 4.
The physico-chemical property of gained catalyst for selectively hydrodesulfurizing is as shown in table 2.
The main physico-chemical property of table 1 catalyst for selectively hydrodesulfurizing
The preparation of octane value recovering catalyst 5～8:
The preparation of catalyzer 5:
HZSM-5 molecular sieve is placed in to alkaline solution by the liquid-solid ratio of 7ml/g, by pH regulator to 9.5, at 80 ℃, stirs 3h, filter, wash to neutral, 120 ℃ of dry, 480 ℃ of roasting 3h; HZSM-5 molecular sieve through alkaline purification is placed in to ammonium solution, wherein molecular sieve: ammonium salt: water weight ratio is 1: 0.8: 10, and stirs 4h at 75 ℃, then product is filtered, washed, 120 ℃ of dry, 500 ℃ of roasting 4h; Gained HZSM-5 molecular sieve is broken into the particle of 20～40 order numbers, puts into hydrothermal treatment consists stove, process 5h in 500 ℃, 100% water vapour after the HZSM-5 molecular sieve of modification.
Modified HZSM-5 molecular sieve is mixed to the support of the catalyst of making after kneading, extruded moulding, dry, 550 ℃ of roasting 6h with binding agent; Then the precursor aqueous solution of preparing molybdenum oxide and nickel oxide metal, is immersed in support of the catalyst, and dry, 500 ℃ of roasting 4h make octane value recovering catalyst 5.
The preparation of catalyzer 6:
HZSM-5 molecular sieve is placed in to alkaline solution by the liquid-solid ratio of 8ml/g, by pH regulator to 10, at 70 ℃, stirs 4h, filter, wash to neutral, 130 ℃ of dry, 480 ℃ of roasting 5h; HZSM-5 molecular sieve through alkaline purification is placed in to ammonium solution, wherein molecular sieve: ammonium salt: water weight ratio is 1: 1.0: 8, and stirs 3h at 80 ℃, then product is filtered, washed, 130 ℃ of dry, 520 ℃ of roasting 2h; Gained HZSM-5 molecular sieve is broken into the particle of 20～40 order numbers, puts into hydrothermal treatment consists stove, process 6h in 480 ℃, 100% water vapour after the HZSM-5 molecular sieve of modification.
Modified HZSM-5 molecular sieve is mixed to the support of the catalyst of making after kneading, extruded moulding, dry, 600 ℃ of roasting 4h with binding agent; Then the precursor aqueous solution of preparing molybdenum oxide and nickel oxide metal, is immersed in support of the catalyst, and dry, 460 ℃ of roasting 5h make octane value recovering catalyst 6.
The preparation of catalyzer 7:
HZSM-5 molecular sieve is placed in to alkaline solution by the liquid-solid ratio of 10ml/g, by pH regulator to 12, at 70 ℃, stirs 5h, filter, wash to neutral, 120 ℃ of dry, 470 ℃ of roasting 6h; HZSM-5 molecular sieve through alkaline purification is placed in to ammonium solution, wherein molecular sieve: ammonium salt: water weight ratio is 1: 1.6: 12, and stirs 4h at 88 ℃, then product is filtered, washed, 120 ℃ of dry, 460 ℃ of roasting 6h; Gained HZSM-5 molecular sieve is broken into the particle of 20～40 order numbers, puts into hydrothermal treatment consists stove, process 3h in 580 ℃, 100% water vapour after the HZSM-5 molecular sieve of modification.
Modified HZSM-5 molecular sieve is mixed to the support of the catalyst of making after kneading, extruded moulding, dry, 550 ℃ of roasting 4h with binding agent; Then the precursor aqueous solution of preparing molybdenum oxide and nickel oxide metal, is immersed in support of the catalyst, and dry, 480 ℃ of roasting 4h make octane value recovering catalyst 7.
The preparation of catalyzer 8:
HZSM-5 molecular sieve is placed in to alkaline solution by the liquid-solid ratio of 7.5ml/g, by pH regulator to 10.5, at 85 ℃, stirs 3h, filter, wash to neutral, 120 ℃ of dry, 520 ℃ of roasting 3h; HZSM-5 molecular sieve through alkaline purification is placed in to ammonium solution, wherein molecular sieve: ammonium salt: water weight ratio is 1: 0.9: 10, and stirs 6h at 75 ℃, then product is filtered, washed, 120 ℃ of dry, 480 ℃ of roasting 3h; Gained HZSM-5 molecular sieve is broken into the particle of 20～40 order numbers, puts into hydrothermal treatment consists stove, process 5h in 550 ℃, 100% water vapour after the HZSM-5 molecular sieve of modification.
Modified HZSM-5 molecular sieve is mixed to the support of the catalyst of making after kneading, extruded moulding, dry, 580 ℃ of roasting 5h with binding agent; Then the precursor aqueous solution of preparing molybdenum oxide and nickel oxide metal, is immersed in support of the catalyst, and dry, 500 ℃ of roasting 4h make octane value recovering catalyst 8.
The physico-chemical property of gained octane value recovering catalyst is as shown in table 2.
The main physico-chemical property of table 2 octane value recovering catalyst
Below by embodiment, further illustrate the present invention, but the present invention is not limited to this.
Raw material adopts full cut FCC gasoline, and its character is in Table 3.
Table 3 stock oil character
Embodiment 1:
Hydro-upgrading is processed and is adopted heat-insulating fixed bed, and two reactors in series, load catalyst for selectively hydrodesulfurizing 1 in first reactor; In second reactor, load octane value recovering catalyst 5.With 50 ℃/h, be warmed up to 150 ℃, under hydrogen flow rate 60L/h, pressure 2.0MPa condition, enter petroleum naphtha (containing 2wt%CS
2) sulfidizing 1h, then sulfidizing 6h respectively under 230 ℃, 290 ℃ and 320 ℃ of conditions, completes the sulfidizing to catalyzer.
After sulfidizing finishes, switch to full cut FCC feed gasoline 1, at reaction pressure 1.2MPa, volume space velocity 4.0h
-1, under the condition of hydrogen-oil ratio 250, first stage reactor temperature in is controlled at 185 ℃, and second stage reactor temperature in is controlled at 300 ℃.Running 800h, every 24h sampling analysis upgraded products composition, sulphur content, octane value and liquid yield, the results are shown in Table 4.
Embodiment 2:
Hydro-upgrading is processed and is adopted heat-insulating fixed bed, and two reactors in series, load catalyst for selectively hydrodesulfurizing 2 in first reactor; In second reactor, load octane value recovering catalyst 6.Sulfurizing treatment method is with embodiment 1.
After sulfidizing finishes, switch to full cut FCC feed gasoline 2, at reaction pressure 1.5MPa, volume space velocity 4.0h
-1, under the condition of hydrogen-oil ratio 300, first stage reactor temperature in is controlled at 190 ℃, and second stage reactor temperature in is controlled at 295 ℃.Running 800h, every 24h sampling analysis upgraded products composition, sulphur content, octane value and liquid yield, the results are shown in Table 4.
Embodiment 3:
Hydro-upgrading is processed and is adopted heat-insulating fixed bed, and two reactors in series, load catalyst for selectively hydrodesulfurizing 3 in first reactor; In second reactor, load octane value recovering catalyst 7.Sulfurizing treatment method is with embodiment 1.
After sulfidizing finishes, switch to full cut FCC feed gasoline 3, at reaction pressure 1.6MPa, volume space velocity 3.5h
-1, under the condition of hydrogen-oil ratio 250, first stage reactor temperature in is controlled at 195 ℃, and second stage reactor temperature in is controlled at 300 ℃.Running 800h, every 24h sampling analysis upgraded products composition, sulphur content, octane value and liquid yield, the results are shown in Table 4.
Embodiment 4:
Hydro-upgrading is processed and is adopted heat-insulating fixed bed, and two reactors in series, load catalyst for selectively hydrodesulfurizing 4 in first reactor; In second reactor, load octane value recovering catalyst 8.Sulfurizing treatment method is with embodiment 1.
After sulfidizing finishes, switch to full cut FCC feed gasoline 4, at reaction pressure 1.8MPa, volume space velocity 4.0h
-1, under the condition of hydrogen-oil ratio 350, first stage reactor temperature in is controlled at 200 ℃, and second stage reactor temperature in is controlled at 305 ℃.Running 800h, every 24h sampling analysis upgraded products composition, sulphur content, octane value and liquid yield, the results are shown in Table 4.
Embodiment 5:
Hydro-upgrading is processed and is adopted heat-insulating fixed bed, and two reactors in series, load catalyst for selectively hydrodesulfurizing 1 in first reactor; In second reactor, load octane value recovering catalyst 7.Sulfurizing treatment method is with embodiment 1.
After sulfidizing finishes, switch to full cut FCC feed gasoline 3, at reaction pressure 1.6MPa, volume space velocity 3.0h
-1, under the condition of hydrogen-oil ratio 250, first stage reactor temperature in is controlled at 190 ℃, and second stage reactor temperature in is controlled at 300 ℃.Running 800h, every 24h sampling analysis upgraded products composition, sulphur content, octane value and liquid yield, the results are shown in Table 4.
Embodiment 6:
Hydro-upgrading is processed and is adopted heat-insulating fixed bed, and two reactors in series, load catalyst for selectively hydrodesulfurizing 1 in first reactor; In second reactor, load octane value recovering catalyst 8.Sulfurizing treatment method is with embodiment 1.
After sulfidizing finishes, switch to full cut FCC feed gasoline 4, at reaction pressure 1.8MPa, volume space velocity 3.5h
-1, under the condition of hydrogen-oil ratio 350, first stage reactor temperature in is controlled at 185 ℃, and second stage reactor temperature in is controlled at 300 ℃.Running 800h, every 24h sampling analysis upgraded products composition, sulphur content, octane value and liquid yield, the results are shown in Table 4.
Comparative example 1:
Two kinds of catalyzer that this comparative example is used are all by the method preparation described in embodiment in CN101508912A 1, and one section of catalyzer forms: cobalt oxide 4.0wt%, molybdenum oxide 15wt%, potassium oxide 3.0wt%, phosphorus oxide 2.0wt%, magnesium oxide 4.0wt%, titanium oxide 8.0wt%, aluminum oxide 64wt%; Two sections of catalyzer form: cobalt oxide 2wt%, molybdenum oxide 6wt%, phosphorus oxide 1wt%, modified HZSM-5 molecular sieve 65wt%, titanium oxide 5wt%, aluminum oxide 21wt%.
Hydro-upgrading is processed and is adopted heat-insulating fixed bed, two reactors in series.Sulfurizing treatment method is with embodiment 1.
After sulfidizing finishes, switch to full cut FCC feed gasoline 1, at reaction pressure 1.2MPa, volume space velocity 4.0h
-1, under the condition of hydrogen-oil ratio 250, first stage reactor temperature in is controlled at 185 ℃, and second stage reactor temperature in is controlled at 300 ℃.Running 800h, every 24h sampling analysis upgraded products composition, sulphur content, octane value and liquid yield, the results are shown in Table 4.
Comparative example 2:
Hydro-upgrading is processed and is adopted heat-insulating fixed bed, two reactors in series, and catalyzer is with comparative example 1.Sulfurizing treatment method is with embodiment 1.
After sulfidizing finishes, switch to full cut FCC feed gasoline 3, at reaction pressure 1.6MPa, volume space velocity 3.5h
-1, under the condition of hydrogen-oil ratio 250, first stage reactor temperature in is controlled at 195 ℃, and second stage reactor temperature in is controlled at 300 ℃.Running 800h, every 24h sampling analysis upgraded products composition, sulphur content, octane value and liquid yield, the results are shown in Table 4.
Comparative example 3:
Prepared by the method that in the Hydrobon catalyst that this comparative example is used, the preparation of carrier press described in CN1137245C embodiment 2, Hydrobon catalyst is pressed the method preparation described in CN1128858C embodiment 1, one section of catalyzer forms: cobalt oxide 3.5wt%, molybdenum oxide 15.6wt%, surplus is modification TiO
2; Two sections of catalyzer adopt octane value recovering catalyst 6.
Hydro-upgrading is processed and is adopted heat-insulating fixed bed, two reactors in series.Sulfurizing treatment method is with embodiment 1.
After sulfidizing finishes, switch to full cut FCC feed gasoline 2, at reaction pressure 1.5MPa, volume space velocity 4.0h
-1, under the condition of hydrogen-oil ratio 300, first stage reactor temperature in is controlled at 190 ℃, and second stage reactor temperature in is controlled at 295 ℃.Running 800h, every 24h sampling analysis upgraded products composition, sulphur content, octane value and liquid yield, the results are shown in Table 4.
Comparative example 4:
Two kinds of catalyzer that this comparative example is used are all by the method preparation described in CN101440306A embodiment 1, and one section of catalyzer forms: nickel oxide 1.0wt%, molybdenum oxide 4.0wt%, potassium oxide 4.0wt%, lanthanum trioxide 1wt%, aluminum oxide 90wt%; Two sections of catalyzer form: nickel oxide 1.5wt%, molybdenum oxide 7.0wt%, HZSM-550wt%, SAPO-1120wt%, 21.5wt% γ-Al
2o
3composite zeolite is catalyst based.
Hydro-upgrading is processed and is adopted heat-insulating fixed bed, two reactors in series.Sulfurizing treatment method is with embodiment 1.
After sulfidizing finishes, switch to full cut FCC feed gasoline 4, at reaction pressure 1.8MPa, volume space velocity 4.0h
-1, under the condition of hydrogen-oil ratio 350, first stage reactor temperature in is controlled at 200 ℃, and second stage reactor temperature in is controlled at 305 ℃.Running 800h, every 24h sampling analysis upgraded products composition, sulphur content, octane value and liquid yield, the results are shown in Table 4.
Comparative example 5
This comparative example difference from Example 1 is that the molecular sieve that two sections of catalyzer are used is unmodified HZSM-5.Sulfuration and hydro-upgrading are processed with embodiment 1, the results are shown in Table 4.
Comparative example 6
This comparative example difference from Example 2 is that in one section of catalyzer, magnesium adds in carrier preparation process.Sulfidizing is with embodiment 1, and hydro-upgrading is processed with embodiment 2, the results are shown in Table 4.
Comparative example 7
This comparative example difference from Example 1 is that one section of support of the catalyst only modifies with magnesium and potassium, with phosphorus, does not modify.Catalyzer consists of: cobalt oxide 4.0wt%, molybdenum oxide 15wt%, potassium oxide 3.0wt%, magnesium oxide 4.0wt%, boron oxide 8.0wt%, aluminum oxide 66wt%; Sulfuration and hydro-upgrading are processed with embodiment 1, the results are shown in Table 4.
As shown in Table 4, for sulphur content and the higher full cut FCC gasoline of olefin(e) centent, catalyzer of the present invention and hydrogenation modification method can make the sulphur content in upgraded products be down to below 30 μ g/g, the average range of decrease of alkene is 19.2v%, aromatic hydrocarbons on average increases by 6～7v%, total liquid yield average out to 98.9wt%, at deep desulfuration, significantly alkene falls and in product octane value substantially do not lose, product boiling range and stock oil are basic identical, show that the inventive method and catalyzer have good hydro-upgrading effect to high-sulfur, high olefin inferior patrol.
Claims (10)
1. a hydro-upgrading method for ungraded gasoline, inferior patrol carries out hydro-upgrading by two insulation fix bed reactors under hydrogen atmosphere, it is characterized in that: first enter the reactor that catalyst for selectively hydrodesulfurizing is housed, catalyzer is that the aluminum oxide of take containing boron oxide is carrier, active ingredient is cobalt and molybdenum, take total catalyst weight as 100wt%, cobalt oxide content 2～4wt%, molybdenum oxide content 14～18wt%; Auxiliary agent is magnesium, potassium and phosphorus, content of magnesia 4～6wt%, potassium oxide content 2～5wt%, phosphorus oxide content 2～4wt%; In carrier, boron oxide accounts for 10～15wt%, and aluminum oxide accounts for 85～90wt%, specific surface area of catalyst 180～230m
2/ g, pore volume 0.4～0.5ml/g; Material after hydrogenating desulfurization enters the reactor that octane value recovering catalyst is housed, mainly carry out the process of hydroisomerizing, aromatization and the cyclisation of alkene, catalyzer is comprised of active ingredient molybdenum, nickel and carrier, take total catalyst weight as 100wt%, wherein containing molybdenum oxide 3～10wt%, nickel oxide 1～5wt%, 20～80wt% modified HZSM-5 molecular sieve and 10～80wt% binding agent, wherein modified HZSM-5 molecular sieve obtains by following method: HZSM-5 molecular sieve is carried out to alkaline purification, ammonium exchange and hydrothermal treatment consists, make modified HZSM-5 molecular sieve; Alkaline purification is that the HZSM-5 molecular sieve of HZSM-5 molecular sieve or process hydrothermal treatment consists is placed in to alkaline solution by liquid-solid ratio 5～15ml/g, by pH regulator to 9～14, at 60～90 ℃, stir 2～6h, then product is filtered, washed, at 110～130 ℃ of dry, 450～520 ℃ of roasting 2～6h.
2. hydrogenation modification method according to claim 1, it is characterized in that: inferior patrol enters the reactor that catalyst for selectively hydrodesulfurizing is housed, its processing condition are: hydrogen dividing potential drop is 1.0～2.5MPa, and temperature of reaction is 180～260 ℃, and volume space velocity is 2.0～4.0h
-1, hydrogen to oil volume ratio is 200～400.
3. hydrogenation modification method according to claim 1, it is characterized in that: the material after hydrogenating desulfurization enters the reactor that octane value recovering catalyst is housed, its processing condition are: hydrogen dividing potential drop is 1.0～2.5MPa, and temperature of reaction is 290～400 ℃, and volume space velocity is 0.5～4.0h
-1, hydrogen to oil volume ratio is 200～400.
4. hydrogenation modification method according to claim 1, is characterized in that: described inferior patrol comprises one or more the mixture in catalytically cracked gasoline, coker gasoline, catalytic cracking gasoline, pressure gasoline and steam cracking gasoline.
5. hydrogenation modification method according to claim 4, is characterized in that: described inferior patrol is catalytic gasoline of whole fraction.
6. hydrogenation modification method according to claim 1, is characterized in that: when HZSM-5 molecular sieve is carried out to alkaline purification, the alkali of employing is selected from NaOH, KOH, Na
2cO
3or K
2cO
3.
7. hydrogenation modification method according to claim 6, is characterized in that: when HZSM-5 molecular sieve is carried out to alkaline purification, the alkali of employing is NaOH.
8. hydrogenation modification method according to claim 1, it is characterized in that: catalyst for selectively hydrodesulfurizing obtains by following method: aluminum oxide and boron oxide are mixed, add sesbania powder and nitric acid to mediate, extruded moulding, 100～120 ℃ dry, and 500～600 ℃ of roasting 4～6h make composite oxide carrier; Then this composite oxide carrier is flooded to magnesium, potassium and phosphorus, 20～30 ℃ of ageing 6～8h, 100～120 ℃ are dry, and 500～600 ℃ of roasting 4～6h obtain addition agent modified composite oxide carrier; Finally active ingredient cobalt and molybdenum are immersed on this carrier, 20～30 ℃ of ageing 6～8h, 100～120 ℃ are dry, and 500～600 ℃ of roasting 4～6h obtain catalyst for selectively hydrodesulfurizing.
9. hydrogenation modification method according to claim 1, it is characterized in that: octane value recovering catalyst obtains by following method: first modified HZSM-5 molecular sieve is mixed with binding agent, through kneading, extruded moulding, dry, 480～650 ℃ of roasting 3～7h, make support of the catalyst, then adopt pickling process that active metal component Ni, Mo are loaded in support of the catalyst, after drying, 450～520 ℃ of roasting 3～5h, make catalyzer.
10. according to the hydrogenation modification method described in claim 1 or 9, it is characterized in that: binding agent is pseudo-boehmite, Al
2o
3, SiO
2, one or more in diatomite.
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| CN103122258B (en) * | 2011-11-18 | 2015-08-12 | 中国石油化工股份有限公司 | Method for desulfuration by selective hydrogenation of light cycle oil |
| CN104107694A (en) * | 2013-04-17 | 2014-10-22 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst, preparation method and application thereof |
| CN114054076A (en) * | 2020-08-06 | 2022-02-18 | 中国石油天然气股份有限公司 | Catalyst for catalyzing aromatization of light gasoline and preparation method thereof |
| CN115536487B (en) * | 2022-10-12 | 2024-06-14 | 宁波巨化化工科技有限公司 | High-purity low-carbon alkane production process and equipment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597865A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Process for hydrogenating modifying faulty gasoline |
| CN1990104A (en) * | 2005-12-30 | 2007-07-04 | 中国科学院大连化学物理研究所 | Molecular sieve catalyst, preparing method and use thereof |
| CN101440305A (en) * | 2007-11-22 | 2009-05-27 | 中国石油大学(北京) | Hydro-upgrading method for FCC gasoline |
| CN101439291A (en) * | 2007-11-19 | 2009-05-27 | 中国石油大学(北京) | Multiple-addition agent modified selective hydrodesulfurization catalyst and preparation method thereof |
-
2010
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597865A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Process for hydrogenating modifying faulty gasoline |
| CN1990104A (en) * | 2005-12-30 | 2007-07-04 | 中国科学院大连化学物理研究所 | Molecular sieve catalyst, preparing method and use thereof |
| CN101439291A (en) * | 2007-11-19 | 2009-05-27 | 中国石油大学(北京) | Multiple-addition agent modified selective hydrodesulfurization catalyst and preparation method thereof |
| CN101440305A (en) * | 2007-11-22 | 2009-05-27 | 中国石油大学(北京) | Hydro-upgrading method for FCC gasoline |
Non-Patent Citations (1)
| Title |
|---|
| 权利要求2，3. |
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