CN115501905A - Catalyst with dehydrogenation function, preparation method and application thereof, and method for preparing small-molecule olefin - Google Patents
Catalyst with dehydrogenation function, preparation method and application thereof, and method for preparing small-molecule olefin Download PDFInfo
- Publication number
- CN115501905A CN115501905A CN202110700081.6A CN202110700081A CN115501905A CN 115501905 A CN115501905 A CN 115501905A CN 202110700081 A CN202110700081 A CN 202110700081A CN 115501905 A CN115501905 A CN 115501905A
- Authority
- CN
- China
- Prior art keywords
- precursor
- weight
- parts
- catalyst
- group
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title claims abstract description 60
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 9
- -1 small-molecule olefin Chemical class 0.000 title claims description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims description 90
- 229910052751 metal Inorganic materials 0.000 claims description 60
- 239000002184 metal Substances 0.000 claims description 57
- 239000002808 molecular sieve Substances 0.000 claims description 38
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 38
- 238000011068 loading method Methods 0.000 claims description 28
- 239000012752 auxiliary agent Substances 0.000 claims description 25
- 230000008569 process Effects 0.000 claims 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 description 18
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 18
- 150000002910 rare earth metals Chemical class 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 238000005470 impregnation Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 4
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 238000013341 scale-up Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 36
- 239000001294 propane Substances 0.000 description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 11
- 230000009467 reduction Effects 0.000 description 11
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 10
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000002149 hierarchical pore Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/647—
-
- 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
-
- 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
Abstract
The invention relates to the field of catalysts, and discloses a catalyst with a dehydrogenation function, a preparation method and application thereof, and a method for preparing micromolecular olefin. The catalyst provided by the invention adopts a carrier which is easy to be produced in an industrial scale-up manner, and the preparation method is simple, the materials are easy to obtain, the cost is low, and the catalyst is convenient for industrial large-scale production and application. Moreover, the catalyst provided by the invention has the advantages of high conversion rate, high selectivity, high stability, excellent catalytic performance, long stable catalysis time and capability of greatly improving the production efficiency.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a catalyst with a dehydrogenation function, a preparation method and application thereof, and a method for preparing micromolecular olefin.
Background
Propane dehydrogenation technology has been the third source of propylene since the 90's of the last century. Currently, the industrial propane dehydrogenation processes mainly include an Oleflex process by UOP corporation, a Catofin process by LUMMUS corporation, a Star process by UHDE corporation, and the like. The most widely used process is the Oleflex process, which mainly adopts a platinum catalyst taking alumina as a carrier to catalyze the dehydrogenation reaction of propane. However, the alumina carrier is highly acidic, and the catalyst is easily coked, so that the catalyst needs to be frequently regenerated in production, and the propylene selectivity of the catalyst needs to be improved.
In recent years, many researches use molecular sieve materials with special pore structure and shape-selective performance as carriers of low-carbon alkane dehydrogenation catalysts to obtain catalysts with better activity, higher selectivity and better stability. For example, CN101066532A discloses a catalyst for preparing propylene by propane dehydrogenation using a ZSM-5 molecular sieve containing Sn in the framework as a carrier, wherein at least one of platinum, palladium, iridium, rhodium, osmium or rhenium is used as an active component, and a group IA and/or group IIA metal is used as an auxiliary agent, so that the catalyst has high activity and strong anti-carbon deposition capability. For another example, CN107303497A uses a hierarchical pore ZSM-5 molecular sieve and alumina as carriers, supported Pt as an active component, and Sn and Na as auxiliaries, to obtain a catalyst with good dehydrogenation activity and selectivity. For another example, CN109746026A discloses a dehydrogenation catalyst, which uses a nano hierarchical pore all-silicon molecular sieve with MFI structure as a carrier to obtain higher propane conversion rate, propylene selectivity and catalytic stability.
However, many of the existing dehydrogenation catalysts including the above-mentioned catalyst only pay attention to the improvement of the catalytic effect and stability of the catalyst during the research process, and neglecting the problem that the adopted carrier is not favorable for industrial production application. For example, carriers such as heteroatom molecular sieves, hierarchical pore molecular sieves and the like have high difficulty in scale-up production due to problems such as production cost or complex preparation process, all-silicon molecular sieves have high requirements for synthesis raw materials, mesoporous molecular sieves have poor high-temperature hydrothermal stability, and the like. Therefore, it is necessary to develop a dehydrogenation catalyst which has an excellent catalytic effect and is suitable for industrial mass production.
Disclosure of Invention
The invention aims to solve the problem that the dehydrogenation catalyst in the prior art cannot simultaneously take catalytic performance and industrial production application convenience into consideration, and provides a catalyst with a dehydrogenation function, a preparation method and application thereof, and a method for preparing micromolecular olefin. The catalyst adopts an industrially easily-amplified (high silica-alumina ratio) ZSM-5 molecular sieve as a carrier, adopts the existing methods in the field such as an impregnation method and the like to load an active component and an auxiliary agent, has simple preparation method, easily-obtained materials and low cost, and simultaneously realizes excellent catalytic performance of high conversion rate, high selectivity and high stability.
In order to achieve the above object, an aspect of the present invention provides a catalyst having a dehydrogenation function, the catalyst comprising a support and an active component and optionally an auxiliary supported on the support;
wherein, the carrier is a ZSM-5 molecular sieve with the silica-alumina ratio of 500-3000;
the active component is at least one of VIII group metals;
the auxiliary agent is at least one of IIA group metal, IVA group metal, IIB group metal and rare earth metal.
The second aspect of the present invention provides a method for preparing a catalyst having a dehydrogenation function, which comprises loading an active component precursor and an optional auxiliary precursor on a carrier, and then sequentially drying and calcining;
wherein, the carrier is a ZSM-5 molecular sieve with the silica-alumina ratio of 500-3000;
the active component precursor comprises at least one of precursors of group VIII metals;
the auxiliary agent precursor comprises at least one of a precursor of IIA group metal, a precursor of IVA group metal, a precursor of IIB group metal and a precursor of rare earth metal.
A third aspect of the invention provides a catalyst obtained by the preparation according to the above process.
A fourth aspect of the invention provides the use of a catalyst as hereinbefore described in a catalytic dehydrogenation reaction.
In a fifth aspect, the invention provides a process for the preparation of a small molecule alkene, the process comprising contacting a small molecule alkane with a catalyst as hereinbefore described and carrying out a dehydrogenation reaction under alkane dehydrogenation conditions.
Through the technical scheme, the invention has the following beneficial effects:
(1) The catalyst provided by the invention adopts the ZSM-5 molecular sieve with high silica-alumina ratio as the carrier, and the carrier is easy to enlarge production, low in cost, simple in preparation method, easy to obtain raw materials and easier to realize industrial production application and popularization;
(2) The catalyst provided by the invention has excellent catalytic performance, has the characteristics of high conversion rate, high selectivity and high stability when being used for preparing propylene by propane dehydrogenation, and can be used for more than 200 hours when being stably catalyzed, so that the production efficiency of preparing propylene by propane dehydrogenation is greatly improved.
Drawings
FIG. 1 is a graph showing the N content of the ZSM-5-1 molecular sieve of example 1 of the present invention 2 Isothermal adsorption and desorption curves.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, unless otherwise specified, the "silica-alumina ratio" of the ZSM-5 molecular sieve means the SiO content of the molecular sieve 2 And Al 2 O 3 Molar ratio (ratio).
In the present invention, the "ZSM-5 molecular sieve" refers to a conventional ZSM-5 molecular sieve, i.e., a ZSM-5 molecular sieve which is not subjected to special modification such as heteroatom doping and hierarchical pore adjustment, unless otherwise specified.
The inventor of the present invention has skillfully discovered in the process of research that when the ZSM-5 molecular sieve with high silica-alumina ratio (for example, the silica-alumina ratio is more than 500) is used as a carrier of a dehydrogenation catalyst, especially a dehydrogenation catalyst of small molecular alkane (for example, propane, etc.), a catalyst with excellent performance can be obtained by combining a specific active component and an auxiliary agent. The ZSM-5 molecular sieve has the characteristics of simple preparation method, low requirement on raw materials, easy amplification production, low cost and the like, so that the small-molecular alkane dehydrogenation catalyst using the ZSM-5 molecular sieve as the carrier has great industrial application and popularization potential.
The invention provides a catalyst with dehydrogenation function, which comprises a carrier and an active component and an optional auxiliary agent which are loaded on the carrier;
wherein the carrier is a ZSM-5 molecular sieve with the silica-alumina ratio of 500-3000;
the active component is at least one of VIII group metals;
the auxiliary agent is at least one of IIA group metal, IVA group metal, IIB group metal and rare earth metal.
According to a preferred embodiment of the present invention, wherein the particle size of the catalyst is 50 to 600nm, preferably 100 to 500nm. It should be understood that the particle size of the catalyst as defined herein is the microscopic particle size (crystallite size) of the (powdered) catalyst. For convenience of use, the reactor is protected, and the catalyst can be subjected to tabletting, crushing, sieving and the like before use to obtain a granular catalyst with a proper particle size (for example, the granular catalyst with the particle size of 0.3-1 mm) for use. The above treatment may be carried out in any manner known in the art.
According to a preferred embodiment of the present invention, wherein the specific surface area of the catalyst is 200 to 600m 2 (ii) in terms of/g. Preferably 350-500m 2 (ii) in terms of/g. For example, it may be 350m 2 /g、360m 2 /g、370m 2 /g、380m 2 /g、390m 2 /g、400m 2 /g、410m 2 /g、420m 2 /g、430m 2 /g、440m 2 /g、450m 2 /g、460m 2 /g、470m 2 /g、480m 2 /g、490m 2 /g、500m 2 G, or an intermediate value between any two of the foregoing values.
According to a preferred embodiment of the present invention, wherein the pore volume of the catalyst is 0.2-0.8cm 3 (ii) in terms of/g. Preferably 0.3-0.5cm 3 (ii) in terms of/g. For example, it may be 0.3cm 3 /g、0.31cm 3 /g、0.32cm 3 /g、0.33cm 3 /g、0.35cm 3 /g、0.36cm 3 /g、0.38cm 3 /g、0.4cm 3 /g、0.41cm 3 /g、0.42cm 3 /g、0.43cm 3 /g、0.44cm 3 /g、0.45cm 3 /g、0.46cm 3 /g、0.48cm 3 /g、0.5cm 3 G, or an intermediate value between any two of the foregoing values.
According to a preferred embodiment of the present invention, wherein the average pore diameter of the catalyst is 2 to 6nm. Preferably 3-5nm. For example, 3nm, 3.2nm, 3.4nm, 3.6nm, 3.8nm, 3.9nm, 4nm, 4.1nm, 4.3nm, 4.5nm, 4.8nm, 5nm, or intermediate values between any two of the foregoing.
In the process of research, the inventor of the invention finds that when the loading amounts of the active component and the auxiliary agent meet a certain proportional relationship, a dehydrogenation catalyst with better catalytic activity/catalytic stability can be obtained.
According to a preferred embodiment of the present invention, in the catalyst, the weight ratio of the active component to the auxiliary is 1:1-10. The ratio is the weight ratio between the active ingredient loading and the total loading of adjuvant.
In the catalyst provided by the invention, the adopted carrier is the ZSM-5 molecular sieve with the silica-alumina ratio within the range of the above conditions. In order to further improve the catalytic performance (e.g. conversion, selectivity, etc.) of the catalyst, according to a preferred embodiment of the present invention, wherein the support is a ZSM-5 molecular sieve having a silica to alumina ratio of 500-2000, preferably 600-2000.
According to a preferred embodiment of the invention, wherein the particle size of the support is between 50 and 600nm, preferably between 100 and 500nm. It should be understood that the particle size of the support as defined herein is the microscopic particle size (crystallite size) of the support (ZSM-5 molecular sieve).
According to a preferred embodiment of the present invention, wherein the specific surface area of the carrier is 300m 2 More than g, preferably 300 to 600m 2 (iv) g. More preferably 350-500m 2 (ii) in terms of/g. For example, it may be 350m 2 /g、360m 2 /g、380m 2 /g、400m 2 /g、420m 2 /g、450m 2 /g、460m 2 /g、480m 2 /g、500m 2 G, or an intermediate value between any two of the foregoing values.
According to a preferred embodiment of the present invention, wherein the pore volume of the support is 0.2 to 0.8cm 3 (ii) in terms of/g. Preferably 0.3-0.5cm 3 (iv) g. For example, it may be 0.3cm 3 /g、0.32cm 3 /g、0.33cm 3 /g、0.35cm 3 /g、0.36cm 3 /g、0.38cm 3 /g、0.39cm 3 /g、0.4cm 3 /g、0.42cm 3 /g、0.43cm 3 /g、0.45cm 3 /g、0.48cm 3 /g、0.5cm 3 G, or an intermediate value between any two of the foregoing values.
According to a preferred embodiment of the present invention, wherein the average pore size of the support is 2 to 6nm. Preferably 3-5nm. For example, 3nm, 3.1nm, 3.2nm, 3.3nm, 3.4nm, 3.5nm, 3.6nm, 3.8nm, 4nm, 4.3nm, 4.5nm, 4.8nm, 5nm, or intermediate values between any two of the foregoing.
In the catalyst provided by the invention, the ZSM-5 molecular sieve used as the carrier can be any ZSM-5 molecular sieve which is in the prior art and has the characteristics, and the ZSM-5 molecular sieve can be a related product obtained by commercial purchase or a related product prepared by self according to the prior art.
In the catalyst provided by the invention, any VIII group metal can be used as an active component. In order to further improve the catalytic performance of the catalyst, according to a preferred embodiment of the present invention, wherein the active component is at least one of group VIII noble metals, preferably Pt.
In the catalyst provided by the invention, the loading amount of the active component is not particularly limited and can be adjusted according to actual conditions. Preferably, in the catalyst, the supported amount (in terms of metal element) of the active component is 0.01 to 5 parts by weight relative to 100 parts by weight of the carrier.
More preferably, the loading amount of the active component is 0.1 to 1 part by weight.
Further preferably, the loading amount of the active component is 0.2 to 0.8 part by weight.
In the catalyst provided by the invention, the content of the auxiliary agent is not particularly limited, and can be adjusted according to actual conditions. According to a preferred embodiment of the present invention, wherein, in the catalyst, the total loading amount (in terms of metal elements) of the promoter is 0.5 to 10 parts by weight relative to 100 parts by weight of the carrier. The total loading of the promoter refers to the sum of the loading of all the promoters contained in the catalyst, when only one promoter is present, the loading of the promoter is referred to, and when a plurality of promoters are present, the loading of all the promoters is referred to.
In order to obtain better catalyst performance/catalytic stability, in the catalyst provided by the invention, when different promoters are selected, the loading amounts of the promoters are different, and the "loading amount of the promoter" refers to the loading amount of one promoter calculated by metal elements.
According to a preferred embodiment of the present invention, wherein the supported amount of the group IIA metal is 0 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, relative to 100 parts by weight of the carrier.
According to a preferred embodiment of the present invention, wherein the supported amount of the group IVA metal is 0 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, relative to 100 parts by weight of the carrier.
According to a preferred embodiment of the present invention, wherein the supported amount of the group IIB metal is 0 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, relative to 100 parts by weight of the carrier.
According to a preferred embodiment of the present invention, wherein the rare earth metal is supported in an amount of 0 to 10 parts by weight, preferably 0.5 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, relative to 100 parts by weight of the support.
The inventor of the present invention also finds in the course of research that the combination of certain auxiliary agents enables the catalytic performance/catalytic stability of the catalyst provided by the present invention to be further improved.
According to a preferred embodiment of the present invention, wherein the auxiliary agent is selected from the group consisting of at least one of group IIA metals and rare earth metals in combination with at least one of group IIB metals.
Preferably, the auxiliary agent is a combination of Zn and at least one of Mg, ca, sm and La.
According to another preferred embodiment of the invention, wherein the promoter is selected from the group consisting of at least one of a group IIA metal and a rare earth metal in combination with at least one of a group IVA metal.
Preferably, the auxiliary agent is a combination of at least one of Mg, ca, la and Sm and Sn.
In the catalyst provided by the invention, the active component exists in the catalyst in an oxidation state and plays a catalytic role in a reduction state.
Therefore, the catalyst provided by the invention should be subjected to reduction treatment before use. The reduction may be performed by any method known in the art for reducing the catalyst, and according to a preferred embodiment of the present invention, the reduction may include subjecting the catalyst to a reducing atmosphere and performing the reduction under the catalyst reducing conditions.
Preferably, the reducing atmosphere is formed by a reducing gas (e.g., H) 2 Etc.) are provided.
Preferably, the catalyst reduction conditions include: the temperature is 300-550 ℃, the time is 2-8h, and the volume space velocity of the reducing gas is 600-2000h -1 。
The second aspect of the present invention provides a method for preparing a catalyst having a dehydrogenation function, which comprises loading an active component precursor and an optional auxiliary precursor on a carrier, and then sequentially drying and calcining;
wherein, the carrier is a ZSM-5 molecular sieve with the silica-alumina ratio of 500-3000;
the active component precursor comprises at least one of precursors of group VIII metals;
the assistant precursor includes at least one of a precursor of a group IIA metal (e.g., nitrate, sulfate, chloride, and the like, hereinafter the same applies), a precursor of a group IVA metal, a precursor of a group IIB metal, and a precursor of a rare earth metal.
In the method provided by the invention, the adopted carrier is the ZSM-5 molecular sieve, and the characteristics of the molecular sieve are as described above and are not described again.
According to a preferred embodiment of the present invention, the active component precursor is at least one of water-soluble acid or salt of group VIII noble metal, preferably chloroplatinic acid.
In the method provided by the invention, the amount of the active component precursor is not particularly limited, and can be adjusted according to actual conditions. According to a preferred embodiment of the present invention, wherein the active component precursor is used in an amount such that the active component (in terms of metal element) is supported in the catalyst in an amount of 0.01 to 5 parts by weight relative to 100 parts by weight of the carrier.
Preferably, the active component precursor is used in an amount such that the active component is supported in the catalyst in an amount of 0.1 to 1 part by weight.
More preferably, the active component precursor is used in an amount such that the loading amount of the active component in the catalyst is 0.2 to 0.8 parts by weight.
According to a preferred embodiment of the present invention, wherein the total amount of the promoter precursor is used so that the total loading amount (in terms of metal element) of the promoter in the catalyst is 0.5 to 10 parts by weight with respect to 100 parts by weight of the carrier.
Preferably, the loading of the group IIA metal is from 0 to 10 parts by weight, preferably from 0.1 to 5 parts by weight, more preferably from 0.1 to 3 parts by weight.
Preferably, the amount of the group IVA metal supported is from 0 to 10 parts by weight, preferably from 0.1 to 5 parts by weight, more preferably from 0.1 to 3 parts by weight.
Preferably, the supported amount of the group IIB metal is 0 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight.
Preferably, the loading amount of the rare earth metal is 0 to 10 parts by weight, preferably 0.5 to 5 parts by weight, more preferably 0.5 to 3 parts by weight.
According to a preferred embodiment of the present invention, the auxiliary precursor is selected from a combination of at least one of a precursor of a group IIA metal and a precursor of a rare earth metal, and a precursor of a group IIB metal.
Preferably, the assistant precursor is a combination of at least one of Mg precursor, ca precursor, sm precursor and La precursor and Zn precursor.
According to another preferred embodiment of the present invention, wherein the promoter precursor is selected from the group consisting of a precursor of a group IIA metal and a precursor of a rare earth metal in combination with a precursor of a group IVA metal.
Preferably, the assistant precursor is a combination of at least one of a Mg precursor, a Ca precursor, a Sm precursor and a La precursor with a Sn precursor.
Any method known in the art that is capable of supporting the active ingredient precursor and the auxiliary precursor on a carrier can be used in the method provided by the present invention. According to a preferred embodiment of the present invention, the method for supporting the active component precursor and the auxiliary agent precursor on the carrier is selected from impregnation and/or spraying, preferably impregnation.
Preferably, the impregnation method is an equal volume impregnation method and/or an excess impregnation method, preferably an excess impregnation method.
In the method provided by the invention, the active component precursor and the auxiliary agent precursor can be simultaneously impregnated (loaded) on the carrier, and can also be impregnated on the carrier step by step. For the sake of simplification of the operation and the like, it is preferable to impregnate the active component precursor and the auxiliary precursor on the support at the same time.
Any drying means known in the art that can be used in the catalyst preparation process can be adapted to the process provided by the present invention. According to a preferred embodiment of the present invention, wherein the drying method is selected from drying and/or vacuum drying.
Preferably, the drying conditions include: the temperature is 100-150 ℃ and the time is 1-6h.
According to a preferred embodiment of the present invention, wherein the firing conditions include: heating to 500-700 deg.C at a rate of 0.5-5 deg.C/min in air atmosphere, and calcining at the temperature for 4-12h.
In the catalyst prepared by the method provided by the invention, the active component exists in an oxidation state in the catalyst and plays a catalytic role in a reduction state.
Therefore, the above method may further comprise a step of reducing the resulting catalyst before use. The reduction method may be any existing method for reducing a catalyst in the art, for example, the reduction method may be the aforementioned reduction method, and details are not repeated here.
A third aspect of the invention provides a catalyst prepared according to the method as described above. The characteristics of the catalyst are as described above and will not be described in detail here.
A fourth aspect of the invention provides the use of a catalyst as hereinbefore described in a catalytic dehydrogenation reaction.
In a fifth aspect, the invention provides a process for the preparation of a small molecule olefin, said process comprising contacting a small molecule alkane with a catalyst as hereinbefore described and carrying out a dehydrogenation reaction under alkane dehydrogenation conditions.
According to a preferred embodiment of the present invention, wherein the small molecule olefin is selected from one of ethylene, propylene, 1-butene and isobutylene.
According to a preferred embodiment of the invention, wherein the alkane dehydrogenation conditions comprise: the reaction temperature is 500-700 ℃, the pressure is 0.08-0.12MPa (namely normal pressure reaction), and the mass space velocity of the micromolecular alkane is 0.5-5h -1 。
Preferably, H is selected 2 As the diluent gas, H is preferred 2 The volume ratio of the small molecule alkane to the small molecule alkane is 1.5-5.
According to a preferred embodiment of the present invention, wherein the method further comprises the step of reducing the catalyst prior to carrying out the dehydrogenation reaction. The reduction can be performed in the manner as described above, and is not described herein again.
The present invention will be described in detail below by way of examples. It should be understood that the following examples are only for illustrative purposes to further explain and illustrate the contents of the present invention in detail, and are not intended to limit the present invention.
In the following examples, ZSM-5 molecular sieves of different Si/Al ratios were purchased from Ziboqi Innovative materials science, inc. and numbered according to the Si/Al ratio (see Table 1 for specific Si/Al ratios). Unless otherwise specified, all other chemicals used were purchased from the normal chemical suppliers and were of analytical purity.
In the following examples, the operation temperature was room temperature (25. + -. 3 ℃ C.) unless otherwise specified.
Example 1
0.1711g of stannous chloride dihydrate and 0.1228g of magnesium nitrate are dissolved in 50mL of deionized water and uniformly mixed with 6.6mL of chloroplatinic acid aqueous solution with the concentration of 1g/100mL to obtain impregnation liquid-1. 5g of ZSM-5-1 was immersed in the immersion liquid-1 at 25 ℃ for 8 hours. And then evaporating excessive moisture by using a rotary evaporator, putting the solid product into a drying box with the temperature of 120 ℃, drying for 3h, then putting the solid product into a muffle furnace, raising the temperature to 550 ℃ at the heating rate of 1 ℃/min in the air atmosphere, and roasting for 6h. Dehydrogenation catalyst A1 was obtained (as detected, catalyst A1 had a crystallite average particle size of about 300 nm).
Example 2
0.2730g of zinc nitrate hexahydrate and 0.0614g of magnesium nitrate are dissolved in 50mL of deionized water and are uniformly mixed with 5.3mL of chloroplatinic acid aqueous solution with the concentration of 1g/100mL to obtain impregnation liquid-2. 5g of ZSM-5-2 was immersed in the immersion liquid-2 at 25 ℃ for 8 hours. And then evaporating excessive moisture by using a rotary evaporator, putting the solid product into a drying box with the temperature of 120 ℃, drying for 3h, then putting the dried product into a muffle furnace, raising the temperature to 550 ℃ at the heating rate of 2 ℃/min in the air atmosphere, and roasting for 6h. Dehydrogenation catalyst A2 was obtained (catalyst A2 was found to have a crystallite average particle size of about 200 nm).
Example 3
0.1996g of stannous chloride dihydrate and 0.0895g of samarium nitrate are dissolved in 50mL of deionized water and are uniformly mixed with 7.9mL of chloroplatinic acid aqueous solution with the concentration of 1g/100mL to obtain impregnation liquid-3. 5g of ZSM-5-3 was immersed in the immersion liquid-3 at 25 ℃ for 8 hours. And then evaporating excessive moisture by using a rotary evaporator, putting the solid product into a drying box with the temperature of 120 ℃, drying for 3h, then putting the dried product into a muffle furnace, raising the temperature to 550 ℃ at the heating rate of 2 ℃/min in the air atmosphere, and roasting for 6h. Dehydrogenation catalyst A3 was obtained (catalyst A3 was found to have a crystallite average particle size of about 400 nm).
Example 4
The method of example 1 was used except that stannous chloride dihydrate was used in an amount of 0.171g, magnesium nitrate was used in an amount of 0.2135g, and chloroplatinic acid was used in an amount of 2.6ml. The remaining operations and conditions were the same as in example 1, to obtain a dehydrogenation catalyst A4.
Example 5
The method of example 1 was used except that the amounts of stannous chloride dihydrate and magnesium nitrate were adjusted to 0.0171g and 0.0123g, respectively. The remaining operations and conditions were the same as in example 1, to obtain a dehydrogenation catalyst A7.
Example 6
The method of example 1 was used except that the amounts of stannous chloride dihydrate and magnesium nitrate were adjusted to 0.8555g and 0.6141g, respectively. The remaining operations and conditions were the same as in example 1, to obtain a dehydrogenation catalyst A8.
Example 7
The method of example 1 was used except that 6.6mL of an aqueous solution of chloroplatinic acid having a concentration of 1g/100mL was uniformly mixed with 50mL of deionized water in place of the immersion liquid-1. The same operation and conditions as in example 1 were applied to obtain dehydrogenation catalyst A9.
Comparative example 1
The method of example 1 was used except that ZSM-5-1 was replaced with an equal amount of ZSM-5-4. The same operation and conditions were the same as in example 1, to obtain a dehydrogenation catalyst D1.
Test example 1
The supports and catalysts in the above examples and comparative examples were tested as follows: n is carried out by adopting a full-automatic adsorption instrument with the model of autosorb iQ of Kangta company of America 2 Testing of isothermal adsorption and desorption curves (FIG. 1 schematically shows the N of the ZSM-5-1 molecular sieve employed in example 1 2 Isothermal adsorption and desorption curves); calculating the specific surface areas of the used ZSM-5 molecular sieve and the catalyst by adopting a BET method; calculating the pore volume by using the accumulated adsorption amount of the highest pressure point; the average pore diameter was calculated using the following formula: average pore diameter =4 × total pore volume/specific surface area.
And calculating the active component and the auxiliary agent content (in terms of metal elements) in the catalyst according to the input amount of the active component precursor and the auxiliary agent precursor.
The results are detailed in tables 1 and 2.
TABLE 1
TABLE 2
Test example 2
0.5g of each of the dehydrogenation catalysts obtained in the above examples and comparative examples (for the convenience of detection, the reactor was protected, the catalyst was subjected to tabletting and crushing, and particles having a particle size of 0.7. + -. 0.1mm were sieved and detected) was charged into a fixed bed quartz reactor, and the mixture was subjected to hydrogenation in the presence of hydrogen 2 Reducing for 2H (H) at 450 ℃ under the atmosphere 2 Volume space velocity of 1200h -1 ) Then, the reaction temperature was controlled at 600 ℃ and the reaction pressure was controlled at 0.1MPa, and a reaction gas (H) was introduced 2 And propane in a volume ratio of 1 to 4), wherein the mass space velocity of the propane is 3h -1 . The reaction product distribution was analyzed by gas chromatography. The propane conversion and propylene selectivity were calculated according to the following formulas. The results are detailed in Table 3.
Propane conversion = moles propane converted/moles propane fed
Propylene selectivity = moles propane converted to propylene/moles propane converted
TABLE 3
| Catalyst numbering | Propane conversion (%) | Propylene selectivity (%) | Reaction time (h) |
| A1 | 40.6 | 90.6 | 220** |
| A2 | 40.8 | 91.2 | 288** |
| A3 | 41.3 | 90.9 | 200** |
| A4 | 33.2 | 86.3 | 48*** |
| A5 | 30.5 | 78.6 | 48*** |
| A6 | 32.4 | 80.5 | 48*** |
| A7 | 18.6 | 83.3 | 8**** |
| D1 | 35.4 | 84.2 | 48*** |
* Propane conversion and propylene selectivity are averages over the reaction time.
* Reaction time is determined by the change in the level of conversion and selectivity as the reaction progresses, and the reaction is stopped when the conversion and/or selectivity begins to decline continuously (by an amount up to or exceeding 5%). Therefore, the length of the reaction time is correlated with the stability of the catalyst.
* Fixed reaction time, used to calculate average conversion and selectivity to reflect catalyst performance.
* Poor catalyst performance, low conversion and selectivity, and short reaction times followed by reaction shutdowns.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A catalyst with dehydrogenation function, which is characterized in that the catalyst comprises a carrier and an active component and an optional auxiliary agent which are loaded on the carrier;
wherein, the carrier is a ZSM-5 molecular sieve with the silica-alumina ratio of 500-3000;
the active component is at least one of VIII group metals;
the auxiliary agent is at least one of IIA group metal, IVA group metal, IIB group metal and rare earth metal.
2. The catalyst of claim 1, wherein the catalyst has a particle size of 50-600nm;
and/or the specific surface area of the catalyst is 200-600m 2 /g；
And/or the pore volume of the catalyst is 0.2-0.8cm 3 /g；
And/or the average pore diameter of the catalyst is 2-6nm;
preferably, in the catalyst, the weight ratio of the active component to the auxiliary agent is 1:1-10.
3. The catalyst according to claim 1 or 2, wherein the support is a ZSM-5 molecular sieve having a silica to alumina ratio in the range of 500-2000, preferably in the range of 600-2000;
and/or the active component is at least one of group VIII noble metals, preferably Pt;
preferably, the specific surface area of the carrier is 300m 2 A ratio of at least one of the compounds to the total amount of the compound (s)/g, preferably 300 to 600m 2 /g；
Preferably, in the catalyst, the loading amount of the active component is 0.01 to 5 parts by weight with respect to 100 parts by weight of the carrier;
more preferably, the loading amount of the active component is 0.1 to 1 part by weight;
further preferably, the loading amount of the active component is 0.2 to 0.8 part by weight.
4. The catalyst according to claim 1 or 2, wherein in the catalyst, the total loading amount of the promoter is 0.5 to 10 parts by weight relative to 100 parts by weight of the carrier;
preferably, the loading of group IIA metal is from 0 to 10 parts by weight, preferably from 0.1 to 5 parts by weight, more preferably from 0.1 to 3 parts by weight;
preferably, the amount of the group IVA metal supported is from 0 to 10 parts by weight, preferably from 0.1 to 5 parts by weight, more preferably from 0.1 to 3 parts by weight;
preferably, the supported amount of the group IIB metal is 0 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight;
preferably, the rare earth metal is supported in an amount of 0 to 10 parts by weight, preferably 0.5 to 5 parts by weight, more preferably 0.5 to 3 parts by weight;
more preferably, the adjuvant is selected from the group consisting of a combination of at least one of a group IIA metal and a rare earth metal with at least one of a group IIB metal;
more preferably, the promoter is selected from the group consisting of a combination of at least one of a group IIA metal and a rare earth metal with at least one of a group IVA metal;
further preferably, the auxiliary agent is a combination of Zn and at least one of Mg, ca, sm and La;
further preferably, the auxiliary agent is a combination of Sn and at least one of Mg, ca, sm and La.
5. A preparation method of a catalyst with a dehydrogenation function is characterized by comprising the steps of loading an active component precursor and an optional auxiliary agent precursor on a carrier, and then sequentially drying and roasting;
wherein the carrier is a ZSM-5 molecular sieve with the silica-alumina ratio of 500-3000;
the active component precursor comprises at least one of precursors of group VIII metals;
the auxiliary agent precursor comprises at least one of a precursor of IIA group metal, a precursor of IVA group metal, a precursor of IIB group metal and a precursor of rare earth metal.
6. The process of claim 5, wherein the support is a ZSM-5 molecular sieve having a silica to alumina ratio of 500-2000, preferably 600-2000;
and/or the active component precursor is at least one of water-soluble acid or salt of VIII group noble metal, preferably chloroplatinic acid;
preferably, the specific surface area of the carrier is 300m 2 A ratio of at least one of the compounds to the total amount of the compound (s)/g, preferably 300 to 600m 2 /g；
Preferably, the active component precursor is used in an amount such that the active component is supported in the catalyst in an amount of 0.01 to 5 parts by weight relative to 100 parts by weight of the carrier;
more preferably, the active component precursor is used in an amount such that the active component is supported in the catalyst in an amount of 0.1 to 1 part by weight;
further preferably, the active component precursor is used in an amount such that the active component is supported in the catalyst in an amount of 0.2 to 0.8 parts by weight.
7. The method according to claim 5, wherein the total amount of the promoter precursor used is such that the total loading amount of the promoter in the catalyst is 0.5 to 10 parts by weight relative to 100 parts by weight of the carrier;
preferably, the loading of group IIA metal is from 0 to 10 parts by weight, preferably from 0.1 to 5 parts by weight, more preferably from 0.1 to 3 parts by weight;
preferably, the amount of the group IVA metal supported is from 0 to 10 parts by weight, preferably from 0.1 to 5 parts by weight, more preferably from 0.1 to 3 parts by weight;
preferably, the supported amount of the group IIB metal is 0 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight;
preferably, the rare earth metal is supported in an amount of 0 to 10 parts by weight, preferably 0.5 to 5 parts by weight, more preferably 0.5 to 3 parts by weight;
more preferably, the promoter precursor is selected from the group consisting of a combination of at least one of a precursor of a group IIA metal and a precursor of a rare earth metal with a precursor of a group IIB metal;
more preferably, the promoter precursor is selected from the group consisting of a combination of at least one of a precursor of a group IIA metal and a precursor of a rare earth metal with a precursor of a group IVA metal;
further preferably, the assistant precursor is a combination of at least one of a Mg precursor, a Ca precursor, a Sm precursor and a La precursor with a Zn precursor;
further preferably, the additive precursor is a combination of at least one of Mg precursor, ca precursor, sm precursor and La precursor and Sn precursor.
8. The method according to claim 5, wherein the method of supporting the active component precursor and the auxiliary agent precursor on the carrier is selected from impregnation and/or spraying, preferably impregnation;
and/or, the drying method is selected from drying and/or vacuum drying;
and/or the roasting mode comprises the following steps: heating to 500-700 deg.C at a rate of 0.5-5 deg.C/min in air atmosphere, and calcining at the temperature for 4-12h;
preferably, the impregnation method is an equal volume impregnation method and/or an excess impregnation method, preferably an excess impregnation method;
preferably, the drying conditions include: the temperature is 80-150 ℃ and the time is 1-6h.
9. A catalyst prepared according to the process of any one of claims 5 to 8.
10. Use of a catalyst as claimed in any one of claims 1 to 4 and 9 in a catalytic dehydrogenation reaction.
11. A process for the preparation of a small molecule olefin, which process comprises contacting a small molecule alkane with a catalyst as claimed in any one of claims 1 to 4 and 9, and carrying out the dehydrogenation reaction under alkane dehydrogenation conditions.
12. The method of claim 11, wherein the small molecule olefin is selected from one of ethylene, propylene, 1-butene, and isobutylene;
preferably, the conditions for the dehydrogenation of the alkane comprise: the reaction temperature is 500-700 ℃, the pressure is 0.08-0.12MPa, and the mass space velocity of the small molecular alkane is 1-5h -1 ；
More preferably, H is selected 2 As the diluent gas, H is preferred 2 The volume ratio of the small molecule alkane to the small molecule alkane is 1.5-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110700081.6A CN115501905A (en) | 2021-06-23 | 2021-06-23 | Catalyst with dehydrogenation function, preparation method and application thereof, and method for preparing small-molecule olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110700081.6A CN115501905A (en) | 2021-06-23 | 2021-06-23 | Catalyst with dehydrogenation function, preparation method and application thereof, and method for preparing small-molecule olefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115501905A true CN115501905A (en) | 2022-12-23 |
Family
ID=84499545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110700081.6A Pending CN115501905A (en) | 2021-06-23 | 2021-06-23 | Catalyst with dehydrogenation function, preparation method and application thereof, and method for preparing small-molecule olefin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115501905A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108362A (en) * | 2006-07-19 | 2008-01-23 | 中国石化集团金陵石油化工有限责任公司 | Catalyzer used for low carbon alkane catalytic dehydrogenation and method of manufacturing propylene by paraffin hydrocarbons catalytic dehydrogenation with the same as catalyzer |
| CN101138734A (en) * | 2007-09-28 | 2008-03-12 | 东南大学 | Method for improving catalyst reacting activity in the propylene producing through propane dehydrogenation |
| CN104275179A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Light alkane dehydrogenation catalyst and preparation method |
| CN106964392A (en) * | 2016-01-13 | 2017-07-21 | 中国石油化工股份有限公司 | Oxidative dehydrogenation of propane catalyst and application thereof |
| CN109746026A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | A kind of dehydrogenation and the preparation method and application thereof |
| CN112536065A (en) * | 2019-09-20 | 2021-03-23 | 中国石油化工股份有限公司 | Method for preparing propylene by propane dehydrogenation |
| CN112619690A (en) * | 2019-10-09 | 2021-04-09 | 中国石油化工股份有限公司 | Supported catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof |
-
2021
- 2021-06-23 CN CN202110700081.6A patent/CN115501905A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108362A (en) * | 2006-07-19 | 2008-01-23 | 中国石化集团金陵石油化工有限责任公司 | Catalyzer used for low carbon alkane catalytic dehydrogenation and method of manufacturing propylene by paraffin hydrocarbons catalytic dehydrogenation with the same as catalyzer |
| CN101138734A (en) * | 2007-09-28 | 2008-03-12 | 东南大学 | Method for improving catalyst reacting activity in the propylene producing through propane dehydrogenation |
| CN104275179A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Light alkane dehydrogenation catalyst and preparation method |
| CN106964392A (en) * | 2016-01-13 | 2017-07-21 | 中国石油化工股份有限公司 | Oxidative dehydrogenation of propane catalyst and application thereof |
| CN109746026A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | A kind of dehydrogenation and the preparation method and application thereof |
| CN112536065A (en) * | 2019-09-20 | 2021-03-23 | 中国石油化工股份有限公司 | Method for preparing propylene by propane dehydrogenation |
| CN112619690A (en) * | 2019-10-09 | 2021-04-09 | 中国石油化工股份有限公司 | Supported catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2292238C2 (en) | Fischer-tropsch process catalyst (variations) and a method for preparation thereof | |
| JP5065255B2 (en) | Catalyst production method | |
| WO2015072573A1 (en) | Production method for catalyst for fischer-tropsch synthesis, and production method for hydrocarbon | |
| US9278344B2 (en) | Hybrid fischer-tropsch catalysts | |
| EP3738670A1 (en) | Catalyst, method for producing same, and method for producing diene compound using said catalyst | |
| JP5543150B2 (en) | Selective hydrogenation catalyst for aromatic nitro compounds, process for producing and regenerating the same, and process for selective hydrogenation of aromatic nitrated compounds using the same | |
| JPWO2007083684A1 (en) | Catalyst and method for producing olefin using the same | |
| EP3083038A1 (en) | Heterogeneous alkane dehydrogenation catalyst | |
| WO2022143275A1 (en) | Method for treating or regenerating metal catalyst and application | |
| US9023899B2 (en) | Hybrid fischer-tropsch catalysts and processes for use thereof | |
| US20150353446A1 (en) | Passivation of a zeolite catalyst in a fluidized bed | |
| US9248435B2 (en) | Process for preparing a cobalt-containing fischer tropsch catalyst | |
| WO2020059889A1 (en) | Catalyst, and method for producing 1,3-butadiene using same | |
| Wei et al. | Hydrogenation of pentenal over supported Pt nanoparticles: Influence of Lewis-acid sites in the conversion pathway | |
| CN115501905A (en) | Catalyst with dehydrogenation function, preparation method and application thereof, and method for preparing small-molecule olefin | |
| WO2013141982A1 (en) | Improved hybrid fischer-tropsch catalysts and processes for use thereof | |
| Álvarez-Rodríguez et al. | Surface and structural effects in the hydrogenation of citral over RuCu/KL catalysts | |
| CN102209699A (en) | Method for manufacturing unsaturated hydrocarbon and oxygenated compound, catalyst, and manufacturing method therefor | |
| Álvarez-Rodríguez et al. | Surface changes in Ru/KL supported catalysts induced by the preparation method and their effect on the selective hydrogenation of citral | |
| JP2022549727A (en) | Catalyst for producing isopropylbenzene and its production method and use | |
| JP2017144421A (en) | Catalyst for acetaldehyde synthesis, apparatus for manufacturing acetaldehyde, and method for manufacturing acetaldehyde | |
| KR101988374B1 (en) | Method of preparation of ethylamine or acetonitrile by reductive amination of ethanol | |
| CN115138356B (en) | Application of dehydrogenation catalyst in ethylbenzene direct dehydrogenation reaction and dehydrogenation method | |
| RU2788375C1 (en) | Method for producing a catalyst for the fischer-tropsch synthesis | |
| CN113856738B (en) | Catalyst with function of catalyzing propane dehydrogenation to prepare propylene, preparation method and application thereof, and method for preparing propylene |
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 |