CN112812752B - Heat storage material with specific pore structure for preparing propylene by propane dehydrogenation and preparation method thereof - Google Patents
Heat storage material with specific pore structure for preparing propylene by propane dehydrogenation and preparation method thereof Download PDFInfo
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- CN112812752B CN112812752B CN202011412899.XA CN202011412899A CN112812752B CN 112812752 B CN112812752 B CN 112812752B CN 202011412899 A CN202011412899 A CN 202011412899A CN 112812752 B CN112812752 B CN 112812752B
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000005338 heat storage Methods 0.000 title claims abstract description 69
- 239000011232 storage material Substances 0.000 title claims abstract description 68
- 239000001294 propane Substances 0.000 title claims abstract description 48
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 39
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 37
- 239000011148 porous material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 230000008929 regeneration Effects 0.000 claims abstract description 19
- 238000011069 regeneration method Methods 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 14
- 230000009467 reduction Effects 0.000 claims abstract description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012876 carrier material Substances 0.000 claims abstract description 9
- 239000004005 microsphere Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920002472 Starch Polymers 0.000 claims abstract description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004202 carbamide Substances 0.000 claims abstract description 4
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 4
- 239000005011 phenolic resin Substances 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- 239000008107 starch Substances 0.000 claims abstract description 4
- 235000019698 starch Nutrition 0.000 claims abstract description 4
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 3
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 3
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 3
- 235000015165 citric acid Nutrition 0.000 claims abstract description 3
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 3
- 239000010439 graphite Substances 0.000 claims abstract description 3
- 238000000465 moulding Methods 0.000 claims abstract description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims abstract description 3
- 239000008117 stearic acid Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 61
- 230000008569 process Effects 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000007654 immersion Methods 0.000 claims description 9
- 238000010926 purge Methods 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910009116 xCuO Inorganic materials 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 18
- 238000005303 weighing Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000008685 targeting Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/67—Pore distribution monomodal
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- 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
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- C07C2523/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with alkali- or alkaline earth metals or beryllium
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Abstract
The invention discloses a heat storage material with a specific pore structure for preparing propylene by catalytic dehydrogenation of propane and a preparation method thereof, wherein the heat storage material is Al with a specific pore structure2O3Supported CuO-based materials. Adding pore-forming agent to Al2O3The carrier material is subjected to pore structure modulation and molding treatment, and the pore-forming agent is one or more of citric acid, oxalic acid, benzoic acid, polyvinyl alcohol, polyvinyl butyral, polymer microspheres, starch, stearic acid, activated carbon, graphite, phenolic resin, urea and the like. The synthesized heat storage material with a specific pore structure is mixed with a catalyst and used in a reaction process for preparing propylene by propane catalytic dehydrogenation, the conversion rate of propane and the selectivity of propylene can be further improved, and heat is released in a reduction stage and an air regeneration stage, so that the temperature distribution of a bed layer is more uniform, the service life of the catalyst is expected to be prolonged in industrial application, the inlet temperature of regenerated air or the flow of the regenerated air is reduced, and the energy consumption of a device is reduced.
Description
Technical Field
The invention aims at a propane catalytic dehydrogenation process, relates to a high-performance heat storage material for improving the temperature distribution of a catalyst bed layer of a fixed bed reactor and improving the product yield and a preparation method thereof, and belongs to the field of chemical industry.
Background
Propylene is an important petrochemical basic raw material second only to ethylene, and is widely used for producing polypropylene, butanol and octanol, acrylonitrile, propylene oxide, epichlorohydrin, acetone, acrylic acid and the like. At present, propylene mainly comes from ethylene co-production and catalytic cracking, in recent years, the development speed of propylene in China gradually exceeds that of ethylene, in 2017, the annual average growth rate of the equivalent demand of propylene in China reaches 7.6 percent, and the growth rate of the production capacity of propylene is exceeded. In view of equivalent demand, the contradiction between supply and demand of propylene is increasingly prominent, so that the production process prospect of PDH (PDH) propylene from which propylene is derived is very wide in recent years.
Since the catalytic dehydrogenation reaction is a strongly endothermic reaction process, the temperature distribution of the bed and the heat reserve have an important influence on the propylene product yield. In the process of the Catofin propane dehydrogenation process, the heat of a catalyst bed mainly comes from reheated air, different bed heights have different temperature ranges, and on the other hand, the fact that the bed pressure drop is not uniform objectively exists, in the reaction process, the temperature drop amplitude of different positions of the bed is not uniform due to bias flow, so that the reaction is not uniform, and the service life of the catalyst and the yield of propylene products are seriously influenced. Therefore, in order to improve the problems of temperature distribution, heat storage and the like of a propane dehydrogenation reaction bed layer, the invention develops a CuO-loaded heat storage material with a special pore channel structure.
Disclosure of Invention
The invention provides a heat storage material with a specific pore structure and a preparation method thereof, which are applied to a reaction process for preparing propylene by catalytic dehydrogenation of propane, wherein the heat storage material has oxidation and reduction properties at the same time, has no catalytic activity on the dehydrogenation reaction of propane, and cannot cause other side reactions; and can be selectively added into any place where heat is needed in the catalyst bed layer of the fixed bed reactor according to the characteristics of propane dehydrogenation reaction, so that the bed layer temperature can reach an accurate targeting type uniform distribution state, the heat generated by hot air or gas injection combustion can be partially replaced, the propane conversion rate and the propylene selectivity can be further improved, the service life of the catalyst is prolonged, and the energy consumption of the device is reduced.
A preparation method of a heat storage material with specific pore size distribution applied to a reaction process for preparing propylene by propane catalytic dehydrogenation comprises the following steps:
(1) by using pore-forming agent to Al2O3The carrier material is subjected to pore structure modulation treatment, and the pore-forming agent is one or more of citric acid, oxalic acid, benzoic acid, polyvinyl alcohol, polyvinyl butyral, polymer microspheres (such as polybutadiene microspheres, polyisoprene microspheres and the like), starch, stearic acid, activated carbon, graphite, phenolic resin, urea and the like; pore-forming agent and Al2O3The weight ratio of (1) is 0.05-0.25: 1.
(2) carrying out molding treatment on the carrier material obtained in the step (1), wherein the molded carrier material has the shape characteristics that: one of columnar, spherical or sheet-like, preferably columnar.
(3) And (3) roasting the carrier material formed in the step (2) for 3-10 hours at 500-1000 ℃ in an air atmosphere.
(4) Preparing xCuO + yM by using the material obtained in the step (3) as a carrier and adopting an impregnation methodzO/Carrier Supported Material (Al)2O3Supported CuO-based materials) where M ═ one or more of alkali metals or alkaline earth metals, MzThe precursor of O is nitrate, carbonate or hydroxide of alkali metal or alkaline earth metal, such as Na, and alkaline earth metal such as Ca; precursor materials of the CuO metal oxide are corresponding (Cu) soluble nitrate, chloride, oxalate, acetate or citrate; z is 1-2, x and y are CuO and MzO loading: x is 5-10 wt%, and y is 10-20 wt%;
(5) the xCuO + yM prepared in the step (4)zThe O/carrier-loaded heat storage material is roasted for 3-10 hours at 700-1500 ℃ in an air atmosphere.
The invention also provides a heat storage material which is prepared by the method and has a specific pore structure and is used for preparing propylene by catalytic dehydrogenation of propane.
The third aspect of the invention also provides the application of the heat storage material in the reaction for preparing the propylene by directly dehydrogenating the propane, and the heat storage material is mixed with the catalyst for preparing the propylene by dehydrogenating the propaneAnd mixing and applying the catalyst to the reaction of preparing propylene by propane dehydrogenation, wherein the weight ratio of the catalyst to the heat storage material is 2-10: 1; the reaction conditions are as follows: the reaction pressure is 40-60 kPa, the reaction temperature is 560-620 ℃, and the propane reaction space velocity is 300-400 ml/g-1·h-1(ii) a The specific reaction conditions are as follows: the reaction is 4 processes controlled automatically and sequentially, wherein in the first process, the propane dehydrogenation reaction is carried out for 5-10 min under 40-60 kPa; in the second process, purging with water vapor at 40-60 kPa for 2-5 min; in the third process (regeneration stage), air regeneration reaction is carried out for 5-10 min under normal pressure; the fourth process (reduction stage) is H under 10-30 kPa2Carrying out reduction treatment reaction for 5-10 min; preferably: the first process, dehydrogenation reaction of propane under 50kPa for 7 min; the second process, purging with 50kPa steam for 2 min; the third process (regeneration stage) is air regeneration reaction for 6min under normal pressure; fourth procedure (reduction stage), H at 20kPa2Reduction treatment reaction for 6 min.
Has the advantages that:
the heat storage material with the specific pore structure is mixed with a catalyst and then used in a reaction process for preparing propylene by direct dehydrogenation of propane, can further improve the conversion rate of propane and the selectivity of propylene, releases a large amount of heat in a reduction stage and an air regeneration stage of the reaction, accurately positions the heat distribution in a targeting manner according to the characteristics of the propane dehydrogenation reaction, is favorable for long-period operation of the catalyst, and is expected to prolong the service life of the catalyst by about half a year to 1 year in industrial application. In addition, the temperature distribution of a catalyst bed layer of the fixed bed reactor is improved, the temperature of a regeneration air inlet or the flow of regeneration air is greatly reduced, the probability of occurrence of a thermal cracking side reaction is reduced, the conversion rate of propane and the selectivity of the product propylene are improved, the energy consumption of a device is also reduced, and therefore investment is saved and economic benefits are improved.
The heat storage material and the preparation method thereof provided by the invention are simple, low in cost and good in repeatability.
Drawings
FIG. 1 is a graph showing the distribution of pore diameters of the heat storage materials prepared in examples 1 to 5 and comparative example 2 (from top to bottom, the heat storage materials of examples 1 to 5 and comparative example 2, respectively).
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
Example 1
According to the pore-forming agent and Al2O3Adding activated carbon to Al in a weight ratio of 0.10:12O3In the method, a columnar carrier is prepared by adopting a way of extrusion molding of a strip extruding machine. The support was calcined in a muffle furnace at 600 ℃ for 3 hours. Preparing a 5 wt% CuO +15 wt% CaO/carrier heat storage material by adopting an immersion method, weighing a certain amount of copper nitrate and calcium nitrate according to a chemical formula, dissolving in deionized water, stirring for 25min, adding into a columnar carrier, and drying the obtained heat storage material in a 100 ℃ oven at an interval of night. And roasting the dried heat storage material in a muffle furnace at 1200 ℃ for 3 hours. The pore structure is shown in figure 1.
Example 2
According to the pore-forming agent and Al2O3Adding citric acid to Al at a weight ratio of 0.10:12O3In the method, a columnar carrier is prepared by adopting a way of extrusion molding of a strip extruding machine. The support was calcined in a muffle furnace at 600 ℃ for 3 hours. Preparing a 5 wt% CuO +15 wt% CaO/carrier heat storage material by adopting an immersion method, weighing a certain amount of copper nitrate and calcium nitrate according to a chemical formula, dissolving in deionized water, stirring for 25min, adding into a columnar carrier, and drying the obtained heat storage material in a 100 ℃ oven at an interval of night. And roasting the dried heat storage material in a muffle furnace at 1200 ℃ for 3 hours. The pore structure is shown in figure 1.
Example 3
According to the pore-forming agent and Al2O3Adding starch to Al in a weight ratio of 0.10:12O3In the method, a columnar carrier is prepared by adopting a way of extrusion molding of a strip extruding machine. The support was calcined in a muffle furnace at 600 ℃ for 3 hours. Preparing a 5 wt% CuO +15 wt% CaO/carrier heat storage material by adopting an immersion method, weighing a certain amount of copper nitrate and calcium nitrate according to a chemical formula, dissolving in deionized water, stirring for 25min, adding into a columnar carrier, and drying the obtained heat storage material in a 100 ℃ oven at an interval of night. Heat storage material after dryingThe mixture was calcined in a muffle furnace at 1200 ℃ for 3 hours. The pore structure is shown in figure 1.
Example 4
According to the pore-forming agent and Al2O3Adding phenolic resin into Al at a weight ratio of 0.10:12O3In the method, a columnar carrier is prepared by adopting a way of extrusion molding of a strip extruding machine. The support was calcined in a muffle furnace at 600 ℃ for 3 hours. Preparing a 5 wt% CuO +15 wt% CaO/carrier heat storage material by adopting an immersion method, weighing a certain amount of copper nitrate and calcium nitrate according to a chemical formula, dissolving in deionized water, stirring for 25min, adding into a columnar carrier, and drying the obtained heat storage material in a 100 ℃ oven at an interval of night. And roasting the dried heat storage material in a muffle furnace at 1200 ℃ for 3 hours. The pore structure is shown in figure 1.
Example 5
According to the pore-forming agent and Al2O3Adding urea to Al in a weight ratio of 0.10:12O3In the method, a columnar carrier is prepared by adopting a way of extrusion molding of a strip extruding machine. The support was calcined in a muffle furnace at 600 ℃ for 3 hours. Preparing a 5 wt% CuO +15 wt% CaO/carrier heat storage material by adopting an immersion method, weighing a certain amount of copper nitrate and calcium nitrate according to a chemical formula, dissolving in deionized water, stirring for 25min, adding into a columnar carrier, and drying the obtained heat storage material in a 100 ℃ oven at an interval of night. And roasting the dried heat storage material in a muffle furnace at 1200 ℃ for 3 hours. The pore structure is shown in figure 1.
Example 6
In the embodiments 1 to 5, the heat storage materials with different pore structures and specific surface areas are mixed with a self-made propylene catalyst (Chinese patent, 202010076239.2) prepared by propane catalytic dehydrogenation and used for the reaction of preparing propylene by propane direct dehydrogenation. Weighing 10g of forming catalyst, mixing 8g of heat storage material, wherein the reaction raw material gas is pure propane, the reaction pressure is 50kPa, the reaction temperature is 575 ℃ and 605 ℃, and the reaction space velocity is 320 ml/g-1·h-1The reaction is 4 processes which are automatically controlled in sequence, wherein in the first process, the propane dehydrogenation reaction is carried out for 7min under 50 kPa; the second process, purging with 50kPa steam for 2 min; the third process (regeneration stage) is air regeneration reaction for 6min under normal pressure; the fourth process (reduction stage)) H at 20kPa2Reduction treatment reaction for 6 min. The reaction results are shown in table 1.
Example 7
According to the pore-forming agent and Al2O3Adding activated carbon to Al in a weight ratio of 0.10:12O3In the method, a columnar carrier is prepared by adopting a way of extrusion molding of a strip extruding machine. The support was calcined in a muffle furnace at 600 ℃ for 3 hours. Preparing 10wt% of CuO and 15 wt% of CaO/carrier heat storage material by adopting an impregnation method, weighing a certain amount of copper nitrate and calcium nitrate according to a chemical formula, dissolving in deionized water, stirring for 25min, adding into a columnar carrier, and drying the obtained heat storage material in a 100 ℃ oven at an interval of night. And roasting the dried heat storage material in a muffle furnace at 1200 ℃ for 3 hours.
Example 8
According to the pore-forming agent and Al2O3Adding activated carbon to Al in a weight ratio of 0.10:12O3In the method, a columnar carrier is prepared by adopting a way of extrusion molding of a strip extruding machine. The support was calcined in a muffle furnace at 600 ℃ for 3 hours. Preparing a 5 wt% CuO +15 wt% CaO/carrier heat storage material by adopting an immersion method, weighing a certain amount of copper nitrate and calcium nitrate according to a chemical formula, dissolving in deionized water, stirring for 25min, adding into a columnar carrier, and drying the obtained heat storage material in a 100 ℃ oven at an interval of night. And roasting the dried heat storage material in a muffle furnace at 1400 ℃ for 3 hours.
Example 9
According to the pore-forming agent and Al2O3Adding activated carbon to Al in a weight ratio of 0.20:12O3In the method, a columnar carrier is prepared by adopting a way of extrusion molding of a strip extruding machine. The support was calcined in a muffle furnace at 600 ℃ for 3 hours. Preparing a 5 wt% CuO +15 wt% CaO/carrier heat storage material by adopting an immersion method, weighing a certain amount of copper nitrate and calcium nitrate according to a chemical formula, dissolving in deionized water, stirring for 25min, adding into a columnar carrier, and drying the obtained heat storage material in a 100 ℃ oven at an interval of night. And roasting the dried heat storage material in a muffle furnace at 1200 ℃ for 3 hours.
Example 10
Examples 7 to 9Under the same condition, the heat storage material prepared by adding activated carbon is mixed with a self-made propylene catalyst (Chinese patent, 202010076239.2) prepared by propane catalytic dehydrogenation for direct propylene preparation reaction by propane dehydrogenation. Weighing 10g of forming catalyst, mixing 8g of heat storage material, wherein the reaction raw material gas is pure propane, the reaction pressure is 50kPa, the reaction temperature is 575 ℃ and 605 ℃, and the reaction space velocity is 320 ml/g-1·h-1The reaction is 4 processes which are automatically controlled in sequence, wherein in the first process, the propane dehydrogenation reaction is carried out for 7min under 50 kPa; the second process, purging with 50kPa steam for 2 min; the third process (regeneration stage) is air regeneration reaction for 6min under normal pressure; fourth procedure (reduction stage), H at 20kPa2Reduction treatment reaction for 6 min. The reaction results are shown in Table 2.
Comparative example 1
The heat storage material is not added in the reaction of preparing the propylene by propane dehydrogenation: the performance test of propylene prepared by propane dehydrogenation at 575 ℃ is carried out by only using the self-made catalyst (Chinese patent, 202010076239.2), and the results are shown in Table 2. The test process is as follows: weighing 10g of formed catalyst, wherein the reaction raw material gas is pure propane, the reaction pressure is 50kPa, the reaction temperature is 575 ℃, and the reaction space velocity is 320 ml/g-1·h-1The reaction is 4 processes which are automatically controlled in sequence, wherein in the first process, the propane dehydrogenation reaction is carried out for 7min under 50 kPa; the second process, purging with 50kPa steam for 2 min; the third process (regeneration stage) is air regeneration reaction for 6min under normal pressure; fourth procedure (reduction stage), H at 20kPa2Reduction treatment reaction for 6 min. As can be seen from table 1, the amount of heat released (change in temperature difference) during the reduction stage and the air regeneration stage of the reaction was the lowest without adding a heat storage material.
Comparative example 2
Preparing a pore-forming agent-free heat storage material: mixing Al2O3Directly extruding into a columnar carrier, and roasting the carrier in a muffle furnace at 600 ℃ for 3 hours. Preparing a 5 wt% CuO +15 wt% CaO/carrier heat storage material by adopting an immersion method, weighing a certain amount of copper nitrate and calcium nitrate according to a chemical formula, dissolving in deionized water, stirring for 25min, adding into a columnar carrier, and drying the obtained heat storage material in a 100 ℃ oven at an interval of night. Putting the dried heat storage material in a muffle furnace at 1200 DEG CAnd roasting for 3 hours to obtain the pore-forming agent-free heat storage material. The catalyst is mixed with a self-made catalyst (Chinese patent, 202010076239.2) for preparing propylene by catalytic dehydrogenation of propane and is used for the reaction of preparing propylene by direct dehydrogenation of propane. 10g of the shaped catalyst was weighed and mixed with 8g of the pore-forming agent-free heat storage material prepared in this comparative example, the reaction feed gas was pure propane, the reaction pressure was 50kPa, the reaction temperature was 575 ℃, and the reaction space velocity was 320 ml/g-1·h-1The reaction is 4 processes which are automatically controlled in sequence, wherein in the first process, the propane dehydrogenation reaction is carried out for 7min under 50 kPa; the second process, purging with 50kPa steam for 2 min; the third process (regeneration stage) is air regeneration reaction for 6min under normal pressure; fourth procedure (reduction stage), H at 20kPa2Reduction treatment reaction for 6 min. As can be seen from table 1, the heat storage material without pore-forming agent releases less heat during the reduction stage and the air regeneration stage of the reaction than the heat storage material system with pore-forming agent, and the propylene concentration, propane conversion and propylene selectivity in the product are also slightly lower than those of the heat storage material system with pore-forming agent.
TABLE 1 Effect of the addition of Heat storage materials on the exotherm and Performance of propane dehydrogenation reactions in examples 1-5
TABLE 2 Effect of the addition of Heat storage materials on the exotherm and performance of propane dehydrogenation reactions in examples 7-9
Claims (8)
1. A preparation method of a heat storage material with a pore structure for preparing propylene by propane catalytic dehydrogenation is characterized by comprising the following steps: the method comprises the following steps:
(1) by using pore-forming agent to Al2O3The carrier material is processed by pore structure modulation, and the pore-forming agent is citric acid, oxalic acid, benzoic acid, polyvinyl alcohol, polyvinyl butyral, polymer microsphere, starch, stearic acid, and active carbonOne or more of graphite, phenolic resin and urea; pore-forming agent and Al2O3The weight ratio of (A) to (B) is 0.05-0.25: 1; the polymer microspheres are polybutadiene microspheres or polyisoprene microspheres;
(2) carrying out molding treatment on the carrier material obtained in the step (1), wherein the shape of the molded carrier material is columnar, spherical or flaky;
(3) subjecting the carrier material formed in the step (2) to 500-1000 ℃ in air atmosphereoC, roasting for 3-10 hours;
(4) preparing xCuO + yM by using the heat storage material obtained in the step (3) as a carrier and adopting an immersion methodzThe O/carrier-loaded heat storage material comprises M, z = 1-2, and x and y are CuO and M respectivelyzLoading of O: x = 5-10 wt%, and y = 10-20 wt%;
(5) the xCuO + yM prepared in the step (4)zThe O/carrier-loaded heat storage material is subjected to 700-1500 times of treatment in an air atmosphereoAnd C, roasting for 3-10 hours.
2. The method of claim 1, wherein: the precursor material of the CuO is correspondingly soluble nitrate, chloride, oxalate, acetate or citrate; the M iszThe precursor material of O is nitrate, carbonate or hydroxide of alkali metal or alkaline earth metal.
3. The production method according to claim 1 or 2, characterized in that: the alkali metal is Na, and the alkaline earth metal is Ca.
4. The heat storage material with pore structure for preparing propylene by catalytic dehydrogenation of propane prepared by the method of any one of claims 1-3.
5. The use of the heat storage material of claim 4 in the reaction of direct dehydrogenation of propane to propylene.
6. Use according to claim 5, characterized in that: the heat storage material is mixed with a catalyst for preparing propylene by catalytic dehydrogenation of propane, and the weight ratio of the catalyst to the heat storage material is (2-10): 1.
7. use according to claim 6, characterized in that: the reaction conditions are as follows: the reaction pressure is 40-60 kPa, and the reaction temperature is 560-620 kPaoC, propane reaction space velocity of 300-400 ml/g-1·h-1。
8. Use according to claim 6 or 7, characterized in that: the specific reaction comprises 4 processes: in the first process, carrying out propane dehydrogenation reaction for 5-10 min under 40-60 kPa; in the second process, purging with water vapor at 40-60 kPa for 2-5 min; in the third process, air regeneration reaction is carried out for 5-10 min under normal pressure; the fourth process is H under 10-30 kPa2And carrying out reduction treatment reaction for 5-10 min.
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| CN106029612A (en) * | 2014-03-14 | 2016-10-12 | 科莱恩公司 | Improved dehydrogenation process with heat generating material |
| CN107074683A (en) * | 2014-11-26 | 2017-08-18 | 沙特基础工业全球技术有限公司 | Parallel reduction for improving dehydrating alkanes performance |
| CN107249733A (en) * | 2015-02-23 | 2017-10-13 | 沙特基础工业全球技术有限公司 | Catalytic composite materials and the improved method for hydrocarbon dehydrogenation |
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| CN107074683A (en) * | 2014-11-26 | 2017-08-18 | 沙特基础工业全球技术有限公司 | Parallel reduction for improving dehydrating alkanes performance |
| CN107249733A (en) * | 2015-02-23 | 2017-10-13 | 沙特基础工业全球技术有限公司 | Catalytic composite materials and the improved method for hydrocarbon dehydrogenation |
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