CN103623860B - For catalyst and the Synthesis and applications of the oligomerisation of Fischer-Tropsch synthetic low-carbon alkene - Google Patents
For catalyst and the Synthesis and applications of the oligomerisation of Fischer-Tropsch synthetic low-carbon alkene Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 125
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 45
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 36
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 36
- 239000002808 molecular sieve Substances 0.000 claims abstract description 94
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 94
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 59
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 38
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 26
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 13
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 239000011787 zinc oxide Substances 0.000 claims abstract description 13
- 239000000446 fuel Substances 0.000 claims abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 37
- 150000003839 salts Chemical class 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- 229910052710 silicon Inorganic materials 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 9
- 235000019353 potassium silicate Nutrition 0.000 claims description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 8
- 229910003243 Na2SiO3·9H2O Inorganic materials 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- -1 carbon olefins Chemical class 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- 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 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 239000003502 gasoline Substances 0.000 abstract description 18
- 239000002283 diesel fuel Substances 0.000 abstract description 17
- 150000001336 alkenes Chemical class 0.000 abstract description 15
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000011973 solid acid Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- JOJYUFGTMHSFEE-YONYXQDTSA-M Cytarabine ocfosphate Chemical compound [Na+].O[C@H]1[C@H](O)[C@@H](COP([O-])(=O)OCCCCCCCCCCCCCCCCCC)O[C@H]1N1C(=O)N=C(N)C=C1 JOJYUFGTMHSFEE-YONYXQDTSA-M 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of catalyst for the oligomerisation of Fischer-Tropsch synthetic low-carbon alkene and Synthesis and applications; Catalyst forms primarily of ZSM-5 molecular sieve, and containing one or more in zirconia, zinc oxide, lanthana, nickel oxide or non-metal assistant, the preparation relating to catalyst comprises the synthesis of ZSM-5 molecular sieve and the modification of molecular sieve, and the catalyst prepared produces liquid fuel for the olefin(e) oligomerization of high temperature fischer-tropsch synthesizing low-carbon.Compared with prior art, the present invention, in the modifying process of carrier, adds the auxiliary agents such as fluorine, boron, phosphorus, zirconium, zinc, lanthanum, nickel, improves surface acidity and the pore passage structure of carrier; It is active that the catalyst that the present invention obtains has higher low-carbon alkene oligomerisation reaction, and petrol and diesel oil product is controlled, and wherein gasoline selective is up to 95.2%, and diesel oil is selective is up to 60.5%.
Description
Technical Field
The invention relates to a catalyst for oligomerization of low-carbon olefin, preparation and application thereof, in particular to a catalyst for oligomerization of low-carbon olefin of Fischer-Tropsch synthesis product, preparation and application thereof, belonging to the field of petrochemical industry.
Background
The rapid increase of world economy causes more demands on petrochemical raw materials, so that the crude oil reserves in the world are gradually reduced, the petroleum price is continuously increased, and the external dependence of China is gradually increased. Therefore, research and development of alternative energy sources for petroleum is urgently needed. The fischer-tropsch synthesis process is one of the most feasible ways to achieve the conversion of coal, natural gas and biomass into liquid fuels. The coal-to-liquid process relieves the contradiction between energy supply and demand in China at present and promotes the diversification of national energy and the sustainable development of economy.
The gas phase product of high temperature Fischer-Tropsch synthesis is mainly C2-C6Lower olefins of which C4According to the method, the gasoline or the diesel oil is obtained by oligomerization, so that the yield of the coal-to-oil process can be improved, and the comprehensive utilization of carbon is improved. The oligomerization products of the butylene comprise dimerization, trimerization, tetramerization and pentapolymerization products, and the oligomerization reaction is accompanied by the oligomerization reactionWith the occurrence of two side reactions of isomerization and cracking, the reaction product becomes more complex, which is beneficial to improving the octane number of gasoline and the cetane number of diesel oil.
At present, the low-carbon olefin oligomerization catalysts mainly comprise homogeneous catalysts, heterogeneous catalysts and ionic liquid catalytic systems developed in recent years. Homogeneous catalysts are mainly ziegler-type complex catalysts, the representative reaction process of which is the DimersolX process developed by IFP corporation, and the homogeneous catalysts have the outstanding advantages of high activity and high selectivity, and lower reaction temperature, and are easier to control than corresponding heterogeneous catalytic reactions. However, the homogeneous catalysis process has the problems of difficult separation of reaction products and catalysts, environmental pollution caused by solvents, high operation cost and the like. In view of this, the 20 th century and the 70 th century have been more focused on the solid acid catalyst multi-phase butene oligomerization process.
Heterogeneous catalysts can be divided into solid acid catalysts and supported catalysts. Solid acid catalysts can in turn be divided into molecular sieve type and non-molecular sieve type catalysts, with solid phosphoric acid catalyst (SPA) and molecular sieve catalyst being the two most important solid acid catalysts. The solid phosphoric acid catalyst has the characteristics of narrow oligomer distribution and high branching degree, and the mixed C4The oligomerization-hydrogenation is used for producing industrial isooctane, the high-octane component of gasoline can replace isobutane or butylene, and the liquid acid catalyst is used for producing the industrial isooctane through alkylation. The technology called alkylate production without liquid acid has developed rapidly in recent years and has a wide prospect. The solid phosphoric acid catalyst is one of the industrial catalysts for butene oligomerization. The catalyst is also the most widely used butene oligomerization catalyst at present, such as the nonselective olefin oligomerization SPAC process developed by UOP company. The SPAC belongs to medium-strong acid, and butene oligomerization products are mainly dimers, so that the catalyst has the advantages of high catalytic activity, low requirement on impurities, long one-way service life, low production cost and the like. C in Sasol F-T synthesis product by Sasol company in south Africa using solid phosphoric acid as catalyst3、C4The olefin component is oligomerized to increase the yield of the liquid fuel. Generally, the catalyst life is the amount of catalyst produced per kilogram of catalyst1200kg of gasoline, the catalyst is abandoned due to high-pressure inactivation under the state that the conversion rate is not reduced, solid phosphoric acid is easy to be argillized and agglomerated and cannot be regenerated, an oligomerization product is easy to be highly branched, and the catalyst is particularly not suitable for synthesizing diesel oil. In addition, if the reaction temperature of the solid phosphoric acid catalyst is too low during the use process, the catalyst has no activity; if the reaction temperature is too high, the probability of hydrocarbon cracking reaction is increased, and the requirements on the control conditions of the production process are strict.
In recent years, with the development of pollution-free and corrosion-free zeolite catalysts, solid phosphoric acid catalysts are gradually replaced by zeolite catalysts in the production of gasoline oligomers or diesel fuels.
The molecular sieve catalyst is an aluminosilicate system with molecular size and pore diameter, acts in the form of protonic acid in olefin oligomerization reaction, has a unique pore channel structure and extremely strong screening capacity on olefin molecules, so that the molecular sieve catalyst has high catalytic activity and shape-selective catalytic action, particularly has high selectivity of liquid fuels such as gasoline, diesel oil and the like in oligomerization products, and is non-corrosive, pollution-free, strong in anti-poisoning capacity and renewable. Therefore, the series of catalysts immediately attract attention of researchers in olefin oligomerization once appearing. Currently, various molecular sieves have been investigated for the catalytic oligomerization of olefins, of which the medium pore ZSM-5 molecular sieve developed by the company Mobile is considered to be the best zeolitic molecular sieve catalyst for olefin oligomerization performance.
The Mobil corporation of America developed ZSM-5 molecular sieves first in the early 70 s of the 20 th century and MOGD technology in the 80 s, using a medium pore ZSM-5 molecular sieve (the ratio of the amount of silicon to the amount of aluminum is about 70) and 35% by mass Al2O3Kneading into strip catalyst to convert low carbon olefin into gasoline and diesel oil effectively. The ZSM-5 molecular sieve catalyst is beneficial to generating diesel fractions under the reaction conditions of high pressure (5MPa) and low temperature (200-220 ℃), is beneficial to generating gasoline fractions under the reaction conditions of high temperature (285-375 ℃) and low pressure (0.4-3 MPa), and has higher aromatic hydrocarbon content. It has also been shown that a medium pore ZSM-5 molecular sieve catalyst (silica/alumina mole) is used79 mol ratio), Al2O3Is used as a carrier, and a product which takes gasoline as a main product or a product which takes diesel oil as a main product is respectively obtained by changing process conditions. The reaction process adopts a fixed bed reactor, and the reaction is carried out at 190-310 ℃, 4-10 MPa and WHSV of 0.5-1.0 h-1Under conditions such that about 80% of the product is a diesel product (with a cetane number of about 55 and a viscosity of greater than 3 mm)2S); changing the reaction conditions, wherein the product is mainly gasoline under the conditions of 285-375 ℃ and 0.4-3 MPa, and the octane number of the product is as high as 92-95.
Chinese patent CN1387947A discloses and reports synthesis of C from low-carbon olefin12-C18The ZrZSM-5 molecular sieve catalyst and the preparation method thereof, the weight percentage of the catalyst is as follows: zr: 2.0-7.0% of molecular sieve ZSM-5, 93.0-98.0% of molecular sieve ZSM-5, wherein the molecular sieve ZSM is a hydrogen type ZSM-5 molecular sieve with the Si/Al molar ratio of 24-78, Zr ions are introduced into zeolite by ion exchange in an acid solution, and the physical property of the zeolite is adjusted so that the active center of strong acid of the molecular sieve is modulated to the center of weak acid of medium strong acid. Modified oligomerization activity under the same reaction conditions and C12～C18The selectivity of the catalyst is increased from 40% to about 78%, so that the synthesis of diesel oil from low-carbon olefin is possible.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a catalyst for oligomerization of low-carbon olefins in Fischer-Tropsch synthesis products, and preparation and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a catalyst for oligomerization of low-carbon olefin of Fischer-Tropsch synthesis product is mainly composed of ZSM-5 molecular sieve, and contains one or more of zirconia, zinc oxide, lanthanum oxide, nickel oxide or nonmetal auxiliary agent, and the weight percentage of each component is as follows:
preferably, the catalyst is selected from the following components in percentage by weight:
0.1-8.0% of zirconium oxide; 0-8.0% of zinc oxide; 0-5.0% of lanthanum oxide; 0-5.0% of nickel oxide; 0-6.5% of a non-metal additive; 67.5-99.9% of ZSM-5 molecular sieve.
Preferably, the catalyst is prepared from the following components in percentage by weight:
0.5-5.0% of zirconium oxide; 0-5.0% of zinc oxide; 0-2.0% of lanthanum oxide; 0-5.0% of nickel oxide; 0-6.5% of a non-metal additive; 76.5-99.5% of ZSM-5 molecular sieve.
The nonmetal auxiliary agent is selected from one or more of fluorine, boron oxide or phosphorus pentoxide.
A preparation method of a catalyst for oligomerization of low-carbon olefin of a Fischer-Tropsch synthesis product comprises the following steps:
step one, preparing a ZSM-5 molecular sieve:
1) preparing Si salt and Al salt into solution respectively, wherein the Si salt is Na2SiO3·9H2O, silica sol or water glass, Al salt being Al2(SO4)3·18H2O、Al(NO3)3·9H2O-alumina sol or NaAlO2；
2) Slowly adding an Al salt solution into a Si salt solution, wherein the molar ratio of silicon to aluminum is 10-200: 1, and stirring for 3-10 minutes to obtain a Si and Al mixed solution;
3) weighing a template agent according to the molar ratio of the template agent to Si of 0.2-0.6, preparing a solution, wherein the template agent is one or more of tetrapropylammonium bromide, 1, 6-hexamethylenediamine, ethylenediamine or n-butylamine, slowly adding the template agent solution into the Si and Al mixed solution, and stirring for 5-15 minutes;
4) by H2SO4、HNO3Or H3PO4Adjusting the pH value of the solution to 8.0-11.0 to form gel;
5) transferring the gel into a crystallization kettle, and crystallizing at 130-200 ℃ for 20-120 hours;
6) carrying out suction filtration, washing and drying on the crystallized crystals, and roasting at 400-600 ℃ for 4-8 hours to obtain a Na-type ZSM-5 molecular sieve;
7) by HNO3、NH4NO3Or (NH)4)2SO4The solution is used as a proton exchanger to carry out proton exchange on the Na-type ZSM-5 molecular sieve, wherein the proton exchange temperature is 50-90 ℃, and the exchange time is 1-3 hours;
8) drying the proton exchanged molecular sieve, and roasting at 300-600 ℃ for 4-8 hours to obtain a proton type ZSM-5 molecular sieve;
and secondly, modifying the proton type ZSM-5 molecular sieve to obtain the catalyst for oligomerization of the low-carbon olefin of the Fischer-Tropsch synthesis product.
The modification of the proton type ZSM-5 molecular sieve comprises two methods:
1) firstly, modifying the synthesized proton type ZSM-5 molecular sieve by using a non-metal auxiliary agent, and then modifying the catalyst by using one or more of nitrates or sulfates of zirconium, zinc, lanthanum or nickel by using an ion exchange method or an impregnation method; or,
2) one or more of fluoride, boron, phosphorus, zirconium, zinc, lanthanum or nickel nitrate or sulfate is adopted for modification at the same time.
The specific surface area of the prepared catalyst is 250-450 m2The pore volume is 0.008-0.2 cm3/g。
The application of the catalyst for the oligomerization of low-carbon olefin of a Fischer-Tropsch synthesis product is used for producing liquid fuel by the oligomerization of the low-carbon olefin synthesized by a high-temperature Fischer-Tropsch synthesis process, and the process conditions are as follows: reaction temperature 1The temperature is 90-375 ℃, the reaction pressure is 1.0-6.0 MPa, and the volume airspeed is 0.2-5.0 h-1。
Compared with the prior art, the invention has the following advantages:
the catalyst prepared by the invention has higher low-carbon olefin oligomerization reaction activity, and the proportion of gasoline and diesel oil in the product can be adjusted by changing reaction conditions, wherein the highest selectivity of gasoline is 95.2 percent, and the highest selectivity of diesel oil is 60.5 percent.
Detailed Description
The present invention will be described in detail with reference to specific examples, but the scope of the present invention is not limited to these examples.
Example 1
Preparation of molecular sieve catalysts
(1) Firstly weighing 72.2g of water glass, putting the water glass into a 1000ml three-neck glass flask, adding 289ml of deionized water, stirring to dissolve, and preheating to 50 ℃;
(2) 1.8202gAl are weighed out2(SO4)3·18H2Placing O into a 50ml glass beaker, adding 16ml deionized water, and stirring for dissolving;
(3) weighing 25.6g of tetrapropylammonium bromide (TPABr) and putting the weighed tetrapropylammonium bromide (TPABr) into a 200ml glass beaker, adding 102ml of deionized water, and stirring to dissolve;
(4) slowly adding Al salt into the Si salt, and stirring for 5 minutes;
(5) slowly adding TPABr into the mixed solution of Si and Al, and stirring for 10 minutes;
(6) with 20% H2SO4Adjusting the pH value of the mixed solution to 10.0 +/-0.2 to generate gel;
(7) stirring and aging the gel in a water bath at 50 ℃ for 3 hours;
(8) putting the aged gel into a crystallization kettle, and crystallizing for 50 hours at 170 ℃;
(9) carrying out suction filtration on the crystallized crystals, washing the crystals to be neutral by using deionized water, then putting the crystals into a 120 ℃ oven for drying overnight, putting the dried crystals into a muffle furnace, and roasting the crystals for 6 hours at 500 ℃ to obtain the Na-type ZSM-5 molecular sieve;
(10) removing 1mol/L of HNO3Carrying out proton exchange modification on the calcined catalyst according to the solid-to-liquid ratio of 1:10, wherein the exchange temperature is 50 ℃, and the exchange time is 3 hours;
(11) and drying the proton-exchanged molecular sieve at 120 ℃, and roasting at 500 ℃ to obtain the proton-type ZSM-5 molecular sieve.
Example 2
The auxiliary agent ZrO is added on the basis of the proton type ZSM-5 molecular sieve of example 12，ZrO2The mass percentage of Zr (NO) is 2 percent, and an isometric immersion method is adopted to add Zr (NO)3)4·5H2And O, standing at room temperature for 6 hours, drying at 120 ℃, and roasting at 300 ℃ for 6 hours to obtain the catalyst A.
Example 3
Adding an auxiliary agent NiO into the proton type ZSM-5 molecular sieve in the example 1, wherein the mass percentage of the NiO is 3 percent, and adding Ni (NO) by adopting an equal volume impregnation method3)2·6H2And O, standing at room temperature for 6 hours, drying at 120 ℃, and roasting at 300 ℃ for 6 hours to obtain the catalyst B.
Example 4
A lanthanum promoter was added to the proton type ZSM-5 molecular sieve of example 1. Using 0.3mol/LLa (NO)3Solution pairThe proton type ZSM-5 molecular sieve carries out ion exchange in water bath at 50 ℃ for 3 hours. And then carrying out suction filtration, washing, drying and roasting at 300 ℃ to obtain the phosphorus modified catalyst C.
Example 5
A phosphorus adjuvant was added to the proton type ZSM-5 molecular sieve of example 1. Using 1mol/LH3PO4The proton type ZSM-5 molecular sieve is subjected to ion exchange in a water bath at 50 ℃, and the exchange time is 3 hours. And carrying out suction filtration, washing, drying and roasting at 300 ℃ to obtain the lanthanum modified catalyst D.
Evaluation of catalyst Activity for olefin oligomerization
In order to further illustrate the high activity of the catalysts in examples 1 to 5, the catalysts in examples 1 to 5 were used to perform oligomerization evaluation experiments on low carbon olefins using high temperature fischer-tropsch synthesized low carbon olefins as raw materials. The evaluation of the catalyst was carried out on a 10ml fixed bed micro-reactor, with a catalyst loading of 3.0 g. The pretreatment conditions of the catalyst are N2Pretreatment at 450 ℃ for 6 hours, N2The flow rate was 60 ml/min. The reaction conditions are as follows: the reaction temperature is 260 ℃, the reaction pressure is 3MPa, and the volume space velocity is 2.0h-1. The evaluation results of the catalysts A to D in examples 1 to 5 are shown in Table 1.
TABLE 1 olefin oligomerization Performance of catalysts prepared in examples 1-4
| Catalyst and process for preparing same | Gasoline selectivity/%) | Diesel oil selectivity/%) |
| A | 69.1 | 30.9 |
| B | 49.9 | 50.1 |
| C | 83.3 | 16.7 |
| D | 82.3 | 17.7 |
In order to further improve the reaction activity of the catalyst and the selectivity of gasoline and diesel oil in the product, a method for modulating the reaction temperature is adopted to carry out an olefin oligomerization evaluation experiment on the catalyst C, and the evaluation conditions of the catalyst are as follows: the space velocity is 2.0h-1The reaction pressure was 5.0MPa, and the evaluation results are shown in Table 2.
Table 2 olefin oligomerization performance of the catalyst prepared in example 3 at different temperatures
| Catalyst and process for preparing same | Temperature/. degree.C | Gasoline selectivity/%) | Diesel oil selectivity/%) |
| B | 260 | 49.9 | 50.1 |
| B | 300 | 77.9 | 22.1 |
| B | 370 | 95.2 | 4.8 |
In order to further improve the reaction activity of the catalyst and the selectivity of gasoline and diesel oil in the product, a method of adjusting space velocity is adopted to carry out an olefin oligomerization evaluation experiment on the catalyst A, and the evaluation conditions of the catalyst are as follows: the reaction temperature was 260 ℃ and the reaction pressure was 5.0MPa, and the evaluation results are shown in Table 3.
Table 3 performance of the catalyst prepared in example 2 for oligomerization of olefins at different space velocities
| Catalyst and process for preparing same | Space velocity/h-1 | Gasoline selectivity/%) | Diesel oil selectivity/%) |
| A | 1.0 | 39.5 | 60.5 |
| A | 2.0 | 69.1 | 30.9 |
Example 6
A catalyst for oligomerization of low-carbon olefin of Fischer-Tropsch synthesis products is mainly composed of a ZSM-5 molecular sieve and contains zirconia, and the weight percentage of each component is as follows: 99.9 percent of ZSM-5 molecular sieve and 0.1 percent of zirconia.
The preparation method of the catalyst comprises the following steps:
step one, preparing a ZSM-5 molecular sieve:
1) preparing Si salt and Al salt into solution respectively, wherein the Si salt is Na2SiO3·9H2O, silica sol or water glass, Al salt being Al2(SO4)3·18H2O；
2) Slowly adding an Al salt solution into a Si salt solution, wherein the molar ratio of silicon to aluminum is 10: 1, stirring for 3 minutes to obtain a mixed solution of Si and Al;
3) weighing the template agent according to the molar ratio of the template agent to Si of 0.2:1, preparing a solution, wherein the template agent is 1, 6-hexanediamine, slowly adding the template agent solution into the mixed solution of Si and Al, and stirring for 5 minutes;
4) by H2SO4Adjusting the pH value of the solution to 8.0-8.2 to form gel;
5) transferring the gel into a crystallization kettle, and crystallizing at 130 ℃ for 120 hours;
6) carrying out suction filtration, washing and drying on the crystallized crystals, and roasting at 400 ℃ for 8 hours to obtain the Na-type ZSM-5 molecular sieve;
7) by HNO3The solution is used as a proton exchanger to carry out proton exchange on the Na-type ZSM-5 molecular sieve, wherein the proton exchange temperature is 50 ℃, and the exchange time is 3 hours;
8) drying the proton exchanged molecular sieve, and roasting at 300 ℃ for 8 hours to obtain a proton type ZSM-5 molecular sieve;
and secondly, modifying the proton type ZSM-5 molecular sieve by using nitrate of zirconium and adopting an ion exchange method or an impregnation method to obtain the catalyst for oligomerization of the low-carbon olefin of the Fischer-Tropsch synthesis product.
The specific surface area of the prepared catalyst is 250m2Per g, pore volume of 0.008cm3/g。
The application of the catalyst is that the catalyst is used for producing liquid fuel by oligomerization of low-carbon olefin synthesized by high-temperature Fischer-Tropsch, and the process conditions are as follows: the reaction temperature is 190 ℃, the reaction pressure is 1.0MPa, and the volume space velocity is 0.2h-1。
Example 7
A catalyst for oligomerization of low-carbon olefin of Fischer-Tropsch synthesis products is mainly composed of a ZSM-5 molecular sieve and contains zirconia, and the weight percentage of each component is as follows: 99.5 percent of ZSM-5 molecular sieve and 0.5 percent of zirconia.
The preparation method of the catalyst comprises the following steps:
step one, preparing a ZSM-5 molecular sieve:
1) preparing Si salt and Al salt into solution respectively, wherein the Si salt is Na2SiO3·9H2O, silica sol or water glass, Al salt being Al (NO)3)3·9H2O-alumina sol;
2) slowly adding an Al salt solution into a Si salt solution, wherein the molar ratio of silicon to aluminum is 200:1, stirring for 10 minutes to obtain a mixed solution of Si and Al;
3) according to the mol ratio of the template agent to Si of 0.6: 1, weighing a template agent according to the proportion of 1, preparing a solution, wherein the template agent is ethylenediamine, slowly adding the template agent solution into the mixed solution of Si and Al, and stirring for 15 minutes;
4) with HNO3Adjusting the pH value of the solution to 9.0-10.0 to form gel;
5) transferring the gel into a crystallization kettle, and crystallizing at 200 ℃ for 20 hours;
6) carrying out suction filtration, washing and drying on the crystallized crystals, and roasting for 4 hours at 600 ℃ to obtain the Na-type ZSM-5 molecular sieve;
7) by NH4NO3The solution is used as a proton exchanger to carry out proton exchange on the Na-type ZSM-5 molecular sieve, wherein the proton exchange temperature is 90 ℃, and the exchange time is 1 hour;
8) drying the proton exchanged molecular sieve, and roasting at 600 ℃ for 4 hours to obtain a proton type ZSM-5 molecular sieve;
and secondly, modifying the proton type ZSM-5 molecular sieve by using nitrate of zirconium and adopting an ion exchange method or an impregnation method to obtain the catalyst for oligomerization of the low-carbon olefin of the Fischer-Tropsch synthesis product.
The specific surface area of the prepared catalyst is 450m2Per g, pore volume of 0.2cm3/g。
Use of the above catalyst, catalystThe method is used for producing liquid fuel by oligomerization of low-carbon olefin through Fischer-Tropsch synthesis at high temperature, and has the following process conditions: the reaction temperature is 375 ℃, the reaction pressure is 6.0MPa, and the volume space velocity is 5.0h-1。
Example 8
A catalyst for oligomerization of low-carbon olefin of Fischer-Tropsch synthesis product is mainly composed of ZSM-5 molecular sieve, and contains zirconium oxide, zinc oxide, lanthanum oxide, nickel oxide and non-metal auxiliary agent (fluorine), and the weight percentage of each component is as follows: 8.0% of zirconium oxide; 8.0 percent of zinc oxide; 5.0 percent of lanthanum oxide; 5.0% of nickel oxide; 6.5 percent of non-metal additive; ZSM-5 molecular sieve 67.5.
The preparation method of the catalyst comprises the following steps:
step one, preparing a ZSM-5 molecular sieve:
1) preparing Si salt and Al salt into solution respectively, wherein the Si salt is Na2SiO3·9H2O, silica sol or water glass, Al salt is NaAlO2；
2) Slowly adding an Al salt solution into a Si salt solution, wherein the molar ratio of silicon to aluminum is 100:1, and stirring for 5 minutes to obtain a Si and Al mixed solution;
3) weighing the template agent according to the molar ratio of the template agent to Si of 0.4:1, preparing a solution, wherein the template agent is n-butylamine, slowly adding the template agent solution into the mixed solution of Si and Al, and stirring for 10 minutes;
4) by H3PO4Adjusting the pH value of the solution to 11.0 to form gel;
5) transferring the gel into a crystallization kettle, and crystallizing at 180 ℃ for 60 hours;
6) carrying out suction filtration, washing and drying on the crystallized crystals, and roasting for 6 hours at 500 ℃ to obtain the Na-type ZSM-5 molecular sieve;
7) by (NH)4)2SO4The solution is used as a proton exchanger to carry out proton exchange on the Na-type ZSM-5 molecular sieve, wherein the proton exchange temperature is 70 ℃, and the exchange time is 2 hours;
8) drying the proton exchanged molecular sieve, and roasting at 400 ℃ for 6 hours to obtain a proton type ZSM-5 molecular sieve;
and secondly, modifying the synthesized proton type ZSM-5 molecular sieve by using a non-metal auxiliary agent, and modifying the catalyst by using a sulfate of zirconium, zinc, lanthanum or nickel by using an ion exchange method or an impregnation method to obtain the catalyst for oligomerization of the low-carbon olefin of the Fischer-Tropsch synthesis product.
The specific surface area of the prepared catalyst is 350m2Per g, pore volume of 0.1cm3/g。
The application of the catalyst is that the catalyst is used for producing liquid fuel by oligomerization of low-carbon olefin synthesized by high-temperature Fischer-Tropsch, and the process conditions are as follows: the reaction temperature is 250 ℃, the reaction pressure is 4.0MPa, and the volume space velocity is 2.0h-1。
Example 9
A catalyst for oligomerization of low-carbon olefin of Fischer-Tropsch synthesis product is mainly composed of ZSM-5 molecular sieve, and contains zirconium oxide, zinc oxide, lanthanum oxide, nickel oxide and non-metal auxiliary agent (boron oxide), and the weight percentage of each component is as follows: 5.0% of zirconium oxide; 5.0 percent of zinc oxide; 2.0 percent of lanthanum oxide; 5.0% of nickel oxide; 6.5 percent of non-metal additive; ZSM-5 molecular sieve 76.5.
The preparation method of the catalyst comprises the following steps:
step one, preparing a ZSM-5 molecular sieve:
1) preparing Si salt and Al salt into solution respectively, wherein the Si salt is Na2SiO3·9H2O, silica sol or water glass, Al salt being Al2(SO4)3·18H2O；
2) Slowly adding an Al salt solution into a Si salt solution, wherein the molar ratio of silicon to aluminum is 50:1, and stirring for 6 minutes to obtain a Si and Al mixed solution;
3) weighing the template agent according to the molar ratio of the template agent to Si of 0.3:1, preparing a solution, wherein the template agent is tetrapropylammonium bromide, slowly adding the template agent solution into the Si and Al mixed solution, and stirring for 8 minutes;
4) by H2SO4Adjusting the pH value of the solution to 8.0 to form gel;
5) transferring the gel into a crystallization kettle, and crystallizing at 150 ℃ for 80 hours;
6) carrying out suction filtration, washing and drying on the crystallized crystals, and roasting at 400 ℃ for 7 hours to obtain the Na-type ZSM-5 molecular sieve;
7) by (NH)4)2SO4The solution is used as a proton exchanger to carry out proton exchange on the Na-type ZSM-5 molecular sieve, wherein the proton exchange temperature is 70 ℃, and the exchange time is 2 hours;
8) drying the proton exchanged molecular sieve, and roasting at 400 ℃ for 7 hours to obtain a proton type ZSM-5 molecular sieve;
and step two, modifying the proton type ZSM-5 molecular sieve by adopting nitrates of boron, zirconium, zinc, lanthanum or nickel simultaneously to obtain the catalyst for oligomerization of the Fischer-Tropsch synthesis product low-carbon olefin.
The specific surface area of the prepared catalyst is 250-450 m2The pore volume is 0.008-0.2 cm3/g。
The application of the catalyst is that the catalyst is used for producing liquid fuel by oligomerization of low-carbon olefin synthesized by high-temperature Fischer-Tropsch, and the process conditions are as follows: the reaction temperature is 190-375 ℃, the reaction pressure is 1.0-6.0 MPa, and the volume airspeed is 0.2-5.0 h-1。
Example 10
A catalyst for oligomerization of low-carbon olefin of Fischer-Tropsch synthesis product is mainly composed of ZSM-5 molecular sieve, and contains zirconium oxide, zinc oxide, lanthanum oxide, nickel oxide and non-metallic auxiliary agent (phosphorus pentoxide), and the weight percentages of the components are as follows: 10.0% of zirconium oxide; 10.0 percent of zinc oxide; 7.0 percent of lanthanum oxide; 15.0% of nickel oxide; 10.5 percent of non-metal additive; ZSM-5 molecular sieve 48.0.
The preparation method of the catalyst comprises the following steps:
step one, preparing a ZSM-5 molecular sieve:
1) preparing Si salt and Al salt into solution respectively, wherein the Si salt is Na2SiO3·9H2O, silica sol or water glass, Al salt is NaAlO2；
2) Slowly adding an Al salt solution into a Si salt solution, wherein the molar ratio of silicon to aluminum is 100:1, and stirring for 5 minutes to obtain a Si and Al mixed solution;
3) weighing the template agent according to the molar ratio of the template agent to Si of 0.4:1, preparing a solution, wherein the template agent is n-butylamine, slowly adding the template agent solution into the mixed solution of Si and Al, and stirring for 10 minutes;
4) by H3PO4Adjusting the pH value of the solution to 11.0 to form gel;
5) transferring the gel into a crystallization kettle, and crystallizing at 180 ℃ for 60 hours;
6) carrying out suction filtration, washing and drying on the crystallized crystals, and roasting for 6 hours at 500 ℃ to obtain the Na-type ZSM-5 molecular sieve;
7) by (NH)4)2SO4The solution is used as a proton exchanger to carry out proton exchange on the Na-type ZSM-5 molecular sieve, wherein the proton exchange temperature is 70 ℃, and the exchange time is 2 hours;
8) drying the proton exchanged molecular sieve, and roasting at 400 ℃ for 6 hours to obtain a proton type ZSM-5 molecular sieve;
and secondly, modifying the proton type ZSM-5 molecular sieve to obtain the catalyst for oligomerization of low-carbon olefin of the Fischer-Tropsch synthesis product, modifying the synthesized proton type ZSM-5 molecular sieve by using a non-metallic auxiliary agent, and modifying the catalyst by using a sulfate of zirconium, zinc, lanthanum or nickel and adopting an ion exchange method or an impregnation method.
The specific surface area of the prepared catalyst is 250-450 m2The pore volume is 0.008-0.2 cm3/g。
The application of the catalyst is that the catalyst is used for producing liquid fuel by oligomerization of low-carbon olefin synthesized by high-temperature Fischer-Tropsch, and the process conditions are as follows: the reaction temperature is 190-375 ℃, the reaction pressure is 1.0-6.0 MPa, and the volume airspeed is 0.2-5.0 h-1。
Claims (7)
1. The catalyst for oligomerization of low-carbon olefin of Fischer-Tropsch synthesis product is characterized by mainly comprising a ZSM-5 molecular sieve and one or more of zirconia, zinc oxide, lanthanum oxide, nickel oxide or non-metallic auxiliary agents, and the catalyst comprises the following components in percentage by weight:
2. the catalyst for oligomerization of low carbon olefins from Fischer-Tropsch synthesis of claim 1, wherein the catalyst is selected from the following components and weight percentages:
0.1-8.0% of zirconium oxide; 0-8.0% of zinc oxide; 0-5.0% of lanthanum oxide; 0-5.0% of nickel oxide; 6.5 percent of non-metal additive; 67.5-99.9% of ZSM-5 molecular sieve.
3. The catalyst for oligomerization of low carbon olefins from Fischer-Tropsch synthesis of claim 1, wherein the catalyst is selected from the following components and weight percentages:
0.5-5.0% of zirconium oxide; 0-5.0% of zinc oxide; 0-2.0% of lanthanum oxide; 0-5.0% of nickel oxide; 6.5 percent of non-metal additive; 76.5-99.5% of ZSM-5 molecular sieve.
4. The catalyst for oligomerization of low carbon olefin of Fischer-Tropsch synthesis product of claim 1, wherein the non-metallic auxiliary agent is one or more selected from fluorine, boron oxide and phosphorus pentoxide.
5. The preparation method of the catalyst for oligomerization of low carbon olefins from Fischer-Tropsch synthesis product according to any one of claims 1 to 4, characterized by comprising the following steps:
step one, preparing a ZSM-5 molecular sieve:
1) respectively preparing Si salt and Al salt into solution, wherein the Si salt is Na2SiO3·9H2O, silica sol or water glass, Al salt being Al2(SO4)3·18H2O、Al(NO3)3·9H2O-alumina sol or NaAlO2；
2) Slowly adding an Al salt solution into an Si salt solution, wherein the molar ratio of silicon to aluminum is 10-200: 1, stirring for 3-10 minutes to obtain a Si and Al mixed solution;
3) according to the molar ratio of the template agent to Si of 0.2-0.6: 1, weighing a template agent according to the proportion of 1, preparing a solution, wherein the template agent is one or more of tetrapropylammonium bromide, 1, 6-hexamethylenediamine, ethylenediamine or n-butylamine, slowly adding the template agent solution into the Si and Al mixed solution, and stirring for 5-15 minutes;
4) by H2SO4、HNO3Or H3PO4Adjusting the pH value of the solution to 8.0-11.0 to form gel;
5) transferring the gel into a crystallization kettle, and crystallizing at 130-200 ℃ for 20-120 hours;
6) carrying out suction filtration, washing and drying on the crystallized crystals, and roasting at 400-600 ℃ for 4-8 hours to obtain a Na-type ZSM-5 molecular sieve;
7) by HNO3、NH4NO3Or (NH)4)2SO4The solution is used as a proton exchanger to carry out proton exchange on the Na-type ZSM-5 molecular sieve, wherein the proton exchange temperature is 50-90 ℃, and the exchange time is 1-3 hours;
8) drying the proton exchanged molecular sieve, and roasting at 300-600 ℃ for 4-8 hours to obtain a proton type ZSM-5 molecular sieve;
and secondly, modifying the proton type ZSM-5 molecular sieve to obtain the catalyst for oligomerization of the low-carbon olefin of the Fischer-Tropsch synthesis product:
the modification of the proton type ZSM-5 molecular sieve comprises two methods:
1) firstly, modifying the synthesized proton type ZSM-5 molecular sieve by using a non-metal auxiliary agent, and then modifying the catalyst by using one or more of nitrates or sulfates of zirconium, zinc, lanthanum or nickel by using an ion exchange method or an impregnation method; or,
2) one or more of fluoride, boron, phosphorus, zirconium, zinc, lanthanum or nickel nitrate or sulfate is adopted for modification at the same time.
6. The preparation method of the catalyst for oligomerization of low-carbon olefins from Fischer-Tropsch synthesis products according to claim 5, wherein the specific surface area of the prepared catalyst is 250-450 m2The pore volume is 0.008-0.2 cm3/g。
7. The application of the catalyst for oligomerization of low-carbon olefins obtained by Fischer-Tropsch synthesis according to any one of claims 1 to 4, wherein the catalyst is used for oligomerization production of liquid fuels by low-carbon olefins obtained by Fischer-Tropsch synthesis at high temperature, and the process conditions are as follows: the reaction temperature is 190-375 ℃, the reaction pressure is 1.0-6.0 MPa, and the volume airspeed is 0.2-5.0 h-1。
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| CN115970718B (en) * | 2022-12-26 | 2024-10-22 | 正大能源材料(大连)有限公司 | Catalyst for preparing low-carbon olefin, preparation method and application |
| CN116099554B (en) * | 2023-01-17 | 2025-01-21 | 山东京博石油化工有限公司 | A catalyst for preparing higher carbon olefins and its preparation method and application |
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