CN106076408B - N-alkene isomerization catalyst and its preparation method and application - Google Patents
N-alkene isomerization catalyst and its preparation method and application Download PDFInfo
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- CN106076408B CN106076408B CN201610417288.1A CN201610417288A CN106076408B CN 106076408 B CN106076408 B CN 106076408B CN 201610417288 A CN201610417288 A CN 201610417288A CN 106076408 B CN106076408 B CN 106076408B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims description 11
- 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 113
- 239000002808 molecular sieve Substances 0.000 claims abstract description 110
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 46
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000011859 microparticle Substances 0.000 claims abstract description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 30
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims description 44
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000000395 magnesium oxide Substances 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 9
- 239000011260 aqueous acid Substances 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 5
- 239000011654 magnesium acetate Substances 0.000 claims description 5
- 229940069446 magnesium acetate Drugs 0.000 claims description 5
- 235000011285 magnesium acetate Nutrition 0.000 claims description 5
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- -1 is beaten Substances 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 230000007423 decrease Effects 0.000 abstract description 5
- 230000008929 regeneration Effects 0.000 abstract description 5
- 238000011069 regeneration method Methods 0.000 abstract description 5
- 239000000571 coke Substances 0.000 abstract description 4
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 abstract description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011156 evaluation Methods 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- 239000004615 ingredient Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 210000002966 serum Anatomy 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000011208 chromatographic data Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
- C07C5/2708—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of N-alkene isomerization catalyst, mass containing 50-90%() molecular sieve, remaining is aluminium oxide；The molecular sieve is made of SAPO-11 and ZSM-5, and wherein SAPO-11 accounts for the 75-90%(mass of molecular sieve total amount), ZSM-5 accounts for the 10-25%(mass of molecular sieve total amount)；The microparticle size 1-2um of molecular sieve in catalyst.Catalyst normal olefine isomerization activity with higher, isomeric olefine yield is higher and is able to maintain the long period, with longer one way operation cycle, the multiple coke burning regeneration performance range of decrease is smaller, suitable for the process of isobutene is prepared through isomerization reaction by n-butene, and the process of iso-amylene is prepared through isomerization reaction by n-pentene, especially suitable for four n-butene isomerization of carbon after ether, prepare the process of isobutene.
Description
Technical field
The invention belongs to catalyst field, it is related to a kind of N-alkene isomerization catalyst and its preparation method and application.
Background technique
Methyl tertiary butyl ether(MTBE) (MTBE) in reformulated gasoline and oxygenated gasoline because showing higher octane number, low steam
Pressure, the favorable solubility in gasoline fraction hydro carbons, so becoming excellent gasoline addO-on therapy, its demand was rapid in recent years
Increase, the isobutene yield obtained by traditional petroleum catalytic cracking and hot-working is far from the need for meeting ether-based device production
It wants.
The ether-based device outlet material for producing MTBE, after separating methanol and ether, positive 40% or more structure butene content, therefore
The material rich in n-butene is subjected to skeletal isomerization and produces isobutene, can achieve the purpose that increase production isobutene.The technique is former
Expect that cheap and easy to get, source is wider, not only can solve the overstock problem of linear alkene, but also can be provided for ether-based device largely containing isobutene
Raw material, only need to be in existing ether-based device added downstream isomerisation of olefin device, thus the technique obtains more answer in the recent period
With newly-built or reconstructed four isomerization unit of carbon after more set ethers.
N-butene skeletal isomerization carries out usually on acidic catalyst, and catalyst includes SAPO (silicoaluminophosphate) system
Column molecular sieve, ferrierite etc..Existing this kind of catalyst, within short time such as several days all have preferable n-butene conversion and
Selective isobutene, but performance declines rapidly later, therefore one way is shorter operation cycle, needs frequent coke burning regeneration, and after burning
Performance is easy decline.Have the more prior art and propose various improvement, but usually one way days of operation is no more than 30 days, uses
It is obvious that performance decline is also tended to after 1 year, thus regeneration times are more, catalyst change is frequent, costly.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of N-alkene isomerization catalyst, (quality) containing 50-90%
Molecular sieve, remaining is aluminium oxide；The molecular sieve is made of SAPO-11 and ZSM-5, and wherein SAPO-11 accounts for molecular sieve total amount
75-90% (quality), ZSM-5 accounts for the 10-25% (quality) of molecular sieve total amount；The microparticle size 1- of molecular sieve in catalyst
2um.Catalyst normal olefine isomerization activity with higher, isomeric olefine yield is higher and is able to maintain the long period, tool
There is longer one way operation cycle, the multiple coke burning regeneration performance range of decrease is smaller, different suitable for being prepared by n-butene through isomerization reaction
The process of butylene, and the process of iso-amylene is prepared by n-pentene through isomerization reaction.
N-alkene isomerization catalyst of the invention, it is preferable that molecular sieve content 50-70% (quality)；Preferably,
SAPO-11 accounts for the 80-85% (quality) of molecular sieve total amount, and ZSM-5 accounts for the 15-20% (quality) of molecular sieve total amount.
N-alkene isomerization catalyst of the invention, it is preferable that ZSM-5 molecular sieve silica alumina ratio 40-70.
N-alkene isomerization catalyst of the invention, it is preferable that 0.5-2.0% containing magnesia (quality) in molecular sieve.
The present invention also provides a kind of preparation methods of the N-alkene isomerization catalyst, comprising the following steps:
A, add suitable quantity of water in material-compound tank, the desired amount of SAPO-11 molecular screen primary powder, ZSM-5 molecular sieve original powder and hydrogen is added
Ammonium acetate is added in alumina powder, is beaten, powder total concentration 10-20% (quality) in slurries, acetic acid ammonium concentration 0.5-2.0% (matter
Amount)；The SAPO-11 molecular screen primary powder is the hydrogen type molecular sieve by Crystallizing treatment, is easily dispersed to average grain diameter 1-2um；Institute
Stating ZSM-5 molecular sieve original powder is the hydrogen type molecular sieve by Crystallizing treatment, is easily dispersed to average grain diameter 1-2um；
C, slurries are transferred to autoclave, in 150-220 DEG C of Crystallizing treatment 10-60hr；
D, slurries are spray-dried, and xeraphium adds extrusion after lubricant plus kneading containing aqueous acid, then through drying, 550-600
DEG C roasting, be made catalyst of the present invention.
The preparation method of N-alkene isomerization catalyst of the present invention, it is preferable that step D's contains in aqueous acid, is added
Magnesium acetate is converted into the 0.5-2.0% (quality) that magnesia accounts for molecular sieve, more preferably accounts for 1.0% (quality) of molecular sieve.
The preparation method of N-alkene isomerization catalyst of the present invention, it is preferable that in step C, Crystallizing treatment temperature 170-
200 DEG C, handle time 20-40hr.
The preparation method of N-alkene isomerization catalyst of the present invention, it is preferable that in step D, catalyst is at 560-580 DEG C
Roast 2-4hr.
The preparation method of N-alkene isomerization catalyst of the present invention, it is preferable that before step C, there are also step B: step
Rapid A slurries are further processed with grinding distribution equipment, and powder microparticle is made to refine to average diameter 1-2um.The grinding distribution
Equipment is colloid mill or homogenizer, and wherein colloid mill is relatively cheap and common.
The preparation method of N-alkene isomerization catalyst of the present invention, it is preferable that in step A, the aluminium hydrate powder is
Boehmite dry powder；In step C, it is described acid be one of nitric acid, citric acid, acetic acid or a variety of, wherein acetic acid effect compared with
It is good.
N-alkene isomerization catalyst of the present invention prepares isobutene especially suitable for four n-butene isomerization of carbon after ether
Process.During four n-butene isomerization of carbon prepares isobutene after ether, by controlling technological parameter appropriate, the present invention is just
Structure olefin isomerization catalyst, under conditions of maintaining higher n-butene isomerization activity and higher isobutene yield, tool
There is longer one way operation cycle, can be usually reached 30 days or more, long reached 80 days.Compared to the prior art, one way is transported
Turn number of days to be obviously prolonged, the expense during stopping, burn and going into operation again reduces significantly.
N-alkene isomerization catalyst of the present invention is able to maintain that higher positive structure alkene within longer one way operation cycle
The reason of hydrocarbon isomerization is active and higher isomeric olefine purpose product yield, it may be possible to preferably balance reactivity worth and resistive connection
Burnt, anti-carbon performance, may include:
(1) SAPO-11, ZSM-5 molecular sieve microparticle size are smaller in catalyst, only 1-2um, microparticle external surface area compared with
Greatly, therefore the aperture of microparticle surfaces blocking forming process is slower；Biography of the reactants and products to duct between microparticle in microparticle
Matter is easier to；The size of molecular sieve microparticle is usually above 2um in existing similar catalyst；
(2) SAPO-11 molecular sieve is the major catalytic component of normal olefine isomerization reaction, and reactivity worth declines main
The reason is that coking and the duct carbon distribution of acid centre；The acidity of ZSM-5 molecular sieve is better than SAPO-11, the easy life in olefin feedstock
The alkadienes of by-product, dimer are easier in ZSM-5 molecular sieve microparticle in burnt ingredient such as alkadienes, methanol or isomerization process
Middle coking, carbon distribution and consume, to reduce the coking in SAPO-11 molecular sieve microparticle, carbon distribution, and make catalyst just
Structure olefin isomerization performance is able to maintain for a long time；
(3) SAPO-11 molecular screen primary powder, ZSM-5 molecular sieve original powder and aluminium hydrate powder slurries Crystallizing treatment, reduce
The quantity of acid stronger acid centre, reduces the speed of coking in molecular sieve microparticle, carbon distribution, reduces it in molecular sieve
His side reaction, to improve and maintain the yield of isomerization product.
N-alkene isomerization catalyst of the present invention, in addition to longer one way operation cycle, catalytic performance is also more
Stablize, the decline of the yield of the isomerization activity of normal olefine and isomeric olefine product is smaller after repeatedly regenerating, and this point may
Related with the secondary crystallization processing of molecular sieve, the secondary crystallization processing makes the structure of SAPO-11 molecular sieve, ZSM-5 molecular sieve
Become more stable with performance.
In the present invention, molecular screen primary powder average grain diameter is measured by laser particle analyzer, and slurries carry out ultrasonic disperse before surveying, and is also led to
It crosses electromicroscopic photograph (SEM) to be compareed, two kinds of results are almost the same；With in grinding distribution equipment processing rear slurry microparticle it is flat
Equal diameter, in autoclave in Crystallizing treatment rear slurry microparticle average diameter, measured by laser particle analyzer, before surveying slurries not into
Row ultrasonic disperse；The microparticle size of molecular sieve in catalyst is judged by the electromicroscopic photograph (SEM) of catalyst surface, section.
Specific embodiment
Embodiment 1
Made with the SAPO-11 molecular screen primary powder by Crystallizing treatment and the ZSM-5 molecular sieve original powder by Crystallizing treatment former
Material；SAPO-11 molecular screen primary powder is easily dispersed to average grain diameter 1.2um, crystallinity 95%, chemical component P2O541%, SiO2
12%, Al2O347% (quality)；ZSM-5 molecular sieve original powder is easily dispersed to average grain diameter 1.6um, silica alumina ratio 70, crystallinity
95%.Catalyst is prepared as follows:
A, add 50kg deionized water in 60L material-compound tank, it is former that SAPO-11 molecular screen primary powder 2.0kg, ZSM-5 molecular sieve is added
Ammonium acetate 0.56kg, mashing is added in powder 0.5kg and boehmite dry powder 3.75kg；
C, slurries are transferred to 100L autoclave, in 200 DEG C of Crystallizing treatment 20hr；
D, 200 DEG C of slurries spray drying take xeraphium 5.0kg that sesbania powder 0.15kg is added to mix, add the 0.20kg's containing acetic acid
Φ 2.0mm orifice plate extrusion is used after aqueous solution 4.5kg kneading, then through 120 DEG C of dry 6hr, 570 DEG C of roasting 4hr, catalyst is made
3kg。
It is calculated from ingredient proportion, catalyst obtained by the present embodiment contains the molecular sieve of 50% (quality), contains 50% (quality)
Aluminium oxide；SAPO-11 accounts for 80% (quality) of molecular sieve total amount, and ZSM-5 accounts for 20% (quality) of molecular sieve total amount.From catalysis
Electromicroscopic photograph (SEM) judgement on agent surface, section, the microparticle size 1-2um of molecular sieve in catalyst.
Embodiment 2
Substantially with embodiment 1, difference is in the slurries of step A, SAPO-11 molecular screen primary powder additional amount 2.125kg,
ZSM-5 molecular sieve original powder additional amount 0.375kg.
It is calculated from ingredient proportion, catalyst obtained by the present embodiment contains the molecular sieve of 50% (quality), contains 50% (quality)
Aluminium oxide；SAPO-11 accounts for 85% (quality) of molecular sieve total amount, and ZSM-5 accounts for 15% (quality) of molecular sieve total amount.From catalysis
Electromicroscopic photograph (SEM) judgement on agent surface, section, the microparticle size 1-2um of molecular sieve in catalyst.
Embodiment 3
Substantially with embodiment 1, difference is in the slurries of step A, boehmite dry powder additional amount 1.60kg, Yi Jibu
In rapid D, takes xeraphium 2.5kg that sesbania powder 0.075kg is added to mix, add the aqueous solution 2.3kg of the 0.10kg containing acetic acid.
It is calculated from ingredient proportion, catalyst obtained by the present embodiment contains the molecular sieve of 70% (quality), contains 30% (quality)
Aluminium oxide；SAPO-11 accounts for 80% (quality) of molecular sieve total amount, and ZSM-5 accounts for 20% (quality) of molecular sieve total amount.From catalysis
Electromicroscopic photograph (SEM) judgement on agent surface, section, the microparticle size 1-2um of molecular sieve in catalyst.
Embodiment 4
Substantially with embodiment 1, difference is in the slurries of step A, boehmite dry powder additional amount 0.42kg, Yi Jibu
In rapid D, takes xeraphium 2.5kg that sesbania powder 0.075kg is added to mix, add the aqueous solution 2.5kg of the 0.10kg containing acetic acid.
It is calculated from ingredient proportion, catalyst obtained by the present embodiment contains the molecular sieve of 90% (quality), contains 10% (quality)
Aluminium oxide；SAPO-11 accounts for 80% (quality) of molecular sieve total amount, and ZSM-5 accounts for 20% (quality) of molecular sieve total amount.From catalysis
Electromicroscopic photograph (SEM) judgement on agent surface, section, the microparticle size 1-2um of molecular sieve in catalyst.
Embodiment 5
Substantially with embodiment 1, difference be step D containing in aqueous acid, four water magnesium acetate 0.135kg are added, are converted into
Magnesia accounts for 1.0% (quality) of molecular sieve.
It is calculated from ingredient proportion, catalyst obtained by the present embodiment contains the molecular sieve of 50% (quality), contains 50% (quality)
Aluminium oxide；SAPO-11 accounts for 80% (quality) of molecular sieve total amount, and ZSM-5 accounts for 20% (quality) of molecular sieve total amount, molecular sieve
In another (quality) containing magnesia 1.0%.Judge from the electromicroscopic photograph (SEM) of catalyst surface, section, molecular sieve in catalyst
Microparticle size 1-2um.
Embodiment 6
Substantially with embodiment 2, difference be step D containing in aqueous acid, four water magnesium acetate additional amount 0.068kg, folding
0.5% (quality) of molecular sieve is accounted at magnesia.
It is calculated from ingredient proportion, catalyst obtained by the present embodiment contains the molecular sieve of 50% (quality), contains 50% (quality)
Aluminium oxide；SAPO-11 accounts for 85% (quality) of molecular sieve total amount, and ZSM-5 accounts for 15% (quality) of molecular sieve total amount, molecular sieve
In another (quality) containing magnesia 0.5%.Judge from the electromicroscopic photograph (SEM) of catalyst surface, section, molecular sieve in catalyst
Microparticle size 1-2um.
Embodiment 7
Substantially with embodiment 2, difference be step D containing in aqueous acid, four water magnesium acetate additional amount 0.27kg are converted into
Magnesia accounts for 2.0% (quality) of molecular sieve.
It is calculated from ingredient proportion, catalyst obtained by the present embodiment contains the molecular sieve of 50% (quality), contains 50% (quality)
Aluminium oxide；SAPO-11 accounts for 85% (quality) of molecular sieve total amount, and ZSM-5 accounts for 15% (quality) of molecular sieve total amount, molecular sieve
In (quality) containing magnesia 2.0%.Judge from the electromicroscopic photograph (SEM) of catalyst surface, section, molecular sieve is micro- in catalyst
Particle size 1-2um.
Embodiment 8
Substantially with embodiment 1, difference is in step C, 180 DEG C of Crystallizing treatment temperature, handles time 30hr.
Judge from the electromicroscopic photograph (SEM) of catalyst surface, section, the microparticle size 1-2um of molecular sieve in catalyst.
Embodiment 9
Substantially with embodiment 1, difference is in step C, 170 DEG C of Crystallizing treatment temperature, handles time 40hr.
Judge from the electromicroscopic photograph (SEM) of catalyst surface, section, the microparticle size 1-2um of molecular sieve in catalyst.
Embodiment 10
Substantially with embodiment 1, difference is that before step C, there are also step B: step A slurries are ground with colloid mill
Decentralized processing makes powder microparticle refine to average diameter 1.7um.
In autoclave in Crystallizing treatment rear slurry microparticle average diameter, laser particle analyzer survey 1.9um；Divide in catalyst
Son sieve microparticle size, catalyst surface, section electromicroscopic photograph (SEM) be shown as 1-2um.
Embodiment 11
Substantially with embodiment 1, but the method for combining embodiment 5, embodiment 10, step A slurries are carried out with colloid mill
Grinding distribution processing, makes powder microparticle refine to average diameter 1.8um；Step D's contains in aqueous acid, and four water acetic acid are added
Magnesium 0.135kg is converted into 1.0% (quality) that magnesia accounts for molecular sieve.
In autoclave in Crystallizing treatment rear slurry microparticle average diameter, laser particle analyzer survey 1.9um；Divide in catalyst
Son sieve microparticle size, catalyst surface, section electromicroscopic photograph (SEM) be shown as 1-2um.
Embodiment 12
Substantially with embodiment 1, difference is to use another kind SAPO-11 molecular screen primary powder, is easily dispersed to average grain
Diameter 1.7um, crystallinity 95%, chemical component P2O542%, SiO215%, Al2O343% (quality).
It is calculated from ingredient proportion, catalyst obtained by the present embodiment contains the molecular sieve of 50% (quality), contains 50% (quality)
Aluminium oxide；SAPO-11 accounts for 80% (quality) of molecular sieve total amount, and ZSM-5 accounts for 20% (quality) of molecular sieve total amount.From catalysis
Electromicroscopic photograph (SEM) judgement on agent surface, section, the microparticle size 1-2um of molecular sieve in catalyst.
Embodiment 13
Substantially with embodiment 1, difference is to use another ZSM-5 molecular sieve original powder, is easily dispersed to average grain diameter
1.3um, silica alumina ratio 40, crystallinity 95%.
It is calculated from ingredient proportion, catalyst obtained by the present embodiment contains the molecular sieve of 50% (quality), contains 50% (quality)
Aluminium oxide；SAPO-11 accounts for 80% (quality) of molecular sieve total amount, and ZSM-5 accounts for 20% (quality) of molecular sieve total amount.From catalysis
Electromicroscopic photograph (SEM) judgement on agent surface, section, the microparticle size 1-2um of molecular sieve in catalyst.
Comparative example 1
Substantially with embodiment 1, difference is the Crystallizing treatment of no step C.
Comparative example 2
Substantially with embodiment 5, difference is the Crystallizing treatment of no step C.
Comparative example 3
Substantially with embodiment 10, difference is the Crystallizing treatment of no step C.
Comparative example 4
Substantially with embodiment 1, difference is in step A that ZSM-5 molecular sieve original powder, SAPO-11 molecular screen primary is not added
Powder is 2.5kg.
The surface of each catalyst prepared by the embodiment 1-13, section electromicroscopic photograph (SEM), molecular sieve in catalyst
Microparticle size 1-2um and SAPO-11 molecular screen primary powder, the partial size situation difference of ZSM-5 molecular sieve original powder are unobvious.
By the XRD spectrum of each catalyst prepared by embodiment 1,5,11,12,13, comparative example 1, the XRD spectrum of 2 catalyst
It carries out and the XRD spectrum of SAPO-11 molecular screen primary powder, ZSM-5 molecular sieve original powder is compared repeatedly, embodiment is thought in judgement
1, in 5,11,12,13 catalyst SAPO-11 molecular sieve, ZSM-5 molecular sieve structure, and without carrying out secondary crystallization processing
The structure of SAPO-11 molecular sieve, ZSM-5 molecular sieve in comparative example catalyst, with SAPO-11 molecular screen primary powder, ZSM-5 molecular sieve
The structure of original powder is compared, and difference is unobvious, and without there is other kinds of molecular sieve structure.This explanation, in above-mentioned condition
In the Crystallizing treatment and subsequent catalyst preparation process of lower progress, SAPO-11 molecular sieve, ZSM-5 molecular sieve structure protect substantially
It holds, and without generating other kinds of molecular sieve.
Evaluation test 1
Embodiment 1-13, each catalyst of comparative example 1-4 are subjected to laboratory evaluation respectively, evaluation response is continuous in fixed bed
It is carried out on micro-reaction equipment, tube inner diameter 15mm, catalyst breakage to partial size 0.6-0.8mm (20-30 mesh), loadings
10ml；Go out liquid with the continuous small flow of carbon four after ether and the produced continuous flow that all gasifies makees unstripped gas, raw material is formed such as 1 institute of table
Column, reaction pressure 0.135MPa, according to four steel cylinder loss of weight of carbon after ether and be located at the gas rotameter before reaction tube control it is former
Expect throughput, gas space velocity 800hr-1；Expect to collect into -18 DEG C of refrigerators are cooling in evaluation response outlet.
After four unstripped gas of carbon feeds intake after ether, bed temperature 1-3hr controls 280 DEG C or hereinafter, after 3hr, according to outlet
The yield situation control of isobutene, is gradually warmed up, so that isobutene yield is close to or up to 40-41%, control bed after 10hr in object
Layer temperature makes isobutene yield 40-41%.Bed temperature situation of each catalyst in evaluation time 50,100hr is listed in table
2, with when identical evaluation time with bed temperature junior be it is excellent；By n-butene of each catalyst in evaluation time 50,100hr
Conversion ratio, isobutene yield, isomerized oil yield situation are listed in table 2.
Four raw material of carbon and evaluation response outlet material, are formed with two gas Chromatographic Determinations, all use Liquid sample introduction, liquid after ether
Body and sample injector are all pre-chilled to -18 DEG C.One chromatography carbon determination four and following components, capillary column AT.PLOT aluminium oxide/S, 50m*
0.53mm*20um, detector FID, heat up after constant temperature purging；The main carbon determination five of another chromatography and the above component (light dydrocarbon+, isomery
Carburetion), capillary column OV-1,50m*0.53mm*5 μm, detector FID, temperature programming；Two chromatographic datas by carbon four and with
The content of lower component is fitted, and determines carbon one to 12 constituent content of carbon.2-5hr is surveyed once per hour, 5-10hr is every
It surveys within two hours once, survey in 10-50hr every four hours is primary, it is primary to survey within 50-100hr every six hours.
When needing to measure gas composition once in a while, by evaluation response outlet material not into refrigerator and directly room temperature takes gas and sample introduction.
Hydrogen content is carried out by the gas-chromatography equipped with 13X packed column and thermal conductivity detector (TCD) in evaluation response outlet material,
But in each catalyst 100hr evaluation, the hydrogen content for surveying reaction outlet material is all lower than 0.05% (volume).
Isobutene yield=n-butene conversion X selective isobutene.
Isomerized oil yield=n-butene conversion X light dydrocarbon+selectivity
From table 2-3 data can be seen that molecular sieve, although the secondary crystallization processing of aluminium hydroxide mixed serum makes molecular sieve
Activity slightly reduce, but significantly reduce the deactivation rate of catalyst, extend the service life of catalyst, introduce oxygen in molecular sieve
Change magnesium and also plays similar effect；The introducing of ZSM-5 molecular sieve has been significantly reduced the deactivation rate of catalyst, has mentioned simultaneously
The high conversion ratio of n-butene, and the isomerized oil of higher-value is generated, which is carbon eight, octane number
Higher than MTBE, gasoline component can be directly used as.
Four raw material of carbon forms after 1 ether of table, V%
| Propane | 0.07 |
| Propylene | 0.02 |
| Iso-butane | 35.37 |
| Normal butane | 10.03 |
| Trans-butene-2 | 21.47 |
| Butene-1 | 15.95 |
| Isobutene | 0.05 |
| Cis-butene-2 | 16.65 |
| Total amylene | 0.13 |
| Butadiene | 0.012 |
| Methanol | 0.008 |
| Sulfur content | 0.005 |
| N-butene amounts to | 54.07 |
Table 2 controls the reaction bed temperature of the different durations of runs under the conditions of isobutene yield 40-41%
| Catalyst | 50hr bed temperature, DEG C | 100hr bed temperature, DEG C |
| Embodiment 1 | 330 | 332 |
| Embodiment 2 | 329 | 331 |
| Embodiment 3 | 324 | 326 |
| Embodiment 4 | 320 | 323 |
| Embodiment 5 | 332 | 333 |
| Embodiment 6 | 329 | 331 |
| Embodiment 7 | 332 | 335 |
| Embodiment 8 | 330 | 331 |
| Embodiment 9 | 331 | 333 |
| Embodiment 10 | 328 | 330 |
| Embodiment 11 | 331 | 332 |
| Embodiment 12 | 334 | 336 |
| Embodiment 13 | 331 | 334 |
| Comparative example 1 | 318 | 324 |
| Comparative example 2 | 322 | 327 |
| Comparative example 3 | 315 | 321 |
| Comparative example 4 | 326 | 334 |
N-butene conversion, isobutene yield, isomerized oil yield situation when table 3 50,100hr of evaluation
Evaluation test 2
1,5,10,11 catalyst of embodiment and comparative example 1,4 catalyst are subjected to industrial side line evaluation test respectively.Reaction
Bore 100mm, catalyst are set on bed without broken, Φ 1.8X 3-6mm, loadings 3000ml, bed height 410mm
The Φ 3mm porcelain ball of 1000mm height is as preheating section；Catalyst bed sets three temperature measuring points, and thermocouple is loaded on and is fixed on reaction tube
In the casing of central axes；Reaction tube peripheral hardware copper pipe samming, copper pipe are outside heating furnace body.With carbon four after ether is continuous, whole gasification institutes
The continuous flow of production makees unstripped gas, and raw material composition surveys primary, substantially identical with listed by table 1, reaction pressure control 0.12- daily
0.13MPa controls raw gas flow according to the gas rotameter before reaction tube is located at, and reaction tube outlet is expected into steel cylinder, steel
Bottle can be put into -18 DEG C of refrigerators or taking-up, and coil pipe and sample tap are set before steel cylinder entrance.
Control gas space velocity 400hr-1；Bed temperature 1-3hr controls 280 DEG C hereinafter, after 3hr, according in outlet object
The yield situation of isobutene controls, and is gradually warmed up, suitable control reaction bed temperature after 10hr makes isobutene yield as far as possible
For 40-41%.
2-5hr survey per hour it is primary, survey within 5-10hr every two hours it is primary, survey within 10-50hr every four hours it is primary, the
It surveys within 50-100hr every six hours once, surveys within every six hours after 100hr primary.
The measuring method of outlet material sample is identical with evaluation test 1.
Below 0.05% (volume) before hydrogen content 1000hr in evaluation response outlet material, until evaluation terminates to be below
0.10% (volume).
1,5,10,11 catalyst of embodiment, first one way operating side line evaluation, as a result as listed by table 4,5.
4 catalyst one way of table operates side line evaluation result
5 catalyst one way of table operates side line evaluation result
After one way operates, coke burning regeneration continuously runs, burns four times, and catalyst performance declines smaller, the 4th list
The journey duration of runs only reduces 10-13%, n-butene conversion, isobutene yield, isomerization relative to the first one way duration of runs
Oil yield situation is basically unchanged.
The comparative example 1,4 catalyst, first one way operating side line evaluation, as a result as listed by table 6.
6 catalyst one way of table operates side line evaluation result
Table 4-6 the result shows that, molecular sieve, aluminium hydroxide mixed serum secondary crystallization processing, hence it is evident that reduce catalyst
Deactivation rate, extend the service life of catalyst, magnesia introduced in molecular sieve and also plays similar effect；ZSM-5 molecule
The introducing of sieve, has been significantly reduced the deactivation rate of catalyst, while improving the conversion ratio of n-butene, and generate higher price
The isomerized oil of value.
Claims (8)
1. a kind of N-alkene isomerization catalyst contains the molecular sieve of 50-90% (quality), remaining is aluminium oxide；The molecule
Sieve is made of SAPO-11 and ZSM-5, and wherein SAPO-11 accounts for the 75-90% (quality) of molecular sieve total amount, and ZSM-5 accounts for molecular sieve
The 10-25% (quality) of total amount；1-2 μm of the microparticle size of molecular sieve in catalyst；
The preparation method of the catalyst, comprising the following steps:
A, add suitable quantity of water in material-compound tank, the desired amount of SAPO-11 molecular screen primary powder, ZSM-5 molecular sieve original powder and hydroxide is added
Ammonium acetate is added in aluminium powder, is beaten, powder total concentration 10-20% (quality), acetic acid ammonium concentration 0.5-2.0% (quality) in slurries；
C, it is transferred to autoclave, in 150-240 DEG C of Crystallizing treatment 10-60hr；
D, step C slurries are spray-dried, and xeraphium adds extrusion after lubricant plus kneading containing aqueous acid, then through drying, 550-
600 DEG C of roastings, are made catalyst；The acid is one of nitric acid, citric acid, acetic acid or a variety of.
2. N-alkene isomerization catalyst as described in claim 1, which is characterized in that SAPO-11 accounts for molecular sieve total amount
80-85% (quality), ZSM-5 account for the 15-20% (quality) of molecular sieve total amount.
3. N-alkene isomerization catalyst as described in claim 1, which is characterized in that molecular sieve content 50-70% (matter
Amount).
4. N-alkene isomerization catalyst as described in claim 1, which is characterized in that step D's contains in aqueous acid, adds
Enter magnesium acetate, is converted into the 0.5-2.0% (quality) that magnesia accounts for molecular sieve.
5. N-alkene isomerization catalyst as described in claim 1, which is characterized in that in step C, Crystallizing treatment temperature
170-200 DEG C, handle time 20-40hr.
6. N-alkene isomerization catalyst as described in claim 1, which is characterized in that in step D, catalyst is in 560-
580 DEG C of roasting 2-4hr.
7. N-alkene isomerization catalyst as described in claim 1, which is characterized in that before step C, there are also step B:
Step A slurries are further processed with grinding distribution equipment, and powder microparticle is made to refine to 1-2 μm of average diameter.
8. N-alkene isomerization catalyst as described in claim 1 four n-butene isomerization of carbon after by ether prepares isobutene mistake
Application in journey.
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| CN101081370A (en) * | 2006-05-31 | 2007-12-05 | 中国石油大学(北京) | ZSM-5/SAPO-11 composite zeolite and catalytically cracked gasoline hydrogenation quality-improved catalyzer and the methoer for preparing the same |
| CN103566966A (en) * | 2012-08-03 | 2014-02-12 | 中国石油化工股份有限公司 | N-alkene isomerization catalyst and preparation method thereof |
| CN104117388A (en) * | 2013-04-23 | 2014-10-29 | 上海碧科清洁能源技术有限公司 | SAPO-11/ZSM-5 mixed molecular-sieve catalyst, and preparation and application thereof |
| CN106040293A (en) * | 2016-06-13 | 2016-10-26 | 山东迅达化工集团有限公司 | N-alkene isomerization catalyst, method for preparing same and application of n-alkene isomerization catalyst |
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| CN101081370A (en) * | 2006-05-31 | 2007-12-05 | 中国石油大学(北京) | ZSM-5/SAPO-11 composite zeolite and catalytically cracked gasoline hydrogenation quality-improved catalyzer and the methoer for preparing the same |
| CN103566966A (en) * | 2012-08-03 | 2014-02-12 | 中国石油化工股份有限公司 | N-alkene isomerization catalyst and preparation method thereof |
| CN104117388A (en) * | 2013-04-23 | 2014-10-29 | 上海碧科清洁能源技术有限公司 | SAPO-11/ZSM-5 mixed molecular-sieve catalyst, and preparation and application thereof |
| CN106040293A (en) * | 2016-06-13 | 2016-10-26 | 山东迅达化工集团有限公司 | N-alkene isomerization catalyst, method for preparing same and application of n-alkene isomerization catalyst |
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