CN109608301A - A kind of method that catalytic dehydrogenation of butanes prepares butylene and butadiene - Google Patents
A kind of method that catalytic dehydrogenation of butanes prepares butylene and butadiene Download PDFInfo
- Publication number
- CN109608301A CN109608301A CN201710964985.3A CN201710964985A CN109608301A CN 109608301 A CN109608301 A CN 109608301A CN 201710964985 A CN201710964985 A CN 201710964985A CN 109608301 A CN109608301 A CN 109608301A
- Authority
- CN
- China
- Prior art keywords
- dehydrogenation
- catalyst
- butylene
- butanes
- gallium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 59
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 235000013844 butane Nutrition 0.000 title claims abstract description 40
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 33
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 29
- 239000001273 butane Substances 0.000 claims abstract description 25
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract 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 10
- 239000000047 product Substances 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000282326 Felis catus Species 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- 229920005987 OPPANOL® Polymers 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- SHGUVJPXKKRMRP-UHFFFAOYSA-N [O].CCCC Chemical compound [O].CCCC SHGUVJPXKKRMRP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7088—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of gallium, indium or thallium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of method that catalytic dehydrogenation of butanes prepares butylene and butadiene, use the double activated component composite catalyst comprising zirconium and gallium, butane carries out efficient dehydrogenation, the selectivity of butadiene reaches 17% in product, the selectivity of total butylene reaches 81.5%, and catalyst shows good stability and reproducibility at high temperature.
Description
Technical field
The present invention relates to a kind of method for preparing butylene and butadiene, in particular to a kind of catalytic dehydrogenation of butanes prepares butylene
With the method for butadiene.
Background technique
Butylene is basic petrochemical raw material, and status is only second to ethylene and propylene in petrochemical industry olefin feedstock, is to close
At the important monomer of rubber and high molecular material.It is, in general, that butylene mainly has several isomers, such as n-butene (1- fourth
Alkene), isobutene, cis- dibutene and four kinds of trans- dibutene.N-butene is mainly for the manufacture of methyl ethyl ketone, sec-butyl alcohol, ring
Oxygen butane and butene polymers and copolymer.Isobutene is mainly for the manufacture of butyl rubber, Oppanol and various plastics.
It is, in general, that 1- butylene and 2- butylene can carry out many important basic organic chemical industries of chemical process production together and produce without separation
Product, such as hydration are sec-butyl alcohol and then produce methyl ethyl ketone, oxidative dehydrogenation butadiene, catalysis oxidation maleic anhydride with
And acetic acid.In addition, butylene is also used as raw material manufacture butadiene.Butadiene is the basic material of petrochemical industry, in petroleum
Status is only second to ethylene and propylene in work olefin feedstock, is the important monomer of synthetic rubber and high molecular material.Industrial butylene
Production mainly by C-4-fraction separate obtain.Butylene quality is different in separate sources C-4-fraction.With China's oil
Industry rapid development, oil price is high, and petroleum-based products manufacturing cost is excessively high, and butylene production capacity has lagged far behind reality
The situation of demand, butylene supply and demand shortage is more serious, largely constrains the development of national economy.
In fact, scientist is just making great efforts the new technique for preparing butylene of exploitation, such as utilizes positive fourth since last century
Alkane is raw material, corresponding butylene is prepared by way of dehydrogenation, and have been carried out industrialization.In recent years, with shale gas
Constantly exploration, the minable shale gas total amount in the whole world are huge.Related data shows: the minable shale gas total amount in the whole world is up to
207 cubic metres, wherein the reserves height in China ranks first in the world, and total amount is up to 32 tcms.The main component of shale gas is first
Alkane, ethane, propane and butane, these low-carbon alkanes can further synthesize other chemical intermediates by way of oxidative coupling,
Therefore abundant and cheap raw material is provided for modernization industry.Therefore the technique of butylene is prepared by bigger by raw material of butane
Concern.Process route there are two types of more popular at present: direct dehydrogenation and oxidative dehydrogenation.Although oxidative dehydrogenation is to a certain degree
On can slow down carbon distribution generation, but the oxidant introduced tends to generate carbon monoxide and carbon dioxide, causes the choosing of butylene
Selecting property is very low.And direct dehydrogenation can effectively avoid the generation of other OXO products, olefine selective may be up to 95% or more.Although
Direct dehydrogenation generally requires higher temperature, this may result in the hydrocarbon that the excessive dehydrogenation of butane even chain rupture generates small molecule in this way
Class, but can often realize that c h bond and C-C are selectively living by catalyst regulation.Furthermore the carbon deposit generated can pass through catalyst
Regeneration is realized.Therefore butane direct dehydrogenation prepares butylene and receives extensive favor, and the technique has been carried out industrial metaplasia
At.
Currently used butane dehydrogenation catalyst has following several: (1) Pt base catalyst, noble metal catalyst are anti-in dehydrogenation
It should play the role of vital, but higher cost.Practical application has Uop Inc. and the oil company Philips, they
Select Pt as catalyst activity component, by the way that auxiliary agent is added, carrier improves the stability of catalyst.It is wherein more famous to help
Agent is exactly Sn, and commercialized catalyst is Pt-Sn-Al2O3 at present;(2) V-based catalyst, this catalyst are usually to use
Vanadium oxide is supported on aluminium oxide or silica;(3) Cr base catalyst.Cr base catalyst is that another is important nonmetallic
Catalyst, Catofin has been commercialized at present.Although the report at present about direct dehydrogenation catalyst is commonplace,
It is that butane dehydrogenation still suffers from problems and challenge.For example, thermodynamically, direct dehydrogenation is a strong endothermic reaction, need
It to carry out at high temperature.High temperature be easy to cause sintering of catalyst and inactivates, therefore it is required that catalyst has high stability.Another party
Face, high temperature be easy to cause the excessive dehydrogenation of butane to form carbon deposit, thus to realize selective dehydrogenation to the design of catalyst it is also proposed that
Higher requirement.For current industrial catalyst, Pt catalyst is easy carbon deposit, although high temperature regeneration can burn off carbon deposit,
It is that high temperature easily causes Pt to be sintered and inactivate.Although regenerative process needs it was reported that addition Sn can effectively prevent Pt sintering
Chlorination, this process have corrosiveness to equipment.Cr base catalyst is there is also similar problem, and Cr can move to load under hot conditions
Active component is caused to lose in body aluminium oxide.Another aspect Cr's will also result in environmental pollution using the use of Cr.
In conclusion the exploitation of new catalyst is to realize that butane dehydrogenation prepares the committed step of alkene.Ideal catalysis
Agent should have excellent C-H activity function, and can also shift intermediate product rapidly to avoid excessive dehydrogenation even chain rupture;This
Outside, catalyst should have the anti-caking power of excellent high temperature, be able to maintain activity in circular regeneration in this way;But also it should focus on
Based on base metal, environmental-friendly catalyst is developed, to embody bigger industrial value.
Summary of the invention
In view of the above problems in the prior art, the object of the present invention is to provide a kind of catalytic dehydrogenation of butanes to prepare butylene and fourth
The method of diene realizes the Efficient Conversion of butane.
To solve the above-mentioned problems, technical scheme is as follows:
A kind of method that catalytic dehydrogenation of butanes prepares butylene and butadiene, in the presence of dehydrogenation, by butane into
Row dehydrogenation reaction, and butylene and butadiene are separated from obtained dehydrogenation product;The dehydrogenation includes in zirconium and gallium
One or two are used as active component.
Further, the active component in the dehydrogenation accounts for the 1-10% of catalyst gross mass.
Preferably, the active component in the dehydrogenation accounts for the 3-5% of catalyst gross mass.
Preferably, the active component in the dehydrogenation is zirconium and gallium, and the mass ratio of zirconium and gallium is 0.1-10.
Preferably, the mass ratio of zirconium and gallium is 0.2-5 in the active component in the dehydrogenation.
Dehydrogenation includes active component zirconium and gallium, which is a kind of double activated component composite catalyst.
The composite catalyst is acted synergistically by zirconium gallium based on base metal zirconium and gallium and is realized the efficient dehydrogenation of butane.Pass through regulation
C h bond and the selection activation of C-C are realized, to improve the selectivity of butylene in the interface of composite catalyst.
Zirconium oxide and gallium oxide not only have excellent thermal stability, and it can generate a large amount of oxygen under hydrogen treat
Vacancy can effectively facilitate c h bond activation.
Above-mentioned active component exists with metal or metal oxide form, can individually make dehydrogenation, can also bear
It is loaded on carrier, the carrier is not particularly limited, it is preferable to use sial complex carrier, for example, ZSM Series Molecules
Sieve, MCM Series Molecules sieve, beta-zeolite etc..It is total that active component in dehydrogenation described in loaded catalyst accounts for catalyst
The 1-10% of quality, preferably 3-5%, particularly preferred 4.5%.
Above-mentioned dehydrogenation can be made according to existing various methods, such as a kind of specific implementation according to the present invention
Mode, the dehydrogenation are prepared as follows:
1) it weighs the soluble-salt of a certain amount of zirconium and gallium and is configured to mixed solution;
2) by above-mentioned mixed solution incipient impregnation in sial complex carrier;
3) aging, drying after impregnating, high-temperature calcination is to get catalyst solid powder;
4) above-mentioned catalyst solid powder is passed through into H2/N2The processing of mixed gas high-temperature activation.
A kind of specific embodiment according to the present invention, catalytic dehydrogenation of butanes prepare the reaction condition of butylene and butadiene
Are as follows: reaction temperature is 500-750 DEG C, reaction pressure 0-0.3Mpa, and volume space velocity is 20-300h when gas-1.The butane with
Hydrogen is fed jointly, and wherein the molar ratio of hydrogen and butane is 0.1-10.
The concentration of inert gas dilution hydrogen and butane can also be used, during catalytic dehydrogenating reaction to slow down reaction
Temperature in the process rises.The dosage of the inert gas controls reaction temperature subject within 500-750 DEG C, the inertia
Gas can be one of nitrogen, helium and argon gas or a variety of.
Contain C3 following components and C4 component in the dehydrogenation product in the present invention.C4 component mainly contains butylene (packet
Include 1- butylene, 2- butylene and isobutene), butadiene and unreacted butane.Art technology can be used in the present invention
Method well known to personnel isolates n-butene and butadiene from dehydrogenation product.
Advantages of the present invention is as follows:
1) use base metal zirconium and gallium for the active component of catalyst, it is environmental-friendly, it is at low cost, there is bigger industry
Value and application prospect.
2) the efficient dehydrogenation of butane is realized by zirconium gallium synergistic effect, the selectivity of butadiene reaches 17% or so in product,
The selectivity of total butylene reaches 81.5%.
3) catalyst shows good stability and reproducibility at high temperature.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of the catalyst of different activities constituent content provided in an embodiment of the present invention;
Fig. 2 is butane in the catalyst butane dehydrogenation reaction of different activities constituent content provided in an embodiment of the present invention
Conversion ratio and selective figure;
Fig. 3 is the product distribution of the catalyst butane dehydrogenation of different activities constituent content provided in an embodiment of the present invention
Figure;
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
A certain amount of zirconium nitrate is weighed, and is configured to solution, then incipient impregnation is in sial complex carrier.It is old after dipping
Change to be subsequently placed in 100 DEG C of baking ovens for 1 hour and be dried overnight, gained catalyst passes through 750 DEG C high-temperature roasting 2 hours, obtains catalyst
cat 1。
Zirconium mass fraction is 4.47% in the obtained catalyst of the present embodiment, the specific surface area of the catalyst, Kong Rong and
Aperture is as shown in table 1, and X-ray diffractogram is as shown in Figure 1.
Embodiment 2
It is 3.5:1 by the mass ratio of metal zirconium and gallium, weighs the presoma zirconium nitrate and nitre of a certain amount of zirconium and gallium
Sour gallium is simultaneously configured to mixed solution, and then incipient impregnation is in sial complex carrier.It is subsequently placed within aging 1 hour after dipping
It is dried overnight in 100 DEG C of baking ovens, gained catalyst passes through 750 DEG C high-temperature roasting 2 hours, obtains catalyst cat 2.
The mass fraction of zirconium is 3.53% in the obtained catalyst of the present embodiment, and the mass fraction of gallium is 0.81%.It should
The specific surface area of catalyst, Kong Rong and aperture are as shown in table 1, and X-ray diffractogram is as shown in Figure 1.
Embodiment 3
It is 2:2.5 by the mass ratio of metal zirconium and gallium, weighs the presoma zirconium nitrate and nitre of a certain amount of zirconium and gallium
Sour gallium is simultaneously configured to mixed solution, and then incipient impregnation is in sial complex carrier.It is subsequently placed within aging 1 hour after dipping
It is dried overnight in 100 DEG C of baking ovens, gained catalyst passes through 750 DEG C high-temperature roasting 2 hours, obtains catalyst cat 3.
The mass fraction of zirconium is 1.89% in the obtained catalyst of the present embodiment, and the mass fraction of gallium is 2.23%.It should
The specific surface area of catalyst, Kong Rong and aperture are as shown in table 1, and X-ray diffractogram is as shown in Figure 1.
Embodiment 4
It is 1:3.5 by the mass ratio of metal zirconium and gallium, weighs the presoma zirconium nitrate and nitre of a certain amount of zirconium and gallium
Sour gallium is simultaneously configured to mixed solution, and then incipient impregnation is in sial complex carrier.It is subsequently placed within aging 1 hour after dipping
It is dried overnight in 100 DEG C of baking ovens, gained catalyst passes through 750 DEG C high-temperature roasting 2 hours, obtains catalyst cat 4.
The mass fraction of zirconium is 0.97% in the obtained catalyst of the present embodiment, and the mass fraction of gallium is 3.25%.It should
The specific surface area of catalyst, Kong Rong and aperture are as shown in table 1, and X-ray diffractogram is as shown in Figure 1.
Embodiment 5
It is 0.5:4 by the mass ratio of metal zirconium and gallium, weighs the presoma zirconium nitrate and nitre of a certain amount of zirconium and gallium
Sour gallium is simultaneously configured to mixed solution, and then incipient impregnation is in sial complex carrier.It is subsequently placed within aging 1 hour after dipping
It is dried overnight in 100 DEG C of baking ovens, gained catalyst passes through 750 DEG C high-temperature roasting 2 hours, obtains catalyst cat 5.
The mass fraction of zirconium is 0.51% in the obtained catalyst of the present embodiment, and the mass fraction of gallium is 3.34%.It should
The specific surface area of catalyst, Kong Rong and aperture are as shown in table 1, and X-ray diffractogram is as shown in Figure 1.
Embodiment 6
It weighs a certain amount of gallium nitrate and is configured to solution, then incipient impregnation is in sial complex carrier.It is old after dipping
Change to be subsequently placed in 100 DEG C of baking ovens for 1 hour and be dried overnight, gained catalyst passes through 750 DEG C high-temperature roasting 2 hours, obtains catalyst
cat 6。
The mass fraction of gallium is 4.34% in the obtained catalyst of the present embodiment.The specific surface area of the catalyst, Kong Rong
As shown in table 1 with aperture, X-ray diffractogram is as shown in Figure 1.
The chemical physical property of 1 different catalysts of table
Embodiment 7
Catalyst cat 1~cat 6 prepared by above-described embodiment 1 to embodiment 6 is after preparing, by tabletting
Sieve selects the catalyst 0.4g of 60-80 mesh and quartz sand to be put into quartz reactor after mixing according to 1:3 mass ratio.
Catalyst is needed before the reaction by H2/N2(10%) it handles 30 minutes to 600 degrees Celsius.Then by butane, hydrogen
It is introduced into reaction tube with nitrogen according to the volume ratio of 1:1:8, total flow 100ml/min.Reaction carries out under normal pressure, and temperature is
600 DEG C, volume space velocity is 20-300h when gas-1。
It is as shown in Figures 2 and 3 that product is subjected to gas phase analysis acquired results.The conversion ratio of butane as shown in Figure 2 reaches 90%
Above, selectivity reaches as high as 60%;As shown in figure 3, the selectivity of butadiene is up to 17% or so in product, total butylene
Selectivity be up to 81.5%.
Above description sufficiently discloses a specific embodiment of the invention.It should be pointed out that being familiar with the field
Range of any change that technical staff does a specific embodiment of the invention all without departing from claims of the present invention.
Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (8)
1. a kind of method that catalytic dehydrogenation of butanes prepares butylene and butadiene, it is characterised in that: in the presence of dehydrogenation,
Butane is subjected to dehydrogenation reaction, and separates butylene and butadiene from obtained dehydrogenation product;The dehydrogenation includes zirconium
Active component is used as with one or both of gallium.
2. the method that catalytic dehydrogenation of butanes prepares butylene and butadiene according to claim 1, it is characterised in that: the dehydrogenation
Active component in catalyst accounts for the 1-10% of catalyst gross mass.
3. the method that catalytic dehydrogenation of butanes prepares butylene and butadiene according to claim 2, it is characterised in that: the dehydrogenation
Active component in catalyst accounts for the 3-5% of catalyst gross mass.
4. the method that catalytic dehydrogenation of butanes prepares butylene and butadiene according to claim 1, it is characterised in that: the dehydrogenation
Active component in catalyst is zirconium and gallium, and the mass ratio of zirconium and gallium is 0.1-10.
5. the method that catalytic dehydrogenation of butanes prepares butylene and butadiene according to claim 4, it is characterised in that: the dehydrogenation
The mass ratio of zirconium and gallium is 0.2-5 in active component in catalyst.
6. the method that any one of -5 catalytic dehydrogenation of butanes prepare butylene and butadiene according to claim 1, which is characterized in that
The dehydrogenation is prepared as follows:
1) it weighs the soluble-salt of a certain amount of zirconium and gallium and is configured to mixed solution;
2) by above-mentioned mixed solution incipient impregnation in sial complex carrier;
3) aging, drying after impregnating, high-temperature calcination is to get catalyst solid powder;
4) above-mentioned catalyst solid powder is passed through into H2/N2The processing of mixed gas high-temperature activation.
7. the method that catalytic dehydrogenation of butanes prepares butylene and butadiene according to claim 1, it is characterised in that: the butane
It is fed jointly with hydrogen, wherein the molar ratio of hydrogen and butane is 0.1-10.
8. the method that catalytic dehydrogenation of butanes prepares butylene and butadiene according to claim 1, it is characterised in that: reaction temperature
It is 500-750 DEG C, reaction pressure 0-0.3Mpa, volume space velocity is 20-300h when gas-1。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710964985.3A CN109608301B (en) | 2017-10-17 | 2017-10-17 | Method for preparing butylene and butadiene through catalytic dehydrogenation of butane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710964985.3A CN109608301B (en) | 2017-10-17 | 2017-10-17 | Method for preparing butylene and butadiene through catalytic dehydrogenation of butane |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109608301A true CN109608301A (en) | 2019-04-12 |
CN109608301B CN109608301B (en) | 2021-10-19 |
Family
ID=66001803
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710964985.3A Active CN109608301B (en) | 2017-10-17 | 2017-10-17 | Method for preparing butylene and butadiene through catalytic dehydrogenation of butane |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109608301B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115634678A (en) * | 2022-10-19 | 2023-01-24 | 北京超能活力科技开发有限责任公司 | Ethane dehydrogenation catalyst and method for simultaneously preparing ethylene and hydrogen by ethane dehydrogenation |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1115980A (en) * | 1993-01-04 | 1996-01-31 | 切夫里昂化学公司 | Dehydrogenation processes and equipment therefor |
CN1902149A (en) * | 2003-12-30 | 2007-01-24 | 巴斯福股份公司 | Method for the production of butadiene and 1-butene |
CN101084174A (en) * | 2004-12-21 | 2007-12-05 | 巴斯福股份公司 | Method for producing butadiene from n-butane |
CN101119949A (en) * | 2005-01-17 | 2008-02-06 | 巴斯福股份公司 | Method for producing butadiene from n-butane |
CN103140459A (en) * | 2010-09-30 | 2013-06-05 | 陶氏环球技术有限责任公司 | Non-oxidative dehydrogenative process |
CN103626620A (en) * | 2012-08-22 | 2014-03-12 | 湖南百利工程科技股份有限公司 | Method used for joint production of butadiene and isoprene from mixed C4 |
CN104437456A (en) * | 2013-09-22 | 2015-03-25 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene by isobutane dehydrogenation and preparation method and application of catalyst |
CN105396571A (en) * | 2014-09-16 | 2016-03-16 | 中国石油化工股份有限公司 | Mesoporous Ga/Al composite oxide catalyst, preparation method and applications thereof |
CN105582923A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Catalyst used for producing olefin through light alkane dehydrogenation |
CN105618026A (en) * | 2016-01-05 | 2016-06-01 | 中国石油大学(华东) | Catalyst for catalytic dehydrogenation of alkane as well as preparation method and application method of catalyst |
-
2017
- 2017-10-17 CN CN201710964985.3A patent/CN109608301B/en active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1115980A (en) * | 1993-01-04 | 1996-01-31 | 切夫里昂化学公司 | Dehydrogenation processes and equipment therefor |
CN1902149A (en) * | 2003-12-30 | 2007-01-24 | 巴斯福股份公司 | Method for the production of butadiene and 1-butene |
CN101084174A (en) * | 2004-12-21 | 2007-12-05 | 巴斯福股份公司 | Method for producing butadiene from n-butane |
CN101119949A (en) * | 2005-01-17 | 2008-02-06 | 巴斯福股份公司 | Method for producing butadiene from n-butane |
CN103140459A (en) * | 2010-09-30 | 2013-06-05 | 陶氏环球技术有限责任公司 | Non-oxidative dehydrogenative process |
CN103626620A (en) * | 2012-08-22 | 2014-03-12 | 湖南百利工程科技股份有限公司 | Method used for joint production of butadiene and isoprene from mixed C4 |
CN104437456A (en) * | 2013-09-22 | 2015-03-25 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene by isobutane dehydrogenation and preparation method and application of catalyst |
CN105396571A (en) * | 2014-09-16 | 2016-03-16 | 中国石油化工股份有限公司 | Mesoporous Ga/Al composite oxide catalyst, preparation method and applications thereof |
CN105582923A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Catalyst used for producing olefin through light alkane dehydrogenation |
CN105618026A (en) * | 2016-01-05 | 2016-06-01 | 中国石油大学(华东) | Catalyst for catalytic dehydrogenation of alkane as well as preparation method and application method of catalyst |
Non-Patent Citations (1)
Title |
---|
TATYANA OTROSHCHENKO等: ""Bulk binary ZrO2 -based oxides as highly activealternative-type catalysts for non-oxidative isobutane dehydrogenation"", 《CHEM COMM》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115634678A (en) * | 2022-10-19 | 2023-01-24 | 北京超能活力科技开发有限责任公司 | Ethane dehydrogenation catalyst and method for simultaneously preparing ethylene and hydrogen by ethane dehydrogenation |
CN115634678B (en) * | 2022-10-19 | 2024-05-24 | 北京超能活力科技开发有限责任公司 | Ethane dehydrogenation catalyst and method for simultaneously preparing ethylene and hydrogen through ethane dehydrogenation |
Also Published As
Publication number | Publication date |
---|---|
CN109608301B (en) | 2021-10-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Monai et al. | Propane to olefins tandem catalysis: a selective route towards light olefins production | |
CN106140240B (en) | A kind of low-carbon alkanes or alkylbenzene oxidative dehydrogenation nitridation B catalyst and its preparation method and application | |
CN106478351B (en) | The method of iso-butane and/or dehydrogenating propane | |
CN100464849C (en) | Catalyst propane using aluminium oxide modified mesonore molecular sieve as carrier for dehydrogenation producing propylene | |
CN105312046B (en) | A kind of catalyst for dehydrogenation of low-carbon paraffin and the method for improving its activity and stability | |
CN109833903A (en) | A kind of low-carbon alkanes anaerobic dehydrogenation alkene catalyst and its preparation and application | |
CN109603898B (en) | Low-carbon alkane dehydrogenation catalyst and method for preparing low-carbon olefin | |
US10538711B2 (en) | Process for converting naphtha | |
CN108176405A (en) | A kind of dehydrating alkanes increased response auxiliary agent and its preparation method and application | |
CN106964392A (en) | Oxidative dehydrogenation of propane catalyst and application thereof | |
CN108014832A (en) | The hydrogenation technique of C-2-fraction in selective hydrogenation catalyst and its application and preparing ethylene by steam cracking | |
CN103058814B (en) | Method for producing aromatic hydrocarbon and olefin from liquefied gas | |
CN109608301A (en) | A kind of method that catalytic dehydrogenation of butanes prepares butylene and butadiene | |
CN105233818A (en) | Method for improving stability of low-carbon alkane dehydrogenation catalyst through acidity and alkalinity adjustment | |
CN112742456A (en) | Dehydrogenation cracking catalyst, preparation method thereof and method for producing ethylene and propylene by using hydrocarbon four | |
CN109701615B (en) | Multifunctional catalyst system and application thereof | |
CN101148391B (en) | Method for producing propylene by butylene and ethylene dismutation | |
CN100368356C (en) | Method for producing propylene through catalytic cracking C4 olefin | |
CN103626620B (en) | A kind of method of preparing butadiene and isoprene of being combined by hybrid C 4 | |
CN103121891A (en) | Method for producing low-carbon olefin | |
CN106221786A (en) | A kind of method for transformation of Petroleum | |
CN105732251A (en) | Method for producing aromatic hydrocarbon by catalytic conversion of methanol | |
CN103834435B (en) | Two-stage reaction process for hydro-aromatization of carbon-four liquefied gas | |
CN112246275A (en) | Catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide and preparation method thereof | |
TWI579306B (en) | Preparation of Propylene and Butene by Ethylene Oligomerization at Low Pressure Catalyzed by Organic Acid |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |