CN101380587B - Propane dehydrogenation catalyst to produce propylene and preparation method thereof - Google Patents
Propane dehydrogenation catalyst to produce propylene and preparation method thereof Download PDFInfo
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- CN101380587B CN101380587B CN2008101559084A CN200810155908A CN101380587B CN 101380587 B CN101380587 B CN 101380587B CN 2008101559084 A CN2008101559084 A CN 2008101559084A CN 200810155908 A CN200810155908 A CN 200810155908A CN 101380587 B CN101380587 B CN 101380587B
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 239000001294 propane Substances 0.000 title claims abstract description 34
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 238000006356 dehydrogenation reaction Methods 0.000 title abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 60
- 239000002184 metal Substances 0.000 claims abstract description 60
- 239000002808 molecular sieve Substances 0.000 claims abstract description 27
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 19
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 19
- 150000002739 metals Chemical class 0.000 claims abstract description 18
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 31
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 238000006555 catalytic reaction Methods 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- -1 platinum group metals Chemical class 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 239000004615 ingredient Substances 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a propylene catalyst prepared by propane dehydrogenation and a preparation method thereof, and the catalyst takes skeleton containing molecular sieve of rare earth metals as a carrier and is applied in gas-solid catalytic reaction. The catalyst takes the skeleton containing the molecular sieve of rare earth metals as the carrier, takes platinum group metals as a main catalyst, takes the IVA group metals, the IA group or IIA group metals as accessory ingredients, takes halogen elements as modifying agents and takes heat-resistance inorganic oxide as a caking agent to be formed. Propane transformation ratio is relatively high at the condition of high temperature and low pressure and the catalyst has the advantages of good propylene selectivity, reaction stability and anti-carbon performance.
Description
Technical field
The present invention relates to a kind of molecular sieve that contains rare earth elemental metals with skeleton is the Catalysts and its preparation method of the preparing propylene by dehydrogenating propane of carrier, is applicable to gas solid catalytic reaction, belongs to the catalyst preparation technology of Industrial Catalysis technical field.
Background technology
Propylene is a kind of important Organic Chemicals, is widely used in the preparation of macromolecular materials such as polypropylene, polyacrylonitrile.Current, China has surpassed ethene to propylene growth of requirement speed.And the propane flammable gas aboundresources of China simultaneously, major part is used as domestic fuel, and the big inexpensive propane of amount is made market high added value propylene in short supply by the catalysis dehydrogenation reaction, has important Research Significance.At present, have the technology of the industrialized propane of several covers catalytic dehydrogenation system propylene in the world, with Oleflex technology, the Air Product﹠amp of Uop Inc.; The Catofin. technology of Chemical company is representative.At present, the domestic industrial installation that does not still have preparing propylene by dehydrogenating propane.
The key that realizes the preparing propylene by dehydrogenating propane technology is to develop the propane dehydrogenation catalyst with high stability, high activity and high selectivity.The dehydrogenation of exploitation mainly is with γ-Al at present
2O
3Be carrier, by load platinum family element metal active constituent, and add that various metal promoters prepare, the CN96115049A patent disclosure has been reported with γ-Al
2O
3Be carrier,, be used for C by step impregnation method load regulation IVA family metal element, platinum family element metal, alkali metal successively
2～C
5The catalyst of paraffin dehydrogenation; The CN98114083A patent then discloses the Pt-Sn-K-Mg/Al that is used for dehydrogenation of saturated hydrocarbon
2O
3The Preparation of catalysts method.In recent years, molecular sieve with unique pore passage structure and higher shape selectivity energy is applied to the catalyst carrier that the manufacturing olefin by low-carbon alkane dehydrogenation catalytic reaction is used gradually, the USP5192728 of U.S. Mobile house journal is carrier loaded platinum group metal component, zinc component and magnesium component with ZSM or borosilicate, be used for the dehydrogenating low-carbon alkane reaction, the stability and the reactivity of its catalyst all are higher than with Al
2O
3Catalyst for carrier; It is the preparation method of the propane dehydrogenation catalyst of carrier that CN101066532A and CN101125298A then disclose the ZSM-5 molecular sieve and the alumina modified mesoporous molecular sieve that contain Sn with skeleton respectively.Although alkane conversion and the olefine selective of these catalyst under some reaction condition is higher, owing to the easy coking deactivation of catalyst under hot conditions, cause the poor stability of catalytic reaction, the service life of catalyst is shorter.
Summary of the invention
Technical problem: the object of the present invention is to provide a kind of molecular sieve that contains rare earth elemental metals with skeleton is the Catalysts and its preparation method of the preparing propylene by dehydrogenating propane of carrier, this catalyst has higher conversion of propane, propylene selectivity and reaction stability under the dehydrogenating propane reaction condition, have tangible economy and society benefit.
Technical scheme: the catalyst of preparing propylene by dehydrogenating propane of the present invention is a carrier with the molecular sieve that skeleton contains rare earth elemental metals, with the platinum family element metal is major catalyst, IVA family metal element, IA family or IIA family metal element are auxiliary agent, halogen is a modifier, is the binding agent moulding with resistant to elevated temperatures inorganic oxide.
As the molecular sieve of catalyst carrier is one or several compound of A type or X type or Y type or ZSM type series or MCM type series or SBA type series.
Contain rare earth elemental metals in the framework of molecular sieve as catalyst carrier, the weight percent content of the rare earth elemental metals that contains in the framework of molecular sieve is 0.01～10wt%, and rare earth elemental metals comprises the combination of one or more rare earth elemental metals.
The platinum family element metal is selected from one or several the combination in ruthenium, rhodium, palladium, osmium, iridium or the platinum.
IVA family metal element comprises one or several combination wherein, and IA family metal element comprises one or several combination wherein, and IIA family metal element comprises one or several combination wherein.
Described halogen comprises one or several combination wherein.
The load capacity of each component is calculated as based on the metal element weight in the total catalyst weight: the platinum family element content of metal is 0.01～10wt%, IVA family metal element load capacity is 0.01～10wt%, and IA family metal element load capacity is that 0.01～5wt%, IIA family metal element load capacity are 0.01～5wt%; Calculate based on halogen weight content in the total catalyst weight: halogen content is 0.01～10wt%; The content of inorganic oxide binder calculates with total catalyst weight: inorganic oxide binder content is 2～50wt%, and all the other are carrier.
The Preparation of catalysts method of preparing propylene by dehydrogenating propane is:
Step 1). utilize hydrothermal synthesis method, the preparation skeleton contains the molecular sieve carrier of rare earth elemental metals;
Step 2) under .60～100 ℃, with the alkalinous metal aqueous solution 2～5h of above-mentioned carrier impregnation IA family or IIA family, suction filtration, with the distilled water washing, 60 ℃～100 ℃ oven dry 2～5h, 400～600 ℃ of roasting 3～5h; Then, the carrier of alkalinous metal modification and the aqueous solution that contains platinum family element metal, IVA family metal element are soaked 2～5h altogether under 60～100 ℃, suction filtration is with the distilled water washing, at 60 ℃～100 ℃ oven dry 2～5h;
Step 3). in the above-mentioned catalyst fines for preparing, add inorganic oxide binder and extrusion aid, evenly mix; Simultaneously, drip the Aci-Jel solvent, extruded moulding;
Step 4). the catalyst after the moulding at 60 ℃～180 ℃ oven dry 2～10h, is activated 3～10h then in 400～600 ℃ air;
Step 5). with the catalyst reductase 12～10h in 400～600 ℃ hydrogen stream that obtains; Catalyst after the reduction promptly can be used for the preparing propylene by dehydrogenating propane catalytic reaction.
The extrusion aid that adds in the shaping of catalyst process is sesbania powder, polybasic carboxylic acid or the two compound, and wherein polybasic carboxylic acid can be one or more the sour mixtures in citric acid, oxalic acid and the tartaric acid; The Aci-Jel solvent is one or more the sour mixtures in dilute sulfuric acid, hydrochloric acid, the nitric acid.
The content of extrusion aid and Aci-Jel solvent calculates with total catalyst weight, and the content of extrusion aid is 1～15wt%, and the content of Aci-Jel solvent is 1～10wt%.
Beneficial effect: the invention provides a kind of molecular sieve that contains rare earth elemental metals with skeleton is the catalyst and the preparation side thereof of the preparing propylene by dehydrogenating propane of carrier, this catalyst has higher conversion of propane, propylene selectivity and reaction stability under the condition of high temperature, low pressure, anti-carbon deposit excellent performance.
Characteristics of the present invention are:
(1) molecular sieve that contains rare earth elemental metals with skeleton is a carrier, load platinum family element metal, IVA family metal element, the alkalinous metal of IA family or IIA family makes the catalyst of preparing propylene by dehydrogenating propane, rare earth elemental metals auxiliary agent in the skeleton and strong interaction between the molecular sieve have been made full use of, stablized framework aluminum, the pore structure parameter of modulation carrier, rare earth elemental metals on the skeleton can also effectively be regulated the surface acid performance of catalyst, suppress propane cracking in the dehydrogenating propane course of reaction, the generation of side reactions such as hydrogenolysis, strengthen the heat endurance and the anti-carbon deposit performance of catalyst greatly, improved the selectivity of product propylene and the stability of catalytic reaction.
(2) Preparation of catalysts adopts step impregnation method, flood the alkalinous metal auxiliary agent earlier, after soak platinum family element metal, IVA family metal element altogether, this preparation method helps improving decentralization and the valence stability of platinum group metal active component at carrier surface, strengthens the interaction between metal-auxiliary agent-carrier.
(3) preparing propylene by dehydrogenating propane catalytic reaction of the present invention adopts fluid bed or fixed bed reactors, preferred fixed bed reactors, and its reaction unit is made up of 1 pre-hydrogenator and 1 dehydrogenation reactor of series connection.Wherein, load palladium catalyst in the pre-hydrogenator, reaction temperature is 120～200 ℃, and preferred 140～160 ℃, main effect is that the small amounts of olefins that contains in the unstripped gas propane is carried out preliminary treatment, makes it change alkane fully into; What load in the dehydrogenation reactor is propane dehydrogenation catalyst, and reaction temperature is 450～750 ℃, preferred 550～650 ℃.Pressure is 0.05～0.4MPa, and preferred 0.1～0.2MPa, the mass space velocity of propane are 1.0～5.0h
-1, be preferably 2.0～3.0h
-1Hydrogen hydrocarbon mol ratio in the course of reaction is 0.01～2, preferred 0.2～0.6.
The specific embodiment
Embodiment 1:
By hydrothermal synthesis method, the preparation skeleton contains the MCM-41 mesoporous molecular sieve (Ce content is 1.0%) of Ce, and Ce is present in the skeleton of molecular sieve.Under 80 ℃, the molecular sieve dipping NaCl aqueous solution 3h that makes above-mentioned behind suction filtration, distilled water washing, the 80 ℃ of dry 3h, under 80 ℃, soaks H altogether
2PtCl
6And SnCl
4Aqueous solution 3h behind the washing of suction filtration, distilled water, 80 ℃ of dry 3h, adds the Al of 5wt%
2O
3The sesbania powder of binding agent and 2wt% drips rare HNO of 2wt% simultaneously
3The aqueous solution, extruded moulding.Descend dry 3h at 80 ℃ then, roasting 4h in 500 ℃ the air, reduction 8h obtains catalyst in 500 ℃ the hydrogen.The load capacity of each component is in the catalyst: Pt:0.5wt%, Sn:1wt%, Na:1.5wt%.
Appreciation condition: catalyst quality 2.0g, propane mass space velocity: 3.0h
-1, reaction pressure: 0.1Mpa.Initial reaction temperature is 580 ℃, adjusts response parameter according to the response situation of reality, and latter stage, reaction temperature was 610 ℃.
The result shows: the carrier framework of the present invention's preparation contains the PtSnNa/Ce-MCM-41 catalyst of Ce after estimating 200h continuously, and conversion of propane is 31.2%, and the propylene selectivity is 94.7%.
Embodiment 2:
By hydrothermal synthesis method, the preparation skeleton contains the SBA-15 mesoporous molecular sieve (La content is 1.5%) of La, and La is present in the skeleton of molecular sieve.This molecular sieve is flooded Ca (NO down at 80 ℃
3)
2Aqueous solution 3h behind the washing of suction filtration, distilled water, the 80 ℃ of dry 3h, under 80 ℃, soaks H altogether
2PtCl
6And SnCl
4Aqueous solution 3h behind the washing of suction filtration, distilled water, 80 ℃ of dry 3h, adds the Al of 5wt%
2O
3The sesbania powder of binding agent and 2wt% drips rare HNO of 2wt% simultaneously
3The aqueous solution, extruded moulding.Descend dry 3h at 80 ℃ then, roasting 4h in 500 ℃ the air, reduction 8h obtains catalyst in 500 ℃ the hydrogen.The load capacity of each component is in the catalyst: Pt:0.5wt%, Sn:1.2wt%, Ca:1.5wt%.
Appreciation condition is with embodiment 1.The result shows: the carrier framework that utilizes the present invention to make contains this catalyst of PtSnCa/La-SBA-15 of La after estimating about 300h continuously, and conversion of propane is 30.1%, and the propylene selectivity is 96.4%.
Embodiment 3:
By hydrothermal synthesis method, the preparation skeleton contains the ZSM-5 molecular sieve (La content is 2.0%) of La, and La is present in the skeleton of molecular sieve.Under 80 ℃, earlier with this molecular sieve dipping NaCl aqueous solution 3h, behind suction filtration, distilled water washing, the 80 ℃ of dry 3h, again under 80 ℃, dipping MgCl
2Aqueous solution 3h, suction filtration, distilled water washing, dry (80 ℃) 3h.Then, under 80 ℃, soak H altogether
2PtCl
6And SnCl
4Aqueous solution 3h behind the washing of suction filtration, distilled water, 80 ℃ of dry 3h, adds the Al of 5wt%
2O
3The sesbania powder of binding agent and 2wt% drips rare HNO of 2wt% simultaneously
3The aqueous solution, extruded moulding.Descend dry 3h at 80 ℃ then, roasting 4h in 500 ℃ the air, reduction 8h obtains catalyst in 500 ℃ the hydrogen.The load capacity of each component is in the catalyst: Pt:0.5wt%, Sn:2.0wt%, Na:1.2wt%, Mg:1.0wt%.
Appreciation condition is with embodiment 1 and embodiment 2.The result shows: the carrier framework that the present invention makes contains this catalyst of PtSnNaMg/La-ZSM-5 of La after estimating about 500h continuously, and conversion of propane is 30.5%, and the propylene selectivity is 97.7%.
Claims (3)
1. the catalyst of a preparing propylene by dehydrogenating propane, it is characterized in that this catalyst is a carrier with one or several the compound that skeleton contains the A type, X type, Y type, ZSM type series, MCM type series of rare earth elemental metals or SBA type series molecular sieve, with the platinum family element metal is major catalyst, IVA family metal element, IA family or IIA family metal element are auxiliary agent, halogen is a modifier, is the binding agent moulding with resistant to elevated temperatures inorganic oxide;
Contain rare earth elemental metals in the framework of molecular sieve as catalyst carrier, the weight percent content of the rare earth elemental metals that contains in the framework of molecular sieve is 0.01～10wt%, and rare earth elemental metals comprises the combination of one or more rare earth elemental metals;
The load capacity of each component is calculated as based on the metal element weight in the total catalyst weight: the platinum family element content of metal is 0.01～10wt%, IVA family metal element load capacity is 0.01～10wt%, and IA family metal element load capacity is that 0.01～5wt%, IIA family metal element load capacity are 0.01～5wt%; Calculate based on halogen weight content in the total catalyst weight: halogen content is 0.01～10wt%; The content of inorganic oxide binder calculates with total catalyst weight: inorganic oxide binder content is 2～50wt%, and all the other are carrier.
2. the catalyst of preparing propylene by dehydrogenating propane according to claim 1 is characterized in that the platinum family element metal is selected from one or several the combination in ruthenium, rhodium, palladium, osmium, iridium or the platinum.
3. the catalyst of preparing propylene by dehydrogenating propane according to claim 1, it is characterized in that IVA family metal element comprises one or several combination wherein, IA family metal element comprises one or several combination wherein, and IIA family metal element comprises one or several combination wherein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101559084A CN101380587B (en) | 2008-10-10 | 2008-10-10 | Propane dehydrogenation catalyst to produce propylene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101559084A CN101380587B (en) | 2008-10-10 | 2008-10-10 | Propane dehydrogenation catalyst to produce propylene and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101380587A CN101380587A (en) | 2009-03-11 |
| CN101380587B true CN101380587B (en) | 2010-12-08 |
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|---|---|---|---|
| CN2008101559084A Expired - Fee Related CN101380587B (en) | 2008-10-10 | 2008-10-10 | Propane dehydrogenation catalyst to produce propylene and preparation method thereof |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101513613B (en) * | 2009-04-03 | 2011-12-21 | 南京金炼科技有限公司 | Propane dehydrogenation catalyst with hetero atom molecule sieve as carrier and preparation method thereof |
| CN102049267B (en) * | 2009-10-29 | 2013-01-30 | 中国石油化工股份有限公司 | Catalyst for preparing propylene by dehydrogenating propane as well as preparation method and applications thereof |
| US8609568B2 (en) | 2010-10-04 | 2013-12-17 | King Fahd University Of Petroleum And Minerals | Catalyst for oxidative dehydrogenation of propane to propylene |
| CN101972664B (en) * | 2010-10-13 | 2013-02-27 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of propane for preparing propylene and preparation method thereof |
| EP2689843A1 (en) | 2012-07-26 | 2014-01-29 | Saudi Basic Industries Corporation | Alkane dehydrogenation catalyst and process for its preparation |
| CN104307555A (en) * | 2014-09-22 | 2015-01-28 | 西南化工研究设计院有限公司 | MFI-type zeolite catalyst for propane dehydrogenation conversion to produce propylene and preparation method thereof |
| CN104368364A (en) * | 2014-11-10 | 2015-02-25 | 华玉叶 | Preparation method of catalyst for preparing propylene by virtue of propane dehydrogenation |
| CN105056990B (en) * | 2015-09-11 | 2017-09-08 | 宁波海越新材料有限公司 | Catalyst for preparing propylene with propane dehydrogenation and preparation method thereof |
| CN106944081B (en) * | 2016-01-07 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of preparation method for catalyst for preparing propene by oxidative dehydrogenation of propane |
| CN106622226B (en) * | 2016-12-02 | 2019-03-05 | 东南大学 | A kind of support type platinum based catalyst and preparation method thereof |
| CN107715862B (en) * | 2017-09-30 | 2020-09-25 | 大连理工大学 | Anti-carbon deposition chromium-based catalyst for preparing propylene by propane dehydrogenation, preparation method and application |
| CN111617785B (en) * | 2020-07-09 | 2021-10-15 | 北京化工大学 | Supported ruthenium-based phosphide catalyst and preparation method thereof |
| CN114588899A (en) * | 2020-12-04 | 2022-06-07 | 中国科学院大连化学物理研究所 | Catalyst and preparation and application thereof |
-
2008
- 2008-10-10 CN CN2008101559084A patent/CN101380587B/en not_active Expired - Fee Related
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