CN114618463A - Composite catalyst and preparation method and application thereof - Google Patents
Composite catalyst and preparation method and application thereof Download PDFInfo
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- CN114618463A CN114618463A CN202011456763.9A CN202011456763A CN114618463A CN 114618463 A CN114618463 A CN 114618463A CN 202011456763 A CN202011456763 A CN 202011456763A CN 114618463 A CN114618463 A CN 114618463A
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- gallium
- composite catalyst
- aluminum
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- 239000003054 catalyst Substances 0.000 title claims abstract description 111
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000001294 propane Substances 0.000 claims abstract description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 38
- 238000010335 hydrothermal treatment Methods 0.000 claims description 28
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 26
- 239000011787 zinc oxide Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 229910052733 gallium Inorganic materials 0.000 claims description 21
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- 150000001261 hydroxy acids Chemical class 0.000 claims description 16
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 229940044658 gallium nitrate Drugs 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 150000007522 mineralic acids Chemical class 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004310 lactic acid Substances 0.000 claims description 6
- 235000014655 lactic acid Nutrition 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- -1 hydrogen ions Chemical class 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229910000373 gallium sulfate Inorganic materials 0.000 claims description 3
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 20
- 239000002243 precursor Substances 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- CBIIVSNVIRRJAS-UHFFFAOYSA-N [C].CCC Chemical compound [C].CCC CBIIVSNVIRRJAS-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- JGNPSJMNGPUQIW-UHFFFAOYSA-N [C].CC=C Chemical compound [C].CC=C JGNPSJMNGPUQIW-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a composite catalyst and a preparation method and application thereof. The application provides a low-cost and environment-friendly catalyst for preparing propylene by propane dehydrogenation; the catalyst can be applied to the development of a circulating fluidized bed process, and the development of a new propane dehydrogenation technology is promoted.
Description
Technical Field
The application relates to a composite catalyst, a preparation method and application thereof, and belongs to the technical field of catalysts.
Background
Propylene is a basic chemical raw material and mainly comes from naphtha catalytic cracking, methanol-to-olefin, propane dehydrogenation and the like. Wherein propane dehydrogenation is developed more rapidly due to increased propane production and reduced costs.
At present, propane dehydrogenation catalysts are mainly Pt catalysts and Cr catalysts. The propane dehydrogenation process is limited by thermodynamics, and the reaction temperature has a serious influence on the conversion rate. In order to ensure the conversion rate of propane, the temperature of the propane dehydrogenation reaction is between 580 and 630 ℃. At this temperature, the carbon deposit inactivation of the catalyst is difficult to avoid, and the carbon burning regeneration of the catalyst is the main means for restoring the activity. However, the noble metal Pt is expensive, the chromium oxide has great toxicity to the environment and is difficult to bear the problems of catalyst breakage and loss, so that the circulating fluidized bed process cannot be adopted. The Pt catalyst mainly adopts a moving bed process, while the chromium oxide catalyst adopts a multi-reactor fixed bed reactor connected in parallel, and the operation process is complex and tedious. Therefore, the development of new catalysts with low cost and environmental friendliness is the main development direction of propane dehydrogenation catalysts.
Disclosure of Invention
Aiming at the problems, the invention provides a low-cost and environment-friendly composite catalyst for preparing propylene by propane dehydrogenation, and a preparation method and application thereof.
According to the first aspect of the application, a compound catalyst I is provided, and is prepared by reacting a mixture consisting of a gallium source, an aluminum source and hydroxy acid I, adding zinc oxide and inorganic acid water for heat treatment, and roasting.
Optionally, the composite catalyst I consists of four elements of zinc, aluminum, gallium and oxygen; the molar ratio of the zinc element, the gallium element and the aluminum element is 13.6-62.0: 0.6-7.8: 30.2 to 85.8.
Optionally, the hydroxy acid is selected from at least one of citric acid, tartaric acid, lactic acid and malic acid;
the gallium source is selected from at least one of gallium nitrate, gallium chloride and gallium sulfate;
the aluminum source is selected from at least one of aluminum nitrate, aluminum chloride and aluminum sulfate;
the inorganic acid is at least one of nitric acid, sulfuric acid and hydrochloric acid.
Optionally, the composite catalyst I is prepared by a hydrothermal method.
Optionally, the hydroxy acid functions as a complexing agent.
Optionally, the concentration of the inorganic acid is 0.1-5 mol/L.
According to a second aspect of the present application, there is provided a process for producing the above-mentioned composite catalyst I, which comprises:
(1) reacting a mixture consisting of a gallium source, an aluminum source and hydroxy acid to obtain sol;
(2) carrying out hydrothermal treatment on a mixture containing the sol, zinc oxide and inorganic acid to obtain an intermediate product;
(3) and drying and roasting the intermediate product to obtain the composite catalyst I.
Optionally, the molar ratio of the zinc oxide to the gallium source to the aluminum source is 13.6-62.0: 0.6-7.8: 30.2-85.8;
the mole number of the gallium source is calculated by the mole number of the metal gallium; the moles of the aluminum source are based on the moles of the metallic aluminum; the mole number of the zinc oxide is calculated by the mole number of the metal zinc;
the molar ratio of the metal source to the hydroxy acid is 100: 8.6 to 244;
the mole number of the metal source is the sum of the mole numbers of the zinc oxide, the gallium source and the aluminum source; the number of moles of the hydroxy acid is based on the number of moles of the hydroxy acid itself;
the molar ratio of the metal source to the inorganic acid is 100: 2.7 to 62;
the mole number of the inorganic acid is calculated by the mole number of hydrogen ions; the mole number of the metal source is the sum of the mole numbers of the zinc oxide, the gallium source and the aluminum source.
Optionally, in the step (1), the conditions of the reaction I are: the temperature is 20-80 ℃; the time is 0.5-5 h;
in the step (2), the hydrothermal treatment conditions are as follows: the temperature is 100-200 ℃; the time is 24-96 hours;
in the step (3), the drying conditions are as follows: the temperature is 50-200 ℃; the time is 4-20 h;
in the step (3), the roasting conditions are as follows: the temperature is 300-700 ℃; the time is 4-20 h.
According to a third aspect of the present application, there is provided a hybrid catalyst II composed of a hybrid catalyst I and alumina;
the mass ratio of the composite catalyst I to the alumina is 1-9: 9-1;
the composite catalyst I is at least one selected from the composite catalyst I and the composite catalyst I prepared by the method.
Optionally, the compound catalyst II in the present application has a chemical formula composition of: x (aZnbGacAldO)/y (Al)2O3) (ii) a The mass fraction of each component is as follows: 10-90% of x, 10-90% of y, 20-69% of a, 1-10% of b and 30-70% of c.
Wherein, the upper limit of x can be selected from 90%, 80%, 70%, 60%, 50%, 40%, 30%, 25%, 20%, 15%, 12% or 10.5%, and the lower limit can be selected from 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 40%, 30%, 20%, 12% or 10%;
the upper limit of y can be selected from 90%, 80%, 70%, 60%, 50%, 40%, 30%, 25%, 20%, 15%, 12% or 10.5%, and the lower limit can be selected from 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 40%, 30%, 20%, 12% or 10%;
the upper limit of a can be selected from 20.5%, 25.0%, 30.0%, 35.0%, 40.0%, 45%, 50%, 55%, 60%, 65% or 69%, and the lower limit can be selected from 20.0%, 24.5%, 29.5%, 34.5%, 39.5%, 44.5%, 49.5%, 54.5%, 59.5%, 64.5% or 68.5%;
the upper limit of b can be selected from 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, and the lower limit is selected from 1.0%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%.
The upper limit of the value of c can be 31%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70%, and the lower limit is 30%, 31%, 35%, 40%, 45%, 50%, 55%, 60% or 65%.
Optionally, the method comprises: and mixing the compound catalyst I with alumina to obtain the compound catalyst II.
Specifically, the composite catalyst I of the present application is not simply obtained by physically mixing zinc oxide, aluminum oxide and gallium oxide, but has a specific morphology and structure.
Specifically, zinc oxide and inorganic acid are added to slowly act to obtain zinc ions, the zinc ions enter the catalyst to become one of active components, part of the zinc oxide acts with generated alumina to generate a spinel structure, the acidity of the catalyst is reduced, and the product composite catalyst I has high activity and high selectivity.
Alternatively, the method for preparing the composite catalyst II comprises:
(1) preparing dehydrogenation components aZnbGacAldO by a hydrothermal method and the like, wherein a is 20-69%, b is 1-10%, and c is 30-70%, preparing a precursor containing Ga and Al in a stoichiometric ratio into a solution, adding hydroxy acid into the solution, and adding the hydroxy acid in a molar ratio to Al: uniformly stirring hydroxy acid/Al (0.1-5) to obtain Ga-Al sol, adding zinc oxide into the Ga-Al sol to obtain an aZnbGacAldO precursor mixture, and adding an acid solution into the mixture solution, wherein the molar ratio of the zinc oxide to hydrogen ions in the acid is; 5-1 parts of zinc oxide/hydrogen ions;
(2) transferring the mixture obtained in the step (1) into a synthesis kettle, sealing, heating to 100-200 ℃, and carrying out self-pressure hydrothermal treatment for 24-94 hours to obtain a hydrothermal treatment product;
(3) filtering, washing and separating a hydrothermal treatment product, drying at 50-200 ℃ for 4-20 hours, and roasting at 300-700 ℃ for 4-20 hours in an air atmosphere to obtain a catalyst 1: aZnbGacAldO;
(4) the aZnbGacAldO catalyst and Al are mixed2O3Mixed into x (aZnbGacAldO)/y (Al) according to the proportion2O3) And obtaining the composite catalyst II, wherein x is 10-90%, and y is 10-90%.
According to a final aspect of the present application, there is provided a process for producing propylene, the process comprising: reacting raw material gas containing propane in the presence of a catalyst to obtain propylene;
the catalyst is selected from at least one of a compound catalyst I and a compound catalyst II;
the composite catalyst I is at least one selected from the composite catalyst I and the composite catalyst I prepared by the method;
the composite catalyst II is at least one selected from the composite catalyst II and the composite catalyst II prepared by the method.
Optionally, the method comprises: the raw material gas containing propane passes through the reactor and contacts with the catalyst to react to generate propylene.
Alternatively, the conditions of reaction II are: the reaction temperature is 530 ℃ and 630 ℃; the reaction space velocity is 200-600L Kg- 1h-1。
Alternatively, the pressure of reaction II is atmospheric pressure.
Optionally, the upper limit of the reaction temperature is selected from 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃ or 630 ℃; the lower limit is selected from 530 deg.C, 540 deg.C, 550 deg.C, 560 deg.C, 570 deg.C, 580 deg.C, 590 deg.C, 600 deg.C, 610 deg.C, 620 deg.C, or 625 deg.C.
Alternatively, the upper limit of the propane mass space velocity is selected from 220L Kg-1h-1、240L Kg-1h-1、260L Kg-1h-1、280L Kg-1h-1、300L Kg-1h-1、350L Kg-1h-1、400L Kg-1h-1、450L Kg-1h-1、500L Kg-1h-1、550L Kg-1h-1Or 600L Kg-1h-1(ii) a The lower limit is selected from 200L Kg-1h-1、220L Kg-1h-1、240L Kg-1h-1、260L Kg-1h-1、280L Kg- 1h-1、300L Kg-1h-1、350L Kg-1h-1、400L Kg-1h-1、450L Kg-1h-1、500L Kg-1h-1、550L Kg-1h-1Or 580L Kg-1h-1。
The beneficial effects that this application can produce include:
(1) the catalyst for preparing propylene by propane dehydrogenation is low in cost and environment-friendly;
(2) the catalyst can be applied to the development of a circulating fluidized bed process, and the development of a new propane dehydrogenation technology is promoted.
Drawings
FIG. 1 is an XRD pattern of catalyst 1;
fig. 2 is an XRD spectrum of the mixed catalyst 1.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The analysis method in the examples of the present application is as follows:
the raw materials and the products were detected by Agilent 7890B gas chromatography from Agilent, Inc., using PLOT-Q capillary column from Agilent, Inc.
In the examples of the present application, both propane conversion and propylene selectivity were calculated on a carbon mole basis.
The conversion, selectivity, in the examples of the present application were calculated as follows:
propane conversion ═ [ (moles of propane carbon in feed) - (moles of propane carbon in discharge) ]/(moles of propane carbon in feed) × (100%)
Propylene selectivity [ moles of propylene carbon in the discharge ]/[ (moles of propane carbon in the feed) - (moles of propane carbon in the discharge) ] × (100%)
Example 1
Weighing 0.191g of gallium nitrate and 1.5876g of aluminum nitrate, adding the gallium nitrate and the 1.5876g of aluminum nitrate into 10ml of water, stirring the mixture at 80 ℃ until the mixture is completely dissolved, adding 1.3429g of lactic acid, stirring the mixture until the lactic acid is dissolved, continuing stirring the mixture for 30 minutes to obtain sol, then adding 0.55g of zinc oxide into the Ga-Al sol to obtain a precursor mixture, and then adding 0.1mol/L of sulfur into the precursor mixtureAn acid solution (9.7mL) was added to the mixture solution and stirred well. And transferring the precursor mixture into a synthesis kettle, sealing, heating to 180 ℃, and carrying out hydrothermal treatment for 48h by virtue of autogenous pressure to obtain a hydrothermal treatment product. And filtering, washing and separating the hydrothermal treatment product, drying at 80 ℃ for 18 hours, and then roasting at 500 ℃ in an air atmosphere for 12 hours to obtain the catalyst 1. 0.6g of catalyst 1 and 0.4g of Al are taken2O3And uniformly mixing to obtain the catalyst 2. The XRD pattern of catalyst 1 is shown in fig. 1.
Example 2
0.1879g of gallium chloride and 0.9945g of aluminum chloride are weighed and added into 10mL of water, stirred at 30 ℃ until the gallium chloride and the aluminum chloride are completely dissolved, 2.7617g of malic acid are added, stirred until the malic acid is dissolved, stirred for 60 minutes to obtain sol, then 0.69g of zinc oxide is added into Ga-Al sol to obtain a precursor mixture, 5mol/L hydrochloric acid solution (1.7mL) is added into the mixture solution, and the mixture solution is stirred uniformly. And transferring the precursor mixture into a synthesis kettle, sealing, heating to 100 ℃, and carrying out hydrothermal treatment for 96 hours by means of autogenous pressure to obtain a hydrothermal treatment product. And filtering, washing and separating the hydrothermal treatment product, drying at 50 ℃ for 20 hours, and then roasting at 300 ℃ in an air atmosphere for 20 hours to obtain the catalyst 3. 0.9g of catalyst 3 and 0.1g of Al are taken2O3And uniformly mixing to obtain the catalyst 4.
Example 3
0.2729g of gallium nitrate and 2.0889g of aluminum nitrate are weighed and added into 10mL of water, stirred at 30 ℃ until the gallium nitrate and the aluminum nitrate are completely dissolved, 1.0305g of citric acid is added and stirred until the gallium nitrate and the aluminum nitrate are dissolved, then the mixture is continuously stirred for 240 minutes to obtain sol, then 0.45g of zinc oxide is added into the Ga-Al sol to obtain a precursor mixture, and then 2mol/L nitric acid solution (1.1mL) is added into the mixture solution and stirred uniformly. And transferring the precursor mixture into a synthesis kettle, sealing, heating to 150 ℃, and carrying out hydrothermal treatment for 72h by virtue of autogenous pressure to obtain a hydrothermal treatment product. And filtering, washing and separating the hydrothermal treatment product, drying at 150 ℃ for 10 hours, and then roasting at 650 ℃ for 5 hours in an air atmosphere to obtain the catalyst 5. 0.7g of catalyst 5 and 0.3g of Al are taken2O3And uniformly mixing to obtain a catalyst 6.
Example 4
0.0238g of gallium sulfate and 5.1635g of aluminum sulfate are weighed and added into 10mL of water, stirred at 80 ℃ until being completely dissolved, 0.2326g of tartaric acid is added and stirred until being dissolved, then stirred for 30 minutes to obtain sol, then 0.2g of zinc oxide is added into Ga-Al sol to obtain precursor mixture, and then 0.1mol/L sulfuric acid solution (9.7mL) is added into the mixture solution and stirred uniformly. And transferring the precursor mixture into a synthesis kettle, sealing, heating to 200 ℃, and carrying out hydrothermal treatment for 24h by virtue of autogenous pressure to obtain a hydrothermal treatment product. And filtering, washing and separating the hydrothermal treatment product, drying at 200 ℃ for 4 hours, and then roasting at 700 ℃ in an air atmosphere for 4 hours to obtain the catalyst 7. 0.1g of catalyst 7 and 0.9g of Al are taken2O3The catalyst 8 is obtained after uniform mixing.
Example 5
0.0819g of gallium nitrate and 2.5067g of aluminum nitrate are weighed and added into 10mL of water, stirred at 50 ℃ until the gallium nitrate and the aluminum nitrate are completely dissolved, 7.4195g of citric acid is added, stirred until the gallium nitrate and the aluminum nitrate are dissolved, stirred for 60 minutes to obtain sol, then 0.35g of zinc oxide is added into Ga-Al sol to obtain a precursor mixture, and then 3mol/L hydrochloric acid solution (1mL) is added into the mixture solution, and stirred uniformly. And transferring the precursor mixture into a synthesis kettle, sealing, heating to 120 ℃, and carrying out hydrothermal treatment for 80h by virtue of autogenous pressure to obtain a hydrothermal treatment product. And filtering, washing and separating the hydrothermal treatment product, drying at 110 ℃ for 12 hours, and then roasting at 600 ℃ in an air atmosphere for 6 hours to obtain the catalyst 9. 0.5g of catalyst 9 and 0.5g of Al are taken2O3The catalyst 10 is obtained by mixing homogeneously.
Example 6
0.0546g of gallium nitrate and 3.0498g of aluminum nitrate are weighed and added into 10mL of water, stirred at 60 ℃ until the gallium nitrate and the aluminum nitrate are completely dissolved, 7.4195g of citric acid is added, stirred until the gallium nitrate and the aluminum nitrate are dissolved, then stirred for 40 minutes to obtain sol, then 0.25g of zinc oxide is added into Ga-Al sol to obtain precursor mixture, 1mol/L nitric acid solution (1.5mL) is added into the mixture solution, and the mixture solution is stirred uniformly. And transferring the precursor mixture into a synthesis kettle, sealing, heating to 160 ℃, and carrying out hydrothermal treatment for 72h by virtue of autogenous pressure to obtain a hydrothermal treatment product. Filtering, washing and separating the hydrothermal treatment product, and drying at 100 DEG CFor 12 hours, and then calcined at 550 ℃ for 12 hours in an air atmosphere to obtain catalyst 11. 0.8g of catalyst 11 and 0.2g of Al are taken2O3The catalyst 12 is obtained by mixing homogeneously.
Comparative example 1
0.1804g of copper nitrate and 1.5876g of aluminum nitrate are weighed and added into 10mL of water, stirred at 80 ℃ until the copper nitrate and the aluminum nitrate are completely dissolved, 1.3429g of lactic acid are added, stirred until the lactic acid is dissolved, stirred for 30 minutes to obtain sol, then 0.55g of zinc oxide is added into Ga-Al sol to obtain a precursor mixture, and then 0.1mol/L sulfuric acid solution (9.7mL) is added into the mixture solution, and stirred uniformly. And transferring the precursor mixture into a synthesis kettle, sealing, heating to 180 ℃, and carrying out hydrothermal treatment for 48 hours by means of autogenous pressure to obtain a hydrothermal treatment product. After filtering, washing and separating the hydrothermal treatment product, drying the product at 80 ℃ for 18 hours, and then roasting the product at 500 ℃ in an air atmosphere for 12 hours to obtain a comparative catalyst 1. 0.6g of catalyst 3 and 0.4g of Al are taken2O3And mixed well to give comparative catalyst 2.
Comparative example 2
0.55g of zinc oxide powder, 0.07g of gallium oxide powder and 0.38g of aluminum oxide powder were weighed and physically mixed to obtain a mixed catalyst 1. Fig. 2 is an XRD pattern of the mixed catalyst 1. From the XRD results, it can be seen that catalyst 1 of example 1 and mixed catalyst 1 are completely different substances, i.e., catalyst 1 obtained in example 1 is not obtained by physical mixing of oxides.
Example 7
The catalysts of the preceding examples were subjected to reaction evaluation: the catalyst is loaded into a fixed bed reactor, the reaction temperature is 530 ℃ and 630 ℃, the reaction pressure is normal pressure, and the reaction space velocity is 200-600L Kg-1h-1. The catalyst 1 of the previous example reacted as a comparative example. Samples were taken after 6min of reaction and the results are shown in Table 1.
TABLE 1 results of the catalytic reaction
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A composite catalyst I is characterized in that a mixture consisting of a gallium source, an aluminum source and hydroxy acid is subjected to reaction I, then zinc oxide and inorganic acid water are added for heat treatment, and the composite catalyst I is prepared by roasting.
2. The composite catalyst I according to claim 1, characterized in that the composite catalyst I consists of four elements of zinc, aluminum, gallium and oxygen; the molar ratio of the zinc element, the gallium element and the aluminum element is 13.6-62.0: 0.6-7.8: 30.2 to 85.8.
3. The composite catalyst I according to claim 1, wherein the hydroxy acid is at least one selected from citric acid, tartaric acid, lactic acid, malic acid;
the gallium source is selected from at least one of gallium nitrate, gallium chloride and gallium sulfate;
the aluminum source is selected from at least one of aluminum nitrate, aluminum chloride and aluminum sulfate;
the inorganic acid is at least one selected from nitric acid, sulfuric acid and hydrochloric acid.
4. The process for the preparation of the hybrid catalyst I according to any of claims 1 to 3, characterized in that it comprises:
(1) reacting a mixture consisting of a gallium source, an aluminum source and hydroxy acid to obtain sol;
(2) carrying out hydrothermal treatment on a mixture containing the sol, zinc oxide and inorganic acid to obtain an intermediate product;
(3) and drying and roasting the intermediate product to obtain the composite catalyst I.
5. The preparation method according to claim 4, wherein the molar ratio of the zinc oxide to the gallium source to the aluminum source is 13.6 to 62.0: 0.6-7.8: 30.2-85.8;
the mole number of the gallium source is calculated by the mole number of the metal gallium; the moles of the aluminum source are based on the moles of the metallic aluminum; the mole number of the zinc oxide is calculated by the mole number of the metal zinc;
the molar ratio of the metal source to the hydroxy acid is 100: 8.6 to 244;
the mole number of the metal source is the sum of the mole numbers of the zinc oxide, the gallium source and the aluminum source; the number of moles of the hydroxy acid is based on the number of moles of the hydroxy acid itself;
the molar ratio of the metal source to the inorganic acid is 100: 2.7 to 62;
the mole number of the inorganic acid is calculated by the mole number of hydrogen ions; the mole number of the metal source is the sum of the mole numbers of the zinc oxide, the gallium source and the aluminum source.
6. The production method according to claim 4, wherein in the step (1), the conditions of the reaction I are: the temperature is 20-80 ℃; the time is 0.5-5 h;
in the step (2), the hydrothermal treatment conditions are: the temperature is 100-200 ℃; the time is 24-96 hours;
in the step (3), the drying conditions are as follows: the temperature is 50-200 ℃; the time is 4-20 h;
the roasting conditions are as follows: the temperature is 300-700 ℃; the time is 4-20 h.
7. The composite catalyst II is characterized by consisting of a composite catalyst I and alumina;
the mass ratio of the composite catalyst I to the alumina is 1-9: 1-9;
the hybrid catalyst I is at least one selected from the hybrid catalyst I according to any one of claims 1 to 3, and the hybrid catalyst I prepared by the process according to any one of claims 4 to 6.
8. The method for preparing the composite catalyst II according to claim 7, comprising: and mixing the compound catalyst I with alumina to obtain the compound catalyst II.
9. A process for the production of propylene, comprising: reacting raw material gas containing propane in the presence of a catalyst to obtain propylene;
the catalyst is selected from at least one of a compound catalyst I and a compound catalyst II;
the composite catalyst I is at least one selected from the composite catalyst I according to any one of claims 1 to 3 and the composite catalyst I prepared by the method according to any one of claims 4 to 6;
the composite catalyst II is at least one selected from the composite catalyst II according to claim 7 and the composite catalyst II prepared by the method according to claim 8.
10. The method of claim 9, wherein the conditions of reaction II are: the reaction temperature is 530 ℃ and 630 ℃; the reaction space velocity is 200-600L Kg-1h-1。
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008239363A (en) * | 2007-03-26 | 2008-10-09 | National Institute Of Advanced Industrial & Technology | Method for producing composite metal sulfide and method for producing composite metal sulfide sintered compact |
| CN101785993A (en) * | 2009-01-22 | 2010-07-28 | 复旦大学 | Preparation method of catalyst for producing propylene by propane dehydrogenation under carbon dioxide atmosphere |
| US20130165729A1 (en) * | 2011-12-22 | 2013-06-27 | Saudi Basic Industries Corporation | Zinc and/or manganese aluminate catalyst useful for alkane dehdyrogenation |
| CN104084198A (en) * | 2014-07-15 | 2014-10-08 | 华陆工程科技有限责任公司 | Platinum aluminium oxide series catalyst for preparing propylene by propane dehydrogenation and preparation method of catalyst |
| CN104148069A (en) * | 2014-08-18 | 2014-11-19 | 华陆工程科技有限责任公司 | Quaternary platinum-based catalyst used for production of propylene through propane dehydrogenation, and preparation method and application thereof |
| CN104607235A (en) * | 2015-01-13 | 2015-05-13 | 大连理工大学 | Preparation method of Zn-ZSM-5 and application of Zn-ZSM-5 in preparing propylene via propane dehydrogenation |
| CN105727929A (en) * | 2014-12-11 | 2016-07-06 | 中化近代环保化工(西安)有限公司 | Fluorination catalyst with high specific surface area, preparation method thereof and application |
| CN107899619A (en) * | 2017-10-31 | 2018-04-13 | 西南化工研究设计院有限公司 | A kind of preparing propylene by dehydrogenating propane composite alumina support catalyst and preparation method thereof |
| WO2018080333A1 (en) * | 2016-10-31 | 2018-05-03 | Public Joint Stock Company "Sibur Holding" | Process for production of acrylic acid, process for the selective oxidation of carbon monoxide, catalyst for the selective oxidation of carbon monoxide, process for producing the same |
| CN110368949A (en) * | 2019-07-22 | 2019-10-25 | 太原理工大学 | A kind of CO adds hydrogen low-carbon alcohols GaFe base catalyst and preparation method and application |
| WO2020161263A1 (en) * | 2019-02-08 | 2020-08-13 | Evonik Operations Gmbh | A triphasic reactor |
| CN114618470A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Composite catalyst and preparation method and application thereof |
-
2020
- 2020-12-10 CN CN202011456763.9A patent/CN114618463B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008239363A (en) * | 2007-03-26 | 2008-10-09 | National Institute Of Advanced Industrial & Technology | Method for producing composite metal sulfide and method for producing composite metal sulfide sintered compact |
| CN101785993A (en) * | 2009-01-22 | 2010-07-28 | 复旦大学 | Preparation method of catalyst for producing propylene by propane dehydrogenation under carbon dioxide atmosphere |
| US20130165729A1 (en) * | 2011-12-22 | 2013-06-27 | Saudi Basic Industries Corporation | Zinc and/or manganese aluminate catalyst useful for alkane dehdyrogenation |
| CN104084198A (en) * | 2014-07-15 | 2014-10-08 | 华陆工程科技有限责任公司 | Platinum aluminium oxide series catalyst for preparing propylene by propane dehydrogenation and preparation method of catalyst |
| CN104148069A (en) * | 2014-08-18 | 2014-11-19 | 华陆工程科技有限责任公司 | Quaternary platinum-based catalyst used for production of propylene through propane dehydrogenation, and preparation method and application thereof |
| CN105727929A (en) * | 2014-12-11 | 2016-07-06 | 中化近代环保化工(西安)有限公司 | Fluorination catalyst with high specific surface area, preparation method thereof and application |
| CN104607235A (en) * | 2015-01-13 | 2015-05-13 | 大连理工大学 | Preparation method of Zn-ZSM-5 and application of Zn-ZSM-5 in preparing propylene via propane dehydrogenation |
| WO2018080333A1 (en) * | 2016-10-31 | 2018-05-03 | Public Joint Stock Company "Sibur Holding" | Process for production of acrylic acid, process for the selective oxidation of carbon monoxide, catalyst for the selective oxidation of carbon monoxide, process for producing the same |
| CN107899619A (en) * | 2017-10-31 | 2018-04-13 | 西南化工研究设计院有限公司 | A kind of preparing propylene by dehydrogenating propane composite alumina support catalyst and preparation method thereof |
| WO2020161263A1 (en) * | 2019-02-08 | 2020-08-13 | Evonik Operations Gmbh | A triphasic reactor |
| CN110368949A (en) * | 2019-07-22 | 2019-10-25 | 太原理工大学 | A kind of CO adds hydrogen low-carbon alcohols GaFe base catalyst and preparation method and application |
| CN114618470A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Composite catalyst and preparation method and application thereof |
Non-Patent Citations (10)
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|---|---|
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