CN111018650A - Butene isomerization process - Google Patents
Butene isomerization process Download PDFInfo
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- CN111018650A CN111018650A CN201811175357.8A CN201811175357A CN111018650A CN 111018650 A CN111018650 A CN 111018650A CN 201811175357 A CN201811175357 A CN 201811175357A CN 111018650 A CN111018650 A CN 111018650A
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- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 title claims abstract description 95
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 112
- 238000006243 chemical reaction Methods 0.000 claims abstract description 108
- 239000002808 molecular sieve Substances 0.000 claims abstract description 80
- 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 80
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 25
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract 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 31
- 239000011230 binding agent Substances 0.000 claims description 19
- 230000005496 eutectics Effects 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 238000004523 catalytic cracking Methods 0.000 claims description 4
- 239000000320 mechanical mixture Substances 0.000 claims description 4
- 238000004230 steam cracking Methods 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims 3
- 239000000243 solution Substances 0.000 description 39
- 239000007788 liquid Substances 0.000 description 36
- 238000002425 crystallisation Methods 0.000 description 27
- 230000008025 crystallization Effects 0.000 description 27
- 239000000843 powder Substances 0.000 description 27
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 25
- 229910017604 nitric acid Inorganic materials 0.000 description 25
- 238000001035 drying Methods 0.000 description 22
- 238000003756 stirring Methods 0.000 description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 20
- 238000004458 analytical method Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 241000219782 Sesbania Species 0.000 description 17
- 239000011259 mixed solution Substances 0.000 description 16
- 238000005406 washing Methods 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 12
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000002431 foraging effect Effects 0.000 description 10
- 238000003828 vacuum filtration Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000012527 feed solution Substances 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000004876 x-ray fluorescence Methods 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- -1 Polybutylene Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 239000003361 porogen Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000112 cooling gas Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
- C07C5/2775—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J29/405—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 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/80—Mixtures of different zeolites
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a butene isomerization method. The method comprises the following steps: a) feeding a feed stream containing 2-butene into a first reaction zone to contact with a catalyst A to produce a stream I; b) passing said stream I to at least one second reaction zone for contact with catalyst B to produce a product stream comprising 1-butene; wherein the catalyst A contains molecular sieve Zr-ZSM with a framework of zirconium; the catalyst B contains silicon oxide or magnesium oxide.
Description
Technical Field
The invention relates to a butene isomerization method.
Background
1-butene is α -olefin with relatively active chemical property, is mainly used for producing Linear Low Density Polyethylene (LLDPE), High Density Polyethylene (HDPE), Polybutylene (PB) resin, decanol and the like, and has wide application, in recent years, the global demand for polyethylene is rapidly increased, so the demand for 1-butene serving as a comonomer is increased, however, most of domestic 1-butene manufacturers are self-used and rarely sell the 1-butene to other parts, so the purchase of the 1-butene is relatively difficult, and particularly, enterprises with relatively large gaps for the 1-butene exist.
Currently, there are two main routes for global production of 1-butene, one is oligomerization process using ethylene as raw material, and the other is refiningPlant C4C, cracking4Or coal-to-olefin byproduct mixed C4Is obtained by separating raw materials. The latter is commonly adopted in China for the mixed C4Butadiene extraction and hydrogenation are carried out, isobutene is removed through etherification, and then 1-butene products are obtained through rectification separation. But the yield of 1-butene in this route is limited by the source of 1-butene in the feed. Most petrochemical companies in the world use residual C rich in 2-butene4Hydrocarbons are used as fuels. If the part of 2-butene is converted into 1-butene through isomerization reaction, a new path for producing the 1-butene can be opened up.
In recent years, a great deal of research and development has been carried out on the process for producing 1-butene by isomerizing 2-butene by related petrochemical companies at home and abroad. For example, CN102267853A discloses a method for producing 1-butene by isomerizing 2-butene, which adopts a surface area of 150-210 m2Taking alumina per gram as a carrier, dissolving 0.146-23.82 parts by weight of metal salt in 82-100 parts by weight of deionized water to prepare an aqueous solution, and then soaking 57 parts by weight of catalyst carrier; standing and soaking for 16-24 hours at room temperature, filtering out residual liquid, drying for 4-10 hours at the temperature of 120-160 ℃ until water is completely removed, and roasting for 1-12 hours at the temperature of 500-600 ℃ to obtain the metal composite oxide catalyst. The catalyst prepared by the method is filled in a fixed bed catalytic reactor, 2-butylene gas with the content of 85.0-99.0% passes through a catalyst bed layer, the temperature is 300-480 ℃, the pressure is 0.1-0.5 Mpa, and the gas hourly space velocity of the feed of the 2-butylene is 60-900 hours-1Under the conditions of (1), a double bond isomerization reaction is carried out. And (3) sampling and analyzing the reacted gas at regular time, wherein the content of the 1-butene is 19.0-27.0%. When the reaction temperature is controlled to be lower (300-320 ℃), the content of isobutene serving as an impurity generated by the reaction is lower, the selectivity of 1-butene is higher, and the conversion rate is only 19%. When the reaction temperature is increased and the conversion rate is increased, the content of impurity isobutene in the product is obviously increased, particularly when the conversion rate reaches 24%, the content of isobutene reaches 0.5%, and the selectivity of 1-butene is obviously reduced.
As the isomerization of 2-butene to 1-butene is accompanied by other side reactions such as skeletal isomerization, dehydration and cracking, etc. in addition to butene double bond isomerization, the side reactions affect the selectivity of the reaction on 1-butene. Although a single type of catalyst can perform isomerization reaction under a wide range of conditions, conversion and selectivity cannot be taken into consideration when the reaction conditions are greatly changed.
Disclosure of Invention
The present inventors have assiduously studied on the basis of the prior art and, as a result, have accomplished the present invention by solving at least one of the aforementioned problems by adopting a technical solution of loading catalysts having different catalytic activities in divided regions.
In particular, the invention relates to a butene isomerization method. The method comprises the following steps:
a) feeding a feed stream containing 2-butene into a first reaction zone to contact with a catalyst A to produce a stream I;
b) passing said stream I to at least one second reaction zone for contact with catalyst B to produce a product stream comprising 1-butene;
wherein the catalyst A contains molecular sieve Zr-ZSM with a framework of zirconium; the catalyst B contains silicon oxide or magnesium oxide.
According to one aspect of the invention, the catalyst A comprises 30-90 parts by weight of Zr-ZSM and 10-70 parts by weight of binder, preferably 40-80 parts by weight of Zr-ZSM and 20-60 parts by weight of binder, and more preferably 50-80 parts by weight of Zr-ZSM and 20-50 parts by weight of binder; relative to the total weight parts of the Zr-ZSM and the binder.
According to one aspect of the invention, the Zr-ZSM molecule is selected from one of the group consisting of Zr-ZSM-5, Zr-ZSM-11, Zr-ZSM-35 and Zr-ZSM-39; preferably a mechanical mixture of at least two selected from the group consisting of Zr-ZSM-5, Zr-ZSM-11, Zr-ZSM-35 and Zr-ZSM-39; more preferably eutectic molecular sieves of at least two selected from the group consisting of Zr-ZSM-5, Zr-ZSM-11, Zr-ZSM-35 and Zr-ZSM-39; most preferred is Zr-ZSM-5/ZSM-11 eutectic molecular sieve.
According to an aspect of the present invention, the binder is at least one selected from the group consisting of alumina and silica.
According to one aspect of the invention, in the Zr-ZSM molecular sieve, the molar ratio of silicon to zirconium is 50-1000, preferably 100-500.
According to one aspect of the invention, the catalyst a does not contain an alkaline earth element or an oxide thereof.
According to an aspect of the present invention, the alkaline earth metal element is at least one selected from the group consisting of magnesium, calcium, strontium, and barium; in particular magnesium.
According to one aspect of the invention, the reaction temperature of the first reaction zone is 150-280 ℃, the reaction pressure is 0-1 MPa, and the weight space velocity is 1-20 hours-1(ii) a The preferable reaction temperature is 180-270 ℃, the pressure is 0.5-1 MPa, and the weight space velocity is 2-10 hours-1。
According to one aspect of the invention, the reaction temperature of the second reaction zone is 280-420 ℃, the pressure is 0-1 MPa, and the weight space velocity is 1-20 hours-1(ii) a The preferable contact temperature is 320-400 ℃, the pressure is 0.5-1 MPa, and the weight space velocity is 2-10 hours-1。
According to one aspect of the invention, the reaction temperature of the first reaction zone is lower than the reaction temperature of the second reaction zone.
According to one aspect of the invention, the stream containing 2-butene is derived from a refinery catalytic cracking unit, an ethylene plant steam cracking unit or a coal-to-olefin unit byproduct mixed C-IV stream, preferably a C-IV stream obtained by removing 1, 3-butadiene and isobutene from the refinery catalytic cracking unit, the ethylene plant steam cracking unit or the coal-to-olefin unit byproduct mixed C-IV stream.
According to one aspect of the invention, said 2-butene-containing stream is a mixture comprising 1-butene and 2-butene which does not meet thermodynamic equilibrium values.
According to one aspect of the invention, the 2-butene-containing stream has a mass concentration of 1-butene of less than 4% and a mass concentration of 2-butene of greater than 45%.
According to one aspect of the invention, the mass concentration of 1, 3-butadiene in the 2-butene-containing stream is less than 30 ppm.
According to one aspect of the invention, the weight ratio of the catalyst A to the catalyst B is 0.1 to 8:1, preferably 0.2 to 5:1, more preferably 0.5 to 4: 1.
The invention has the beneficial effects that:
according to the invention, the conversion rate of 2-butene and the selectivity of 1-butene can be simultaneously improved.
The invention is further described below by means of specific embodiments.
Detailed Description
The following describes in detail specific embodiments of the present invention. It is to be noted, however, that the scope of the present invention is not limited thereto, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, procedures, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently in use, but would become known in the art to be suitable for a similar purpose.
In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.
Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.
Where not explicitly stated, reference to pressure within this specification is to gauge pressure.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the following, various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
It should be noted that the 2-butene double bond isomerization reaction to produce 1-butene is typically a reversible reaction, and generally the distribution of butene isomerization products is mainly controlled by thermodynamic factors. Therefore, different thermodynamic equilibrium conversions will be associated at different temperatures. Thermodynamic equilibrium conversion can be thermodynamically calculated for the reaction process by means of the Gibbs free energy minimum principle, which is well known to those skilled in the art.
The invention relates to a butene isomerization method. The method comprises the following steps:
a) feeding a feed stream containing 2-butene into a first reaction zone to contact with a catalyst A to produce a stream I;
b) passing said stream I to at least one second reaction zone for contact with catalyst B to produce a product stream comprising 1-butene;
wherein the catalyst A contains molecular sieve Zr-ZSM with a framework of zirconium; the catalyst B contains silicon oxide or magnesium oxide.
According to the invention, the catalyst A comprises 30-90 parts by weight of Zr-ZSM and 10-70 parts by weight of a first binder, preferably 40-80 parts by weight of Zr-ZSM and 20-60 parts by weight of the first binder, and more preferably 50-80 parts by weight of Zr-ZSM and 20-50 parts by weight of the first binder; relative to the total weight parts of the Zr-ZSM and the first binder.
According to the invention, in the Zr-ZSM molecular sieve, the molar ratio of silicon to aluminum is 50-500, preferably 100-450, and more preferably 200-400; the molar ratio of silicon to zirconium is 50 to 1000, preferably 100 to 500.
According to the present invention, the Zr-ZSM molecular sieve may be one selected from the group consisting of Zr-ZSM-5, Zr-ZSM-11, Zr-ZSM-35 and Zr-ZSM-39; or a mechanical mixture of at least two selected from the group consisting of Zr-ZSM-5, Zr-ZSM-11, Zr-ZSM-35 and Zr-ZSM-39; it may also be an eutectic molecular sieve of at least two selected from the group consisting of Zr-ZSM-5, Zr-ZSM-11, Zr-ZSM-35 and Zr-ZSM-39, preferably Zr-ZSM-5/ZSM-11 eutectic molecular sieve. The eutectic molecular sieves described herein, which may also be referred to in the art as intergrown molecular sieves, are distinguished from simple mechanical mixtures by having two or more distinct phases of intergrown materials of crystalline structure in one molecular sieve composition.
According to the present invention, the binder is at least one selected from the group consisting of alumina and silica.
According to an embodiment of the present invention, the catalyst a does not contain an alkaline earth metal element or an oxide thereof from the viewpoint of more favorable isomerization reaction. The alkaline earth metal element is at least one selected from the group consisting of magnesium, calcium, strontium, and barium; in particular magnesium.
According to the invention, the catalyst A can be prepared by the following method. The method comprises the following steps: crystallizing a mixture (hereinafter, collectively referred to as a first mixture) comprising a template, a zirconium source, a silicon source, an aluminum source, and water to obtain a Zr-ZSM molecular sieve, and molding the Zr-ZSM molecular sieve with a first binder.
Wherein the template is at least one selected from the group consisting of tetrapropylammonium hydroxide, tetrapropylammonium bromide, n-butylamine, tetramethylethylenediamine, cyclohexylamine, n-propylamine, and hexamethyltetramine.
The zirconium source, any zirconium source conventionally used in the art for this purpose may be used, including but not limited to zirconium nitrate, zirconium oxychloride, and zirconium isopropoxide, with zirconium nitrate and zirconium oxychloride being preferred.
As the silicon source, any silicon source conventionally used in the art for this purpose can be used. Examples thereof include sodium silicate, silica sol and silicate ester. These silicon sources may be used singly or in combination in a desired ratio.
As the aluminum source, any aluminum source conventionally used in the art for this purpose can be used. Examples thereof include aluminum sol and aluminum hydroxide. These aluminum sources may be used singly or in combination in a desired ratio.
In the first mixture, the template, the zirconium source (as ZrO)2Calculated), the silicon source (in SiO)2Calculated as Al), an aluminum source (calculated as Al)2O3Calculated) and water in a molar ratio of: 0.1-0.5: 0.001-0.025: 1: 0-0.08: 35-170; preferably: 0.2-0.4: 0.005-0.025: 0.005-0.06: 35-170. Preferably, the first mixture is controlled to have a pH of 4 to 9, and any acid or base conventionally used in the art for this purpose may be used therefor, such as hydrochloric acid, nitric acid, sulfuric acid, NaOH, KOH, and aqueous ammonia may be cited.
The crystallization may be performed in any manner conventionally known in the art, for example, a method of subjecting the mixture to hydrothermal crystallization under crystallization conditions may be exemplified. Crystallization may be in the presence of stirring as desired. The crystallization conditions include: the temperature is 120-200 ℃, and the time is 20-80 hours.
Preferably, an ageing step is included, carried out before crystallization, the ageing conditions including: the aging temperature is 30-75 ℃, and the aging time is 10-48 hours.
After the crystallization is completed, the Zr-ZSM molecular sieve may be separated from the obtained reaction mixture by any separation means conventionally known. The separation method includes, for example, a method of filtering, washing and drying the obtained product mixture. Here, the filtering, washing and drying may be performed in any manner conventionally known in the art. As a specific example, as the filtration, for example, the obtained product mixture may be simply filtered with suction. Examples of the washing include washing with deionized water and/or ethanol. The drying temperature is, for example, 40 to 250 ℃, preferably 60 to 150 ℃, and the drying time is, for example, 8 to 30 hours, preferably 10 to 20 hours. The drying may be carried out under normal pressure or under reduced pressure.
According to the requirement, the Zr-ZSM molecular sieve obtained by crystallization can be roasted to remove the organic template agent, the water and the like possibly existing, thereby obtaining the roasted molecular sieve. The calcination can be carried out in any manner conventionally known in the art, for example, the calcination temperature is generally 300 to 800 ℃, preferably 400 to 650 ℃, and the calcination time is generally 1 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.
And mixing the Zr-ZSM molecular sieve with the binder, and molding to obtain the catalyst A. The catalyst a may be in the form of any molded article (e.g., a bar, a clover, etc.), and may be obtained in any manner conventionally known in the art, without particular limitation. As the first binder, any binder conventionally used in the art for this purpose may be used. For example, alumina or silica can be cited. Preferably, a pore-forming agent may be added during molding. As the porogen, any porogen conventionally used in the art for this purpose can be used. Examples thereof include sesbania powder and methyl cellulose.
The molded catalyst A may be dried and calcined as necessary. The drying may be carried out in any manner conventionally known in the art, and the drying temperature may be, for example, 40 to 250 ℃, preferably 60 to 150 ℃, and the drying time may be, for example, 8 to 30 hours, preferably 10 to 20 hours. The drying may be carried out under normal pressure or under reduced pressure. The calcination can be carried out in any manner conventionally known in the art, for example, the calcination temperature is generally 300 to 800 ℃, preferably 400 to 650 ℃, and the calcination time is generally 1 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.
In the preparation method of the catalyst a, the first mixture does not contain an alkaline earth metal source from the viewpoint of more favorable isomerization reaction. The alkaline earth metal is at least one selected from the group consisting of magnesium, calcium, strontium, and barium; in particular magnesium. The phrase "not including an alkaline earth metal source" as used herein means that the alkaline earth metal source is not intentionally or actively introduced during the production process.
According to the invention, the catalyst a contains Zr-ZSM with a framework of zirconium. The Zr skeleton can improve the acidity of the molecular sieve and ensure that the catalyst A has higher activity. According to this characteristic of the catalyst A, the first reaction zone is controlled at a lower reaction temperature. The reaction conditions of the first reaction zone include: the reaction temperature is 150-280 ℃, the reaction pressure is 0-1 MPa, and the weight space velocity is 1-20 hours-1(ii) a The preferable reaction temperature is 180-270 ℃, the pressure is 0.5-1 MPa, and the weight space velocity is 2-10 hours-1。
According to the invention, the catalyst B contains silicon oxide or magnesium oxide. Silica or magnesia as butene isomerization catalysts are well known in the art, for example from documents US6875901, CN 102649672A. The reaction conditions of the second reaction zone include: the reaction temperature is 280-420 ℃, the pressure is 0-1 MPa, and the weight space velocity is 1-20 hours-1(ii) a The preferable contact temperature is 320-400 ℃, the pressure is 0.5-1 MPa, and the weight space velocity is 2-10 hours-1。
According to the invention, the weight ratio of the catalyst A to the catalyst B is 0.1-8: 1, preferably 0.2-5: 1, and more preferably 0.5-4: 1.
According to the invention, the molecular sieve Zr-ZSM with framework zirconium is adopted in the first reaction zone, the conversion degree of 2-butene in the first reaction zone is higher, and the amount of 2-butene participating in the reaction in the second reaction zone is less, so that the reaction intensity of the second reaction zone is low, and the effects of high conversion rate and high selectivity are achieved.
In the present invention, the composition of the catalyst was analyzed by ICP (inductively coupled plasma) and XRF (X-ray fluorescence) methods. ICP was used to test the zirconium content of the catalyst under the following test conditions: an iCAP7600Duo inductively coupled plasma emission spectrometer of American Sammer Feishell company is adopted, zirconium oxide is used as a standard sample, and the RF power of the instrument is 1.2 KW; the carrier gas flow is 0.72L/min; the flow rate of the cooling gas is 15L/min; the pump flow rate was 1.0ml/min and the analytical wavelength was 335 nm. XRF was used to test the content of molecular sieve in the catalyst under the following test conditions: a Rigaku ZSX 100e type XRF instrument is adopted, a rhodium target is used as an excitation source, the maximum power is 3600W, the tube voltage is 60KV, and the tube current is 120 mA.
The crystal phase of the catalyst A is carried out on a Bruker D8 polycrystalline X-ray diffraction (XRD) instrument, a graphite monochromator is used, a Cu-Ka ray source is used (the K α 1 wavelength lambda is 0.15406nm), the scanning angle 2 theta is 5-50 degrees, and the scanning speed is 1 degree/min.
The existence form of Zr in the catalyst A is determined by adopting a Cary5000 type ultraviolet-visible spectrum (UV-vis) instrument, solid barium sulfate is taken as a reference, and the test wavelength range is 190-800. The multi-coordination zirconium in the molecular sieve framework can generate an absorption peak at the wavelength of 240-280 nm, and the absorption peak of the zirconium oxide is less than 200 nm.
In the invention, the product composition is determined by gas chromatography, the chromatography model is Agilent 7890A, a FID detector is arranged, an FFAP capillary chromatographic column is used for separation, the temperature of the chromatographic column is programmed to be 90 ℃ initially, the chromatographic column is kept for 15 minutes, and then the temperature is increased to 220 ℃ at the speed of 15 ℃/minute and kept for 45 minutes.
The conversion X of 2-butene is calculated as:
X(2-butene)＝(MImport 2-butene-MOutlet 2-butene)/MImport 2-butene×100％
The selectivity Y of 1-butene is calculated by the formula:
Y(1-butene)＝M(Outlet 1-butene)/(MImport 2-butene-MOutlet 2-butene)×100％
The present invention is further illustrated by the following examples.
[ example 1 ]
1) 6g of zirconium oxychloride is dissolved in isopropanol, and then the solution is added into 1000ml of ethyl orthosilicate to prepare a mixed solution I, and the mixed solution I is stirred for 50 minutes at room temperature. 2700ml of aqueous solution containing 10% tetrapropylammonium hydroxide was prepared to prepare solution II. 30g of alumina sol (40% of alumina content) was added to the solution II with stirring to obtain a feed solution III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 6 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃, and then crystallized for 48 hours at the temperature of 170 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain molecular sieve powder Z1-a. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-5/ZSM-11 eutectic molecular sieve containing framework zirconium.
70g of the Z1-a molecular sieve, 30g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are dried for 4 hours at 120 ℃, and then the strips are roasted for 4 hours at 500 ℃ to obtain a catalyst A1, and the catalyst A1 is filled into a first reactor.
2) Mixing 100g of magnesium oxide and 0.5g of methyl cellulose, tabletting and forming, treating the formed catalyst with 200ml of 0.2% citric acid for 3 hours, washing with deionized water, drying at 120 ℃ and roasting at 500 ℃ to obtain a catalyst B1, and filling the catalyst B1 into a second reactor.
The results of the catalyst analysis are shown in Table 1.
[ example 2 ]
1) Take [ example 1 ] molecular Sieve Z1-a 70g, silica sol 75ml (containing 40% SiO)2) Kneading with 5g sesbania powder, extruding into strips, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours to obtain a catalyst A2, and filling into a first reactor.
2) The catalyst B1 prepared in [ example 1 ] was charged into the second reaction zone.
The results of the analytical tests are shown in Table 1.
[ example 3 ]
1) Taking 50g of Z1-a molecular sieve, 50g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder, kneading, extruding into strips, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours to obtain a catalyst A3, and filling the catalyst A3 into a first reactor.
2) The catalyst B1 prepared in [ example 1 ] was charged into the second reaction zone.
The results of the analytical tests are shown in Table 1.
[ example 4 ]
1) 42g of Z1-a molecular sieve, 58g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are taken to be kneaded, extruded into strips, baked at 120 ℃ for 4 hours and baked at 500 ℃ for 4 hours to obtain a catalyst A4, and the catalyst A4 is filled into a first reactor.
2) The catalyst B1 prepared in [ example 1 ] was charged into the second reaction zone.
The results of the analytical tests are shown in Table 1.
[ example 5 ]
1) 31g of Z1-a molecular sieve, 69g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are taken to be kneaded, extruded into strips, baked at 120 ℃ for 4 hours and baked at 500 ℃ for 4 hours to obtain a catalyst A5, and the catalyst A5 is filled into a first reactor.
2) The catalyst B1 prepared in [ example 1 ] was charged into the second reaction zone.
The results of the analytical tests are shown in Table 1.
[ example 6 ]
1) Taking 85g of Z1-a molecular sieve, 15g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder, kneading, extruding into strips, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours to obtain a catalyst A6, and filling the catalyst A6 into a first reactor.
2) The catalyst B1 prepared in [ example 1 ] was charged into the second reaction zone.
The results of the analytical tests are shown in Table 1.
[ example 7 ]
1) 1g of zirconium oxychloride is dissolved in isopropanol, and then added into 1000ml of ethyl orthosilicate to prepare a mixed solution I, and the mixed solution I is stirred for 50 minutes at room temperature. 2700ml of aqueous solution containing 10% tetrapropylammonium hydroxide was prepared to prepare solution II. 30g of alumina sol (40% of alumina content) was added to the solution II with stirring to obtain a feed solution III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 6 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃, and then crystallized for 48 hours at the temperature of 170 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain molecular sieve powder Z7-a. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-5/ZSM-11 eutectic molecular sieve containing framework zirconium.
70g of the Z7-a molecular sieve, 30g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are dried for 4 hours at 120 ℃, and then the strips are roasted for 4 hours at 500 ℃ to obtain a catalyst A7, and the catalyst A7 is filled into a first reactor.
2) The catalyst B1 prepared in [ example 1 ] was charged into the second reaction zone.
The results of the analytical tests are shown in Table 1.
[ example 8 ]
1) 4g of zirconium oxychloride is dissolved in isopropanol, and then the solution is added into 1000ml of ethyl orthosilicate to prepare a mixed solution I, and the mixed solution I is stirred for 50 minutes at room temperature. 2700ml of aqueous solution containing 10% tetrapropylammonium hydroxide was prepared to prepare solution II. 30g of alumina sol (40% of alumina content) was added to the solution II with stirring to obtain a feed solution III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 6 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃, and then crystallized for 48 hours at the temperature of 170 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain molecular sieve powder Z8-a. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-5/ZSM-11 eutectic molecular sieve containing framework zirconium.
70g of the Z8-a molecular sieve, 30g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are dried for 4 hours at 120 ℃, and then the strips are roasted for 4 hours at 500 ℃ to obtain a catalyst A8, and the catalyst A8 is filled into a first reactor.
2) The catalyst B1 prepared in [ example 1 ] was charged into the second reaction zone.
The results of the analytical tests are shown in Table 1.
[ example 9 ]
1) 23g of zirconium oxychloride is dissolved in isopropanol, and then added to 1000ml of ethyl orthosilicate to prepare a mixed solution I, and the mixed solution I is stirred at room temperature for 50 minutes. 2700ml of aqueous solution containing 10% tetrapropylammonium hydroxide was prepared to prepare solution II. 30g of alumina sol (40% of alumina content) was added to the solution II with stirring to obtain a feed solution III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 6 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃, and then crystallized for 48 hours at the temperature of 170 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain molecular sieve powder Z9-a. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-5/ZSM-11 eutectic molecular sieve containing framework zirconium.
70g of the Z9-a molecular sieve, 30g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are dried for 4 hours at 120 ℃, and then the strips are roasted for 4 hours at 500 ℃ to obtain a catalyst A9, and the catalyst A9 is filled into a first reactor.
2) The catalyst B1 prepared in [ example 1 ] was charged into the second reaction zone.
The results of the analytical tests are shown in Table 1.
[ example 10 ]
1) The catalyst A8 prepared in [ example 8 ] was charged into the first reactor.
2) 100g of silicon oxide (specific surface area greater than 400 m) is taken2Per g, average pore diameter of 1.5-4 nm) and 0.5g of methyl cellulose, tabletting and forming, drying at 120 ℃ and roasting at 500 ℃ to obtain a catalyst B10, and loading the catalyst B10 into a second reactor.
The results of the analytical tests are shown in Table 1.
[ example 11 ]
1) 6g of zirconium oxychloride is dissolved in isopropanol, and then the solution is added into 1000ml of ethyl orthosilicate to prepare a mixed solution I, and the mixed solution I is stirred for 50 minutes at room temperature. 2700ml of aqueous solution containing 10% tetrapropylammonium hydroxide was prepared to prepare solution II. 30g of alumina sol (40% of alumina content) was added to the solution II with stirring to obtain a feed solution III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 6 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃, and then crystallized for 48 hours at the temperature of 170 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain molecular sieve powder Z11-a. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-5/ZSM-11 eutectic molecular sieve containing framework zirconium.
70g of the Z11-a molecular sieve, 30g of alumina, 1g of magnesium oxide, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are baked for 4 hours at 120 ℃, and then the strips are baked for 4 hours at 500 ℃ to obtain the catalyst A11.
2) The catalyst B1 prepared in [ example 1 ] was charged into the second reaction zone.
The results of the analytical tests are shown in Table 1.
[ example 12 ]
1) 6g of zirconium oxychloride was dissolved in isopropanol, and then added to 700ml of silica sol (containing 40% of SiO2) to prepare a mixed solution I, which was stirred at room temperature for 50 minutes. 2700ml of water solution containing 8% of n-butylamine is prepared to prepare solution II. 10g of aluminum hydroxide was added to the solution II with stirring to obtain a feed liquid III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 6 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃, and then crystallized for 50 hours at the temperature of 165 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain molecular sieve powder Z12 a-1. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-5 type molecular sieve containing framework zirconium.
6g of zirconium oxychloride was dissolved in isopropanol, and then added to 700ml of silica sol (containing 40% of SiO2) to prepare a mixed solution I, which was stirred at room temperature for 50 minutes. 2700ml of an aqueous solution containing 8% tetrabutylammonium bromide was prepared to prepare a solution II. 10g of aluminum hydroxide was added to the solution II with stirring to obtain a feed liquid III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 4 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃, and then crystallized for 48 hours at the temperature of 135 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain molecular sieve powder Z12 a-2. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-11 type molecular sieve containing framework zirconium.
35g of each of the molecular sieves Z12a-1 and Z12a-2, 30g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are baked at 120 ℃ for 4 hours and then baked at 500 ℃ for 4 hours to obtain a catalyst A12, and the catalyst A12 is filled into a first reactor.
2) The catalyst B1 prepared in [ example 1 ] was charged into the second reaction zone.
The results of the analytical tests are shown in Table 1.
[ example 13 ]
1) 6g of zirconium oxychloride is dissolved in isopropanol, and then the solution is added into 1000ml of ethyl orthosilicate to prepare a mixed solution I, and the mixed solution I is stirred for 50 minutes at room temperature. 2700ml of aqueous solution containing 11% tetramethylethylenediamine was prepared to prepare solution II. And adding 50g of aluminum sulfate into the solution II under the stirring state to obtain a feed liquid III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 6 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃ and then crystallized for 48 hours at the temperature of 180 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain molecular sieve powder Z13-a. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-5/ZSM-35 eutectic molecular sieve containing framework zirconium.
70g of the Z13-a molecular sieve, 30g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are dried for 4 hours at 120 ℃, and then the strips are roasted for 4 hours at 500 ℃ to obtain a catalyst A13, and the catalyst A13 is filled into a first reactor.
2) The catalyst B1 prepared in [ example 1 ] was charged into the second reaction zone.
The results of the analytical tests are shown in Table 1.
[ example 14 ]
1) Preparing Zr-ZSM-5 molecular sieve Z12a-1 by the method of [ example 12 ], kneading 70g of the molecular sieve Z12a-1, 30g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder, extruding into strips, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours to obtain catalyst A14, and filling the catalyst A14 into a first reactor.
2) The catalyst B1 prepared in [ example 1 ] was charged into the second reaction zone.
The results of the analytical tests are shown in Table 1.
[ example 15 ]
1) Preparing Zr-ZSM-11 molecular sieve Z12a-2 by the method of [ example 12 ], kneading and extruding 70g of the molecular sieve, 30g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours to obtain catalyst A15, and filling the catalyst A15 into a first reactor.
2) The catalyst B1 prepared in [ example 1 ] was charged into the second reaction zone.
The results of the analytical tests are shown in Table 1.
[ example 16 ]
1) 6g of zirconium oxychloride was dissolved in isopropanol, and then added to 700ml (containing 40% SiO2) to prepare a mixed solution I, which was stirred at room temperature for 50 minutes. 2700ml of 11% cyclohexylamine-containing aqueous solution is prepared to prepare solution II. And adding 40g of aluminum sulfate into the solution II under the stirring state to obtain a feed liquid III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 6 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃ and then crystallized for 48 hours at the temperature of 180 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain molecular sieve powder Z16-a. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form of the molecular sieve is ZSM-35 molecular sieve containing framework zirconium.
70g of the Z16-a molecular sieve, 30g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are baked for 4 hours at 120 ℃, and then baked for 4 hours at 500 ℃ to obtain a catalyst A16 which is loaded into a first reactor.
2) The catalyst B10 prepared in [ example 10 ] was charged into the second reaction zone.
The results of the analytical tests are shown in Table 1.
[ example 17 ]
1) 6g of zirconium oxychloride was dissolved in isopropanol, and then added to 700ml (containing 40% SiO2) to prepare a mixed solution I, which was stirred at room temperature for 50 minutes. 2700ml of an aqueous solution containing 4% of n-propylamine and 8% of hexamethylenetetramine (R2) was prepared to prepare a solution II. And adding 5g of aluminum sulfate into the solution II under the stirring state to obtain a feed liquid III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH value to 4 by using sulfuric acid to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 60 ℃, and then crystallized for 130 hours at the temperature of 180 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain molecular sieve powder Z17-a. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form of the molecular sieve is ZSM-39 molecular sieve containing framework zirconium.
70g of the Z17-a molecular sieve, 30g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are dried for 4 hours at 120 ℃, and then the strips are roasted for 4 hours at 500 ℃ to obtain a catalyst A17, and the catalyst A17 is filled into a first reactor.
2) The catalyst B1 prepared in [ example 1 ] was charged into the second reaction zone.
The results of the analytical tests are shown in Table 1.
[ COMPARATIVE EXAMPLE 1 ]
[ example 1 ] catalyst A1 was charged into the first and second reaction zones, respectively.
The results of the analytical tests are shown in Table 1.
[ COMPARATIVE EXAMPLE 2 ]
[ example 1 ] catalyst B1 was charged into the first and second reaction zones, respectively.
The results of the analytical tests are shown in Table 1.
[ example 18 ]
Examine [ examples 1-17 ] the application of A/B two catalysts in butene double bond isomerization reaction.
The catalysts of the present invention [ examples 1 to 17 ] were charged into the first and second reaction zones, respectively, in the manner shown in Table 1 to conduct reaction evaluation. The raw material comprises 12.1% of n-butane, 35.6% of cis-2-butene and 51.3% of trans-2-butene mixed C4. The temperature of the reactor I is controlled to be 250 ℃, the reaction pressure is 0.4MPa, and the weight space velocity is 8 hours-1The temperature of the reactor II is 350 ℃, the reaction pressure is 0.4MPa, and the weight space velocity is 8 hours-1The catalysts were evaluated under the conditions and the reaction results are shown in Table 2.
[ COMPARATIVE EXAMPLE 3 ]
The respective first and second reaction zones were charged in the manner as described in Table 1 of the catalyst to conduct evaluation of the reaction. To contain n-butyl12.1 percent of alkane, 35.6 percent of cis-2-butene and 51.3 percent of trans-2-butene mixed with C4 are taken as raw materials. The temperature of the reactor I is controlled to be 250 ℃, the reaction pressure is 0.4MPa, and the weight space velocity is 8 hours-1The temperature of the reactor II is 350 ℃, the reaction pressure is 0.4MPa, and the weight space velocity is 10 hours-1The catalysts were evaluated under the conditions and the reaction results are shown in Table 2.
TABLE 1
TABLE 2
| Catalyst loading | 2-butene conversion% | N-butene selectivity,% |
| Example 1 | 22.27 | 99.21 |
| Example 2 | 22.17 | 99.18 |
| Example 3 | 22.27 | 99.10 |
| Example 4 | 21.97 | 99.10 |
| Example 5 | 21.77 | 99.00 |
| Example 6 | 22.37 | 98.80 |
| Example 7 | 21.87 | 99.10 |
| Example 8 | 22.37 | 98.90 |
| Example 9 | 22.37 | 98.70 |
| Example 10 | 21.87 | 99.30 |
| Example 11 | 19.86 | 99.20 |
| Example 12 | 19.76 | 99.10 |
| Example 13 | 21.97 | 99.00 |
| Example 14 | 22.17 | 98.90 |
| Example 15 | 22.37 | 98.80 |
| Example 16 | 22.27 | 98.90 |
| Example 17 | 22.37 | 99.00 |
| Comparative example 1 | 22.1 | 93.76 |
| Comparative example 2 | 16.33 | 97.68 |
Therefore, the catalyst with different activities is loaded in different areas by adopting the invention, higher conversion rate and selectivity can be obtained at the same time, and the comprehensive performance is obviously higher than that of the comparative example.
[ examples 19 to 25 ]
The catalysts a1 and B1 obtained in the present invention [ example 1 ] were subjected to reaction evaluation in the manner of [ example 18 ], and tests were carried out while changing the process conditions, and the reaction conditions and results are shown in table 3.
TABLE 3
[ COMPARATIVE EXAMPLE 4 ]
By usingThe document CN102649671A discloses a process in which the first reaction zone is SiO2/Al2O3ZSM-11 molecular sieve with the mol ratio of 200, and the second reaction zone is silicon oxide.
The raw material comprises 12.1% of n-butane, 35.6% of cis-2-butene and 51.3% of trans-2-butene mixed C4. The temperature of the first reaction zone is controlled to be 320 ℃, the reaction pressure is 0.8MPa, and the weight space velocity is 20 hours-1The temperature of the second reaction zone is 340 ℃, the reaction pressure is 0.5MPa, and the weight space velocity is 10 hours-1The catalyst was evaluated under the conditions and the reaction results were: the 2-butene conversion was 23.2% and the 1-butene selectivity was only 97.1%.
Comparative example 4 the catalyst used in the first reaction zone was an unmodified ZSM-11 molecular sieve, which was less acidic and less active than the molecular sieve Zr-ZSM with framework zirconium of the present invention. Compared with comparative example 4, the conversion degree of the 2-butene in the first reaction zone is higher, the amount of the 2-butene participating in the reaction in the second reaction zone is less, so that the reaction severity degree of the second reaction zone is lower, and the final high conversion rate and high selectivity are ensured.
Claims (15)
1. A butene isomerization process comprising the steps of:
a) feeding a feed stream containing 2-butene into a first reaction zone to contact with a catalyst A to produce a stream I;
b) passing said stream I to at least one second reaction zone for contact with catalyst B to produce a product stream comprising 1-butene;
wherein the catalyst A contains molecular sieve Zr-ZSM with a framework of zirconium; the catalyst B contains silicon oxide or magnesium oxide.
2. The butene isomerization process according to claim 1, wherein the catalyst A comprises 30 to 90 parts by weight of Zr-ZSM and 10 to 70 parts by weight of binder, preferably 40 to 80 parts by weight of Zr-ZSM and 20 to 60 parts by weight of binder, more preferably 50 to 80 parts by weight of Zr-ZSM and 20 to 50 parts by weight of binder; relative to the total weight parts of the Zr-ZSM and the binder.
3. The butene isomerization process according to any one of claims 1-2, wherein the Zr-ZSM molecule is selected from one of the group consisting of Zr-ZSM-5, Zr-ZSM-11, Zr-ZSM-35 and Zr-ZSM-39; preferably a mechanical mixture of at least two selected from the group consisting of Zr-ZSM-5, Zr-ZSM-11, Zr-ZSM-35 and Zr-ZSM-39; more preferably eutectic molecular sieves of at least two selected from the group consisting of Zr-ZSM-5, Zr-ZSM-11, Zr-ZSM-35 and Zr-ZSM-39; most preferred is Zr-ZSM-5/ZSM-11 eutectic molecular sieve.
4. The butene isomerization method according to claim 2, wherein the binder is at least one selected from the group consisting of alumina and silica.
5. The butene isomerization process according to any one of claims 1 to 4, wherein the Zr-ZSM molecular sieve has a Si/Zr molar ratio of 50 to 1000, preferably 100 to 500.
6. The butene isomerization process according to any one of claims 1 to 5, wherein the catalyst A does not contain an alkaline earth metal element or an oxide thereof.
7. The butene isomerization method according to claim 6, wherein the alkaline earth metal element is at least one selected from the group consisting of magnesium, calcium, strontium and barium; in particular magnesium.
8. The butene isomerization method of claim 1, wherein the reaction temperature of the first reaction zone is 150-280 ℃, the reaction pressure is 0-1 MPa, and the weight space velocity is 1-20 hours-1(ii) a The preferable reaction temperature is 180-270 ℃, the pressure is 0.5-1 MPa, and the weight space velocity is 2-10 hours-1。
9. The butene isomerization process of claim 1, wherein the reaction temperature of the second reaction zone is 280-420 ℃, the pressure is 0-1 MPa, and the weight space velocity is1 to 20 hours-1(ii) a The preferable contact temperature is 320-400 ℃, the pressure is 0.5-1 MPa, and the weight space velocity is 2-10 hours-1。
10. The butene isomerization process of claim 1, wherein the reaction temperature of the first reaction zone is lower than the reaction temperature of the second reaction zone.
11. The butene isomerization method according to claim 1, wherein the stream containing 2-butene is derived from a mixed carbon four stream as a by-product of a refinery catalytic cracking unit, an ethylene plant steam cracking unit or a coal-to-olefin unit, preferably a carbon four stream obtained by removing 1, 3-butadiene and isobutene from a mixed carbon four stream as a by-product of a refinery catalytic cracking unit, an ethylene plant steam cracking unit or a coal-to-olefin unit.
12. The butene isomerization process of claim 1, wherein the 2-butene-containing stream is a mixture comprising 1-butene and 2-butene which does not meet thermodynamic equilibrium values.
13. The butene isomerization process according to claim 1, wherein the 2-butene-containing stream has a mass concentration of 1-butene of less than 4% and a mass concentration of 2-butene of more than 45%.
14. The butene isomerization process of claim 1, wherein the mass concentration of 1, 3-butadiene in the 2-butene-containing stream is less than 30 ppm.
15. The butene isomerization process according to claim 1, wherein the weight ratio of the catalyst A to the catalyst B is 0.1-8: 1, preferably 0.2-5: 1, more preferably 0.5-4: 1.
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| CN102649671A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Butene isomerization reaction method |
| CN103379956A (en) * | 2010-12-21 | 2013-10-30 | 巴斯夫公司 | Isomerization catalysts |
| US20150273450A1 (en) * | 2014-03-28 | 2015-10-01 | Exxonmobil Research And Engineering Company | Synthesis of framework modified zsm-48 crystals |
| CN105268475A (en) * | 2014-07-24 | 2016-01-27 | 中国石油化工股份有限公司 | Method for preparing isobutene through n-butene skeletal isomerization |
| CN105709841A (en) * | 2016-01-18 | 2016-06-29 | 张玲 | Preparation of n-butene skeletal isomerization catalyst |
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| CN1662478A (en) * | 2002-06-18 | 2005-08-31 | 埃克森美孚化学专利公司 | Method for isomerizing a mixed olefin feedstock to 1-olefin |
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| US20150273450A1 (en) * | 2014-03-28 | 2015-10-01 | Exxonmobil Research And Engineering Company | Synthesis of framework modified zsm-48 crystals |
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