CN114733521A - Double-crystal type supported alkane non-oxidative dehydrogenation catalyst - Google Patents
Double-crystal type supported alkane non-oxidative dehydrogenation catalyst Download PDFInfo
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- CN114733521A CN114733521A CN202210373319.3A CN202210373319A CN114733521A CN 114733521 A CN114733521 A CN 114733521A CN 202210373319 A CN202210373319 A CN 202210373319A CN 114733521 A CN114733521 A CN 114733521A
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- Prior art keywords
- catalyst
- oxidative dehydrogenation
- dehydrogenation catalyst
- alkane
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- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 35
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims abstract description 20
- 239000013078 crystal Substances 0.000 title claims abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 28
- 239000011135 tin Substances 0.000 claims abstract description 28
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000011572 manganese Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229910052718 tin Inorganic materials 0.000 claims abstract description 15
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 14
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 22
- 239000011777 magnesium Substances 0.000 claims description 17
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010948 rhodium Substances 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims 1
- 235000011147 magnesium chloride Nutrition 0.000 claims 1
- 235000002867 manganese chloride Nutrition 0.000 claims 1
- 229940099607 manganese chloride Drugs 0.000 claims 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims 1
- 235000005074 zinc chloride Nutrition 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 14
- 239000000571 coke Substances 0.000 abstract description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 12
- 238000006356 dehydrogenation reaction Methods 0.000 description 11
- 239000001294 propane Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910006415 θ-Al2O3 Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000003841 chloride salts Chemical class 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910002846 Pt–Sn Inorganic materials 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910020944 Sn-Mg Inorganic materials 0.000 description 1
- 229910020994 Sn-Zn Inorganic materials 0.000 description 1
- 229910009069 Sn—Zn Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 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
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000009681 x-ray fluorescence measurement Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- 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
- C07C5/3337—Catalytic processes with metals of the platinum group
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a double-crystal type supported alkane non-oxidative dehydrogenation catalyst. It comprises active catalytic metal, active catalytic assistant alkaline earth metal and porous metal oxide catalyst carrier. Wherein the porous metal oxide catalyst carrier of the present invention is delta-theta type Al2O3The active catalytic helper metal is a mixture of tin, zinc and manganese. The catalyst of the present invention has obviously reduced deposited coke amount, long service life and high propylene selectivity.
Description
Technical Field
The invention belongs to the field of catalysis, and relates to a double-crystal type supported alkane non-oxidative dehydrogenation catalyst.
Background
The catalyst is essential in alkane dehydrogenation processes. Olefins such as propylene are widely used as basic raw materials in chemical production processes, for example, in the production of polypropylene, acrylic acid, acrylonitrile, cumene, etc. The demand for olefins (such as propylene) is increasing every year. Therefore, it is necessary to improve the yield of olefins. One process for the synthesis of olefins such as propylene is the non-oxidative catalytic dehydrogenation of alkanes such as propane to produce propylene.
Wherein EP0328507 discloses a process for the catalytic dehydrogenation of propane, the molar ratio of hydrogen to propane being between 0.05 and 0.5 in the presence of hydrogen, the catalyst consisting of a catalyst comprising at least one platinum group metal and additionally a cocatalyst and promoter, the alkane feed being passed through the catalyst bed for the dehydrogenation reaction. The catalyst composition comprises the steps of 0.2-1 wt% of platinum, 0.15-1 wt% of tin as a cocatalyst and 0.8-2 wt% of potassium as a promoter, wherein the catalyst carrier is alumina, and the catalyst is obtained by calcining at the temperature of 450-550 ℃. Furthermore, JP10180101 describes a process for the catalytic dehydrogenation of alkanes in the presence of hydrogen. The catalyst comprises ZnO/Al2O3 carrier, wherein the amount of ZnO is 5-50 wt%. The weight ratio of ZnO/Al2O3 was 30:70 or 44: 55. In addition, the catalyst has a Pt content of 0.05-1.5 wt%, a Sn content of 0.5-10 wt% and an alkali metal content of 0.01-10 wt%.
Disclosure of Invention
The object of the present invention is to overcome the drawbacks of the prior art and to provide a better catalyst for the non-oxidative dehydrogenation of alkanes.
The invention provides a double-crystal type supported alkane non-oxidative dehydrogenation catalyst, which comprises the following 4 active components:
(a) an active catalytic metal (i.e., active metal M) selected from platinum, palladium, rhodium, rhenium, ruthenium, or iridium;
(b) active catalytic helper metals: mixtures of tin, zinc and manganese;
(c) active catalyst promoter alkaline earth metal: selected from magnesium, calcium, strontium, potassium;
(d) a porous metal oxide catalyst support;
wherein the weight ratio of the element (a) to the element (d) is 0.4 to 10 wt%; the weight ratio of the element (c) to the element (d) is 0.5 to 5 wt%.
In the following description, the contents are actually the weight ratios of the porous metal oxide catalyst support to itself.
In the catalyst composition of the present invention, the active metal M is selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh), rhenium (Re), ruthenium (Ru) and iridium (Ir). Platinum (Pt) is preferred. The content of the carrier is 0.4-7.5 wt%.
In the catalyst composition of the invention, the active catalysis assisting metal is selected from tin (Sn)/zinc (Zn)/manganese (Mn), and the content of each metal is at least more than 0.2 wt%, for example, the content of tin (Sn) is 0.4 wt% to 2 wt%; the zinc (Zn) content is 0.3 to 2 weight percent; the content of manganese is 0.2 wt% -1 wt%.
In the catalyst composition of the present invention, the content of alkaline earth metal is at least 0.4 wt% or more, for example, the content of potassium is 1 wt% to 5 wt%. Preferably, the alkaline earth metal is selected from magnesium (Mg), calcium (Ca) and strontium (Sr). More preferably, the alkaline earth metal is magnesium (Mg).
In the catalyst composition of the present invention, the element (d) is selected from Al2O3、TiO2、CeO2、ZrO2Or mixtures thereof.
Preferably, the element (d) is delta-theta type Al2O3Said delta-theta type Al2O3Is delta crystal form Al2O3And theta crystal form Al2O3A mixture of (a); and the delta crystal form Al2O3And theta crystal form Al2O3The weight ratio of (A) to (B) is 0.2-1.5.
Preferably, the BET surface area of the element (d) is from 50 to 500m2/g。
The invention also provides a preparation method of the alkane non-oxidative dehydrogenation catalyst, which comprises the following steps:
(1) mixing an element (d) with a solution containing a salt of the elements (a), (b), (c), followed by evaporating the liquid in the solution to obtain a modified slurry, and washing the modified slurry with a solvent to obtain a catalyst substrate; that is, metals Pt, Sn, Zn, Mn, and alkaline earth metals are embedded on a porous metal oxide catalyst carrier to obtain a catalyst base; (2) calcining the catalyst substrate in an oxygen-containing environment to obtain the alkane non-oxidative dehydrogenation catalyst.
As used herein, "intercalation" refers to techniques capable of placing the metals Pt, Sn, Zn, Mn and alkaline earth metals on the porous metal oxide catalyst support, such as impregnation precipitation, deposition-precipitation, co-precipitation, incipient wetness impregnation, or combinations thereof.
Preferably, the calcination is carried out at a temperature of 400 to 650 ℃ for 2 to 6 hours.
Preferably, the pH value of the solvent is in the range of 5.5-7.5.
The method according to the present invention, wherein the step (a) comprises mixing the porous double-crystal type metal oxide catalyst support with a solution containing a platinum salt, a tin salt (Sn), a zinc salt (Zn), a manganese salt (Mn), and an alkaline earth metal salt, followed by evaporating a liquid in the solution to prepare a modified slurry, and washing the slurry with a solvent to obtain the catalyst substrate. The pH value is advantageously in the range from 3 to 10, preferably from 5 to 7.5. The solvent may be any solvent suitable for removing anions. For example, water may be used. The catalyst substrate needs to be dried before it is calcined in an oxygen-containing environment. The drying of the modified slurry and/or the catalyst substrate may be carried out by subjecting the modified slurry and/or the catalyst substrate to a temperature of 400-750 c, for example for a period of 2 to 4 hours. In principle, any form of metallic platinum salts, tin salts (Sn), zinc salts (Zn), manganese salts (Mn) and alkaline earth metal salt solutions can be used. For example, suitable salts may be in the form of acetates, oxalates, nitrates, chlorides, carbonates and bicarbonates. The salt or salts in the solution comprise metal platinum (Pt), tin (Sn), zinc (Zn), manganese (Mn) and alkaline earth salts are chloride salts, preferably all salts in the solution are chloride salts. The slurry can be washed with deionized water until Cl in the standard silver nitrate test filtrate-Is negative.
Experimental data show that when metals such as Pt, Sn, Zn, Mn and alkaline earth metals are loaded on a catalyst carrier by an 'embedding' method, the catalytic performance is greatly improved, and the selectivity and the yield of propylene and the amount of carbon deposition on the catalyst in the dehydrogenation process are greatly reduced.
Step (b) of the process of the present invention is preferably carried out by calcining the catalyst substrate in an oxygen-containing environment at a temperature of from 400 to 750 ℃, for example at a temperature of from 450 to 650 ℃, for example over a period of from 2 to 6 hours. An oxygen-containing environment refers to the use of oxygen or air during calcination.
The invention also relates to a preparation method of the mixed crystal catalyst carrier delta-theta type alumina, wherein the calcination time in a rotary furnace is 1-5 hours, the temperature is 950-1100 ℃, and the proportion range of the two crystal forms is as follows: 0.5-1.5, the specific surface area is 90-300m2/g
Within the framework of the present invention, by alkane is meant a compound of formula C2H2n+2The hydrocarbon of (1). For example, the alkane may be propane, butane, pentane, hexane, heptane, octane, nonane, decane, or mixtures thereof. Preferably, the alkane is propane. Examples of olefins that may be produced in the process of the present invention include, but are not limited to, propylene and ethylene and butenes. The alkane may be pure alkane or a mixture of alkanes or a mixed feed with an inert gas, e.g. N2. Preferably, the alkane comprises predominantly a feed of one alkane species. .
Preferably, the total amount of alkanes in the feed stream is at least 98 wt%, preferably at least 99 wt%, for example 99.9 wt% based on the total feed. Small amounts of olefins may be present in the feed stream (e.g., 0.1% to 0.5 wt% based on the total feed stream). The feed component may also comprise hydrogen, for example, the molar ratio of hydrogen to alkane in the feed stream may be in the range of about 1: 10. The feed components may also comprise an inert gas as a diluent. The inert gas diluent may be selected from helium, nitrogen and mixtures thereof, preferably nitrogen. For example, the molar ratio of alkane to inert gas diluent may be in the range of about 1: 10 to about 1: 1. As used herein, the term "non-oxidative dehydrogenation" is understood to mean that the dehydrogenation is carried out in the substantial absence of an oxidant (e.g. oxygen), i.e. the amount of oxidant in the feed stream comprising the alkane is at most 1 vol% based on the total amount of feed.
The polycrystalline catalyst material is suitable for dehydrogenation reaction of alkane, especially non-oxidative dehydrogenation of propane into propylene, and has the advantages of high propylene yield, high selectivity and long catalyst life under the action of the catalyst in the process of synthesizing propylene from propane. The catalyst of the present invention has several advantages over existing catalysts in the dehydrogenation of alkanes and, in particular, propane:
1) the coke deposited on the catalyst is obviously reduced, and the service life is prolonged;
2) the amount of ethylene as a high value-added by-product (relative to the total by-product) increases;
3) the active surface area of the catalyst is obviously increased;
4) the selectivity of propylene increases.
Detailed Description
Embodiments of the present application will be described in detail by examples, so that how to apply technical means to solve technical problems and achieve technical effects can be fully understood and implemented.
The raw materials and equipment used in the present application are all common raw materials and equipment in the field, and are all from commercially available products, unless otherwise specified. The methods used in this application are conventional in the art unless otherwise indicated.
There are many other possible embodiments of the present invention, which are not listed here, and the embodiments claimed in the claims of the present invention can be implemented.
"comprising" or "including" is intended to mean that the compositions (e.g., media) and methods include the recited elements, but not excluding others. When used in defining compositions and methods, "consisting essentially of … …" is meant to exclude other elements having any significance to the combination of the stated objects. Thus, a composition consisting essentially of the elements defined herein does not exclude other materials or steps that do not materially affect the basic and novel characteristics of the claimed application. "consisting of … …" refers to trace elements and substantial process steps excluding other components. Embodiments defined by each of these transitional terms are within the scope of this application. Obtained by the preparation method disclosed in the patent.
Example 1
Preparation of Pt-Sn-Zn-Mn-Mg/delta-theta-Al2O3Catalyst (catalyst A)
Mixing 100 g of Al2O3Drying at 150 deg.C for 2 hr, calcining at 950 deg.C for 1.5 hr in rotary furnace to obtain delta-theta type Al2O3The specific surface is 100-110m2Chloroplatinic acid solution H containing 0.4 g of platinum2Cl6Pt·6H2O (density: 1.1 g/cc; platinum content 16.5 wt%, ca. 24 mL) (solution A); 1.9 g of SnCl2·2H2O was dissolved in 60 ml ethanol (solution B); 8.5 g of MgCl2·6H2O was dissolved in 100ml of deionized water (solution C); 0.6 g of ZnCl20.5 g of MnCl2Dissolved in 80 ml of deionized water (solution D) and all salt solutions were clear with no suspension at all. The temperature of the water bath was set at 65 ℃. A total of 500ml deionized water plus water from the salt solution was added to the evaporation flask of the Rotavapor. When the temperature stabilized at 65 ℃, all solutions prepared were added to the evaporation flask to obtain a total solution volume of 500 ml. Al (aluminum)2O3The support was preheated at 65 ℃ and added to the flask, and the solution was rotated at 65 ℃ for 3.5 hours. The solution was then evaporated under vacuum until only a solid slurry remained. The slurry was then dried in an oven at 150 ℃ for 2 hours. The dried catalyst was then washed with hot water to remove chloride ions until AgNO was used3The reagent detects the absence of chloride ions. The washed catalyst was dried again at 150 ℃ for 2 hours and then calcined at 550 ℃ for 8 hours. Calcination temperature the calcination temperature was reached at a heating rate of 10 deg.c/min.
XRF measurements of the resulting catalyst relative to Al2O3The content of the carrier is as follows: 0.4 wt% of Pt, 0.49 wt% of Sn, 0.4 wt% of Zn, 0.3 wt% of Mn and 1 wt% of Mg.
Example 2
Preparation of Pt-Sn-Zn-Mn-Sr/delta-theta-Al2O3Catalyst (catalyst B)
Preparation of Pt-Sn-Zn-one-powder in a similar manner to example 1Mn-Sr/δ-θ-Al2O3Catalyst except that 3.2 grams of SrCl was added2·6H2O was dissolved in 100ml of deionized water.
The catalyst obtained was measured to have various substances relative to Al2O3The content of the carrier is as follows: 0.4 wt% of Pt, 0.49 wt% of Sn, 0.4 wt% of Zn, 0.3 wt% of Mn, Sr: 1 wt%.
Example 3
Preparation of a comparative catalyst (Supported. delta. -theta. -Al)2O3)
A comparative catalyst was prepared in a similar manner to example 1:
Pt-Sn/δ-θ-Al2O3catalyst (comparative catalyst C); the difference lies in that: MgCl without addition of auxiliary agent2And an activity assisting agent ZnCl2/MnCl2(ii) a The catalyst obtained was measured to have various substances relative to Al2O3The content of the carrier is as follows: 0.4 wt% of Pt and 0.49 wt% of Sn.
Pt-Sn-Mg/δ-θ-Al2O3Catalyst (comparative catalyst D); the difference lies in that: ZnCl without addition of active assistant2/MnCl2(ii) a The catalyst obtained was measured to have various substances relative to Al2O3The content of the carrier is as follows: 0.4 wt% of Pt, 0.49 wt% of Sn and 1% of Mg.
Pt-Sn-Zn/Mn/δ-θ-Al2O3Catalyst (comparative catalyst E); the difference lies in that: MgCl without addition of active assistant2The catalyst obtained was measured to have various substances relative to Al2O3The content of the carrier is as follows: 0.4 wt% of Pt, 0.49 wt% of Sn, 0.4 wt% of Zn and 0.3 wt% of Mn.
Example 4
Preparation of Pt-Sn-K/Al2O3Catalyst (comparative catalyst F) (document EP0328507)
The preparation method is similar to the example of patent EP 0328507. The catalyst obtained was measured to have various substances relative to Al2O3The content of the carrier is as follows: pt0.4 wt%, Sn 0.49 wt%, K,1 wt%.
Example 5
Preparation of Pt—Sn/Al2O3Catalyst (comparative catalyst G)
The preparation method is similar to the example of patent EP 0328507. The catalyst obtained was measured to have various substances relative to Al2O3The content of the carrier is as follows: pt0.4 wt% and Sn 0.49 wt%.
Test example:
the performance test of the catalyst for propane dehydrogenation reaction is carried out in a fixed bed reactor, the reaction temperature is 550 ℃ (catalyst bed temperature), and the feed components: h2Propane: the nitrogen is 1:1:5, and the bed space velocity is 3800 hr-1. Before testing the reaction, the catalyst was reduced at a temperature of 550 ℃ for 2 hours.
The results of the experiment are shown in table 1:
TABLE 1
From the above table it can be seen that when the catalysts of the invention (catalysts a and B) are used, the catalysts show a high selectivity to propylene, the yield of propylene is increased by 15% (compared to the catalyst of patent EP0328507) and the yield of valuable ethylene product is also significantly increased. In addition, the invention is also provided. Moreover, the catalyst of the invention has the major advantage of forming a low amount of coke (58% lower than that of the catalyst of EP0328507), which in turn prolongs the catalyst life. This shows that the catalyst composition of the present invention is capable of catalyzing the conversion of propane to propylene in a non-oxidative dehydrogenation process with high yield and high selectivity.
Embodiments of the preparation and method of use of the dehydrogenation catalyst are set forth below.
Example 1: the catalyst composition comprises: (a) the metal M is selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh), rhenium (Re), ruthenium (Ru), and iridium (Ir); (b) tin (Sn); (c) zinc (Zn); manganese (Mn); (d) an alkaline earth metal; (e) a porous metal oxide catalyst support; wherein the amount of each of elements (a), (b) and (d) is in the range of 0.2 to 10 wt%, wherein the amount of element (c) is: the zinc (Zn) content is 0.3 to 2 weight percent; the content of manganese is 0.2 wt% -1 wt%.
Example 2: the catalyst composition of example 1, wherein the alkaline earth metal is selected from the group consisting of magnesium (Mg), calcium (Ca) and strontium (Sr), preferably magnesium (Mg).
Example 3: the catalyst composition is according to example 1 or example 2, wherein the metal M is platinum (Pt).
Example 4: the catalyst composition of any of embodiments 1-3, wherein the porous metal oxide catalyst support is selected from alumina (Al)2O3) Titanium dioxide (TiO)2) Cerium (CeO)2) Zirconium oxide (ZrO)2) And mixtures thereof, preferably delta-theta double crystal form Al2O3。
Example 5: the catalyst composition as described in any of examples 1-4, wherein the porous metal oxide catalyst support has a particle size of 100-300m2BET surface area in g. The catalyst carrier is prepared and calcined at 950-1200 deg.c for 1-5 hr. The crystal form is delta-theta
Example 6: the method for preparing the catalyst comprises the following steps: (a) embedding metals M, Sn, Zn and alkaline earth metal on a porous metal oxide catalyst carrier to obtain a catalyst substrate; (b) the catalyst substrate is subjected to calcination at a temperature of 400 to 650 ℃ for 1 to 6 hours in an atmosphere containing oxygen to obtain a shaped catalyst.
The details not described in the specification of the present application belong to the common general knowledge of those skilled in the art.
In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, and a person skilled in the art can solve the technical problem within a certain error range to substantially achieve the technical effect.
It is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a good or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such good or system. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a commodity or system that includes the element.
The foregoing description shows and describes several preferred embodiments of the present application, but as aforementioned, it is to be understood that the application is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as expressed herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the application, which is to be protected by the claims appended hereto.
Claims (10)
1. A double crystal type supported alkane non-oxidative dehydrogenation catalyst is characterized in that the active components of the catalyst consist of the following 4 kinds:
(a) an active catalytic metal selected from platinum, palladium, rhodium, rhenium, ruthenium or iridium;
(b) active catalytic helper metal: mixtures of tin, zinc and manganese;
(c) active catalyst promoter alkaline earth metal: selected from magnesium, calcium, strontium, potassium;
(d) a porous metal oxide catalyst support;
wherein the weight ratio of the element (a) to the element (d) is 0.4 to 10 wt%; the weight ratio of the element (c) to the element (d) is 0.5 to 5 wt%.
2. The alkane non-oxidative dehydrogenation catalyst of claim 1 wherein the element (a) is platinum and the weight ratio of element (d) is from 0.4 to 7.5 wt%.
3. The alkane non-oxidative dehydrogenation catalyst of claim 1 wherein the weight ratio of tin to element (d) in element (b) is from 0.4 wt% to 2 wt%; the weight ratio of zinc to the element (d) is 0.3 wt% -2 wt%; the weight ratio of manganese to element (d) is 0.2 wt% to 1 wt%.
4. The alkane non-oxidative dehydrogenation catalyst of claim 1 wherein the element (c) is selected from the group consisting of magnesium, calcium, and strontium; further preferably magnesium.
5. The alkane non-oxidative dehydrogenation catalyst of claim 1, wherein the element (d) is selected from Al2O3、TiO2、CeO2、ZrO2Or a mixture thereof.
6. The alkane non-oxidative dehydrogenation catalyst of claim 4 wherein the element (d) is Al of the delta-theta type2O3Said delta-theta type Al2O3Is of delta crystal form Al2O3And theta crystal form Al2O3A mixture of (a); and the delta crystal form Al2O3And theta crystal form Al2O3The weight ratio of (A) is 0.2-1.5; the BET surface area of the element (d) is 50 to 500m2/g。
7. An alkane non-oxidative dehydrogenation catalyst according to any of claims 1 to 6 wherein element (a) is selected from platinum and element (c) is selected from Mg; the content of each metal relative to the element (d) is: 0.4 wt% of Pt0, 0.49 wt% of Sn, 0.4 wt% of Zn, 0.3 wt% of Mn and 1 wt% of Mg.
8. A method of preparing the alkane non-oxidative dehydrogenation catalyst of claim 1, comprising the steps of:
(1) mixing an element (d) with a solution containing a salt of the elements (a), (b), (c), followed by evaporating the liquid in the solution to obtain a modified slurry, and washing the modified slurry with a solvent to obtain a catalyst substrate;
(2) calcining the catalyst substrate in an oxygen-containing environment to obtain the alkane non-oxidative dehydrogenation catalyst.
9. The method according to claim 8, wherein the calcination is carried out at a temperature of 400 to 650 ℃ for 2 to 6 hours; the pH value of the solvent is within the range of 5.5-7.5.
10. The method of claim 8, wherein the salt of element (a) is chloroplatinic acid; the salts of the elements (b) and (c) include stannic chloride, zinc chloride, manganese chloride and magnesium chloride.
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| CN103140459A (en) * | 2010-09-30 | 2013-06-05 | 陶氏环球技术有限责任公司 | Non-oxidative dehydrogenative process |
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| CN104507567A (en) * | 2012-07-26 | 2015-04-08 | 沙特基础工业公司 | Alkane dehydrogenation catalyst and process for its preparation |
| CN106660015A (en) * | 2014-07-28 | 2017-05-10 | 乐天化学株式会社 | Dehydrogenation catalyst, and preparation method therefor |
| CN110352093A (en) * | 2018-02-01 | 2019-10-18 | 晓星化学(株) | Dehydrogenation |
| KR20200091014A (en) * | 2019-01-18 | 2020-07-30 | 효성화학 주식회사 | Method of preparing catalyst support and dehydrogenation catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103140459A (en) * | 2010-09-30 | 2013-06-05 | 陶氏环球技术有限责任公司 | Non-oxidative dehydrogenative process |
| CN104487165A (en) * | 2012-07-26 | 2015-04-01 | 沙特基础工业公司 | Alkane dehydrogenation catalyst and process for its preparation |
| CN104507567A (en) * | 2012-07-26 | 2015-04-08 | 沙特基础工业公司 | Alkane dehydrogenation catalyst and process for its preparation |
| CN106660015A (en) * | 2014-07-28 | 2017-05-10 | 乐天化学株式会社 | Dehydrogenation catalyst, and preparation method therefor |
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| KR20200091014A (en) * | 2019-01-18 | 2020-07-30 | 효성화학 주식회사 | Method of preparing catalyst support and dehydrogenation catalysts |
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