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CN120079400A - Preparation method and application of platinum-based ethane oxidative dehydrogenation catalyst - Google Patents

Preparation method and application of platinum-based ethane oxidative dehydrogenation catalyst Download PDF

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Publication number
CN120079400A
CN120079400A CN202510541070.6A CN202510541070A CN120079400A CN 120079400 A CN120079400 A CN 120079400A CN 202510541070 A CN202510541070 A CN 202510541070A CN 120079400 A CN120079400 A CN 120079400A
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platinum
solution
cobalt
oxidative dehydrogenation
tungstate
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徐林
王琳琳
耿德敏
俎文波
刘利娜
张浩波
刘建路
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Shandong Haihua Co ltd
Shandong Haihua Group Co Ltd
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Shandong Haihua Co ltd
Shandong Haihua Group Co Ltd
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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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • 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
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • 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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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention provides a preparation method and application of a platinum-based ethane oxidative dehydrogenation catalyst, which belong to the technical field of ethane oxidative dehydrogenation catalysts, wherein cobalt salt solution is dripped into sodium tungstate solution and stirred uniformly to obtain precursor solution; dropwise adding a sodium hydroxide solution into a precursor solution, regulating the pH value of the precursor solution to be slightly alkaline, standing, filtering to obtain a cobalt tungstate precursor, washing, drying and calcining the cobalt tungstate precursor to obtain cobalt tungstate, adding a dinitroso diammine platinum aqueous solution serving as an impregnating solution into the impregnating solution, stirring, drying and calcining to obtain an impregnating product, tabletting, granulating and sieving the impregnating product to obtain the platinum-based ethane oxidative dehydrogenation catalyst. The platinum-based ethane oxidative dehydrogenation catalyst prepared by the method is used for carbon dioxide oxidative ethane dehydrogenation reaction, and has high carbon dioxide conversion rate, difficult sintering and strong stability.

Description

Preparation method and application of platinum-based ethane oxidative dehydrogenation catalyst
Technical Field
The invention belongs to the technical field of ethane oxidative dehydrogenation catalysts, and particularly relates to a preparation method and application of a platinum-based ethane oxidative dehydrogenation catalyst.
Background
The ethane source is abundant, and is the second largest component next to methane in shale gas, so that ethane dehydrogenation reaction is a promising and economic ethylene production path, and can replace energy-intensive and environment-unfriendly naphtha and ethylene production path of ethane steam cracking. Capturing and comprehensive utilization of carbon dioxide is becoming more and more important. The method for preparing ethylene by combining ethane and CO 2, namely the method for preparing ethylene by CO 2 assisted ethane oxidative dehydrogenation (CO 2 -ODH), not only can effectively utilize CO 2, but also can prepare ethylene with higher added value.
The Chinese patent document with publication number CN 110170333A discloses a catalyst for preparing ethylene by ethane under carbon dioxide atmosphere and a preparation method thereof, wherein an HZSM-5 molecular sieve is used as a carrier, active metals Ga, co, ni and the like are used as active metals, and in ethane dehydrogenation reaction under CO 2 atmosphere, the catalyst has higher ethane conversion rate, but the catalyst active components are sintered in a high-temperature environment due to the acidity and structure of the HZSM-5 molecular sieve carrier, so that the catalyst has lower stability.
The Chinese patent document with publication number of CN118059918A discloses a preparation method of a low-content Zn-based catalyst for preparing ethylene by CO 2 oxyethane dehydrogenation, and a Silicalite-1 molecular sieve is used as a carrier to load Zn elements and Zr elements to obtain a ZnZr@S-1 catalyst. The catalyst reacts at a space velocity of 9000 mL.g -1·h-1 in a reaction atmosphere with C 2H6:CO2:N2 =5:10:85 at 700 ℃, and the catalyst shows an ethane conversion rate of 34.62% -44.54% according to different component proportions, but active metal is easy to sinter, and the catalyst has poor stability.
The Chinese patent document with publication number CN 116408095A discloses a crystal face adjustable catalyst for the reaction of carbon dioxide and ethane and a preparation method, which uses CeO 2 as a carrier and a crystal face adjustable catalytic system of Fe-Ni double-active metal components, solves the problems that the catalytic direction is difficult to regulate and control and the selectivity of a product is poor, but shows lower carbon dioxide conversion rate.
The Chinese patent document with publication number CN 106984297A discloses a gallium catalyst for preparing ethylene by ethane dehydrogenation under carbon dioxide atmosphere and a preparation method thereof, wherein titanium oxide doped with 1% -20% of silicon oxide is used as a carrier, 1% -15% of gallium oxide is used as a catalytic system of active components, the total reaction gas flow is 30mL/min at the reaction temperature of 650 ℃, the composition ratio of raw material gas is C 2H6:CO2:N2 =3:15:82 for carrying out carbon dioxide ethane oxidation dehydrogenation reaction, the ethylene yield is 28.6%, the reaction temperature required by the reaction is higher, the adsorption and activation capability of the catalyst to CO 2 are lower, and the lower CO 2 conversion rate is shown.
The Chinese patent document with publication number CN1161307C discloses a catalyst for preparing ethylene by oxidative dehydrogenation of carbon dioxide ethane at low temperature, the catalyst is prepared by impregnating an ethane oxidative dehydrogenation catalyst of modified active carbon with transition metal, and the highest ethylene yield is not more than 20 percent under the conditions of 700 ℃ reaction temperature, 0.01-1 MPa reaction pressure and 500-5000 h -1 ethane airspeed.
Disclosure of Invention
The invention aims to provide a preparation method of an anti-sintering platinum-based ethane oxidative dehydrogenation catalyst, which is used for carbon dioxide oxidative ethane dehydrogenation reaction, and has the advantages of high carbon dioxide conversion rate, difficult sintering and strong stability.
In order to achieve the above object, the present invention provides the following technical solutions:
In one aspect, the invention provides a method for preparing a platinum-based ethane oxidative dehydrogenation catalyst, comprising the following steps:
(1) Dripping cobalt salt water solution into sodium tungstate water solution, and uniformly stirring to obtain precursor solution;
(2) Dropwise adding a sodium hydroxide solution into the precursor solution, regulating the pH value of the precursor solution to be neutral or slightly alkaline, standing, and filtering to obtain a cobalt tungstate precursor;
(3) Adding cobalt tungstate into impregnating solution, stirring, drying and calcining to obtain an impregnating product, tabletting, granulating and sieving the impregnating product to obtain the platinum-based ethane oxidative dehydrogenation catalyst.
Further, in the step (1), the molar ratio of cobalt ions in the cobalt salt aqueous solution to tungstate radicals in the sodium tungstate aqueous solution is 1:1-1.1, the stirring temperature is 30-40 ℃, the rotating speed is 300r/min, and the time is 20-30 min.
Further, in the step (2), the concentration of the sodium hydroxide solution is 0.05-0.2 mol/L, the stirring temperature is 30-40 ℃, the rotating speed is 300r/min, the time is 2-3h, and the sodium hydroxide solution is required to be dropwise added, so that the phenomenon that large-particle-size products are caused by overhigh local sodium hydroxide concentration when cobalt tungstate is formed is avoided, and the performance of the catalyst is influenced.
Further, in the step (2), the pH value of the precursor solution is 7-9. In the pH value range, nanometer cobalt tungstate particles with higher oxygen vacancies and uniform particle size and morphology can be formed, the cobalt tungstate morphology can be influenced by the excessively high pH value, OH-occupies the oxygen vacancies and inhibits defect generation, and the coprecipitation reaction can be inhibited by the excessively low pH value, so that incomplete precipitation is caused.
Further, in the step (2), the drying temperature is 80-100 ℃ and the time is 10-12 hours.
Further, in the step (2), the calcination temperature is 550-650 ℃, the time is 2-3 h, the heating rate is 2 ℃ per minute, and the lower heating rate is favorable for uniform generation of cobalt tungstate crystal forms.
Further, in the step (3), the mass ratio of the cobalt tungstate to the platinum ions in the dinitroso diammine platinum aqueous solution is 1 g:0.01-0.015 g.
In the step (3), the impregnating solution further contains a nitrate auxiliary agent, wherein the nitrate auxiliary agent is any one of tin nitrate, indium nitrate, zinc nitrate and potassium nitrate, and is preferably tin nitrate.
Further, in the step (3), the mass ratio of the platinum ions in the cobalt tungstate, dinitroso diammine platinum aqueous solution to the metal ions in the nitrate auxiliary agent is 1 g:0.01-0.015 g:0.005-0.01 g.
Further, in the step (3), the stirring temperature is 30-40 ℃, the rotating speed is 300r/min, the time is 10min, the drying temperature is 110-130 ℃, the time is 10-12 h, the calcining temperature is 550-650 ℃, the time is 2-3 h, and the heating rate is 2 ℃ per min.
Further, in the step (3), the particle size of the platinum-based ethane oxidative dehydrogenation catalyst is required to be 20-40 meshes.
On the other hand, the invention discloses application of the platinum-based ethane oxidative dehydrogenation catalyst prepared by the preparation method in carbon dioxide oxidative ethane dehydrogenation reaction.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) According to the preparation method of the platinum-based ethane oxidative dehydrogenation catalyst, cobalt salt and sodium tungstate are prepared into cobalt tungstate through a coprecipitation method, oxygen vacancies in the reduced cobalt tungstate can be used as active sites of CO 2, C=O bonds of CO 2 are weakened, the problem that CO 2 capturing and activating capacity is poor in a carbon dioxide oxidative ethane dehydrogenation reaction is solved, carbon dioxide conversion rate is improved, when cobalt tungstate is used as a carrier, part of W 6+ can be reduced into W 5+ or W 4+ at high temperature or in a reducing atmosphere, more oxygen vacancies are generated, pt particles are promoted to be embedded into a cobalt tungstate surface layer, a Pt-Co-W-O composite interface is formed, strong metal-carrier interaction is generated, and the method is favorable for stabilizing metal active species and enhancing sintering resistance of Pt metal.
(2) The invention relates to a preparation method of a platinum-based ethane oxidative dehydrogenation catalyst, which prepares cobalt tungstate by coprecipitation of cobalt salt and sodium tungstate. In the preparation process, the pH value of a cobalt tungstate preparation system is regulated to obtain cobalt tungstate with good particle size, morphology and oxygen vacancy, so that the capturing and activating capacity of CO 2 is improved, and the dehydrogenation reaction of carbon dioxide and ethane oxide is promoted.
(3) According to the preparation method of the platinum-based ethane oxidative dehydrogenation catalyst, pt and a nitrate auxiliary agent are loaded on cobalt tungstate, pt metal provides dehydrogenation active sites, the electron density of active metal Pt is regulated and controlled by adding the nitrate auxiliary agent, and CH is inhibitedExcessive hydrogenation promotes dehydrogenation reaction of carbon dioxide and ethane oxide, and improves ethylene selectivity.
Drawings
FIG. 1 shows Transmission Electron Microscopy (TEM) of the catalysts prepared in example 1 and comparative example 5 before and after the reaction, wherein (a) is the catalyst of example 1:1.2Pt-0.7Sn/CoWO 4 before the reaction, (b) is the catalyst of example 1:1.2Pt-0.7Sn/CoWO 4 after the reaction, (c) is the catalyst of comparative example 5:1.2Pt-0.7Sn/HZSM-5 before the reaction, and (d) is the catalyst of comparative example 5:1.2Pt-0.7Sn/HZSM-5 after the reaction.
FIG. 2 is a bar graph of the Pt particle size distribution before and after the reaction of the catalysts prepared in example 1 and comparative example 5, wherein (a) is before the reaction of the catalyst of example 1:1.2Pt-0.7Sn/CoWO 4, (b) is after the reaction of the catalyst of example 1:1.2Pt-0.7Sn/CoWO 4, (c) is before the reaction of the catalyst of comparative example 5:1.2Pt-0.7Sn/HZSM-5, and (d) is after the reaction of the catalyst of comparative example 5:1.2Pt-0.7 Sn/HZSM-5.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention.
In each of the examples and comparative examples, the chemicals used were commercially available chemically pure reagents.
Example 1
2.91G of cobalt nitrate hexahydrate was weighed into a beaker, 18mL of deionized water was added, 3.085g of sodium tungstate was weighed into another beaker, and 18mL of deionized water was added. The two beakers were placed on a constant temperature magnetic stirrer to dissolve them uniformly at a stirring temperature of 35 ℃. And then dropwise adding the cobalt nitrate solution into the sodium tungstate solution, and stirring for 30min to obtain a cobalt tungstate precursor solution.
Dropwise adding 0.05mol/L sodium hydroxide solution into the cobalt tungstate precursor solution, regulating the pH to 8, stirring for 2.5 hours, closing a magnetic stirrer, standing for 3 hours, filtering to obtain a cobalt tungstate precursor, washing the cobalt tungstate precursor with deionized water for 4 times, placing the product into a drying oven, drying at 80 ℃ for 11 hours, placing the dried product into a muffle furnace, calcining at a temperature rising rate of 2 ℃ per minute to 600 ℃, calcining for 2.5 hours, cooling the product to normal temperature, and taking out to obtain cobalt tungstate.
Respectively weighing dinitroso diammine platinum containing 0.024g of platinum and tin nitrate containing 0.014g of tin, putting into a beaker, adding 10mL of deionized water, stirring and dissolving uniformly to obtain the required impregnating solution, adding 2g of cobalt tungstate into the impregnating solution, stirring for 10min, putting into a drying oven, drying at 120 ℃ for 11h, putting the dried product into a muffle furnace, calcining at a temperature rising rate of 2 ℃ per min to 600 ℃ for 2.5h, cooling the product to normal temperature after calcining, and taking out to obtain the solid impregnated product.
Loading the solid impregnated product into a tabletting grinding tool, tabletting by a tabletting machine, granulating, and sieving by a 20-40-mesh stainless steel standard sleeve sieve to obtain the platinum-based ethane oxidative dehydrogenation catalyst, which is recorded as 1.2Pt-0.7Sn/CoWO 4.
Example 2
1.55G of cobalt sulfate was weighed into a beaker, 18mL of deionized water was added, 2.938g of sodium tungstate was weighed into another beaker, and 18mL of deionized water was added. The two beakers were placed on a constant temperature magnetic stirrer to dissolve them uniformly at a stirring temperature of 30 ℃. And then dropwise adding the cobalt nitrate solution into the sodium tungstate solution, and stirring for 25min to obtain a cobalt tungstate precursor solution.
Dropwise adding 0.2mol/L sodium hydroxide solution into the cobalt tungstate precursor solution, regulating the pH to 9, stirring for 3 hours, closing a magnetic stirrer, standing for 3 hours, filtering to obtain a cobalt tungstate precursor, washing the cobalt tungstate precursor with deionized water for 4 times, placing the product into a drying oven, drying at 100 ℃ for 10 hours, placing the dried product into a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃ per minute, calcining for 2 hours, cooling the product to normal temperature, and taking out to obtain the cobalt tungstate.
Respectively weighing dinitroso diammine platinum containing 0.02g of platinum and tin nitrate containing 0.02g of tin, putting into a beaker, adding 10mL of deionized water, stirring and dissolving uniformly to obtain the required impregnating solution, adding 2g of prepared cobalt tungstate into the impregnating solution, stirring for 10min, putting into a drying box, drying at 110 ℃ for 12h, putting the dried product into a muffle furnace, calcining at a temperature rising rate of 2 ℃ per min to 550 ℃ for 3h, cooling the product to normal temperature after the calcining is finished, and taking out to obtain the solid impregnating product.
And (3) loading the solid impregnated product into a tabletting grinding tool, tabletting by a tabletting machine, granulating, and sieving by a 20-40-mesh stainless steel standard sleeve sieve to obtain the platinum-based ethane oxidative dehydrogenation catalyst which is recorded as 1Pt-1Sn/CoWO 4.
Example 3
1.3G of cobalt chloride was weighed into a beaker, 18mL of deionized water was added, 3.232g of sodium tungstate was weighed into another beaker, and 18mL of deionized water was added. The two beakers were placed on a constant temperature magnetic stirrer to dissolve them uniformly at a stirring temperature of 40 ℃. And then dropwise adding the cobalt nitrate solution into the sodium tungstate solution, and stirring for 20min to obtain a cobalt tungstate precursor solution.
Dropwise adding 0.1mol/L sodium hydroxide solution into a cobalt tungstate precursor solution, regulating the pH to 7, stirring for 2 hours, closing a magnetic stirrer, standing for 3 hours, filtering to obtain a cobalt tungstate precursor, washing the cobalt tungstate precursor with deionized water for 4 times, placing the product into a drying oven, drying at 90 ℃ for 12 hours, placing the dried product into a muffle furnace, heating to 650 ℃ at a heating rate of 2 ℃/min, calcining for 3 hours, cooling the product to normal temperature, and taking out to obtain cobalt tungstate.
Respectively weighing dinitroso diammine platinum containing 0.03g of platinum and tin nitrate containing 0.01g of tin, putting into a beaker, adding 10mL of deionized water, stirring and dissolving uniformly to obtain the required impregnating solution, adding 2g of prepared cobalt tungstate into the impregnating solution, stirring for 10min, putting into a drying box, drying at 130 ℃ for 10h, putting the dried product into a muffle furnace, calcining at the temperature rising rate of 2 ℃ per min to 650 ℃ for 2h, cooling the product to normal temperature after the calcining is finished, and taking out to obtain the solid impregnating product.
Loading the solid impregnated product into a tabletting grinding tool, tabletting by a tabletting machine, granulating, and sieving by a 20-40-mesh stainless steel standard sleeve sieve to obtain the platinum-based ethane oxidative dehydrogenation catalyst, which is recorded as 1.5Pt-0.5Sn/CoWO 4.
Example 4
2.91G of cobalt nitrate hexahydrate was weighed into a beaker, 18mL of deionized water was added, 3.085g of sodium tungstate was weighed into another beaker, and 18mL of deionized water was added. The two beakers were placed on a constant temperature magnetic stirrer to dissolve them uniformly at a stirring temperature of 35 ℃. And then dropwise adding the cobalt nitrate solution into the sodium tungstate solution, and stirring for 30min to obtain a cobalt tungstate precursor solution.
Dropwise adding 0.05mol/L sodium hydroxide solution into the cobalt tungstate precursor solution, regulating the pH to 8, stirring for 2.5 hours, closing a magnetic stirrer, standing for 3 hours, filtering to obtain a cobalt tungstate precursor, washing the cobalt tungstate precursor with deionized water for 4 times, placing the product into a drying oven, drying at 80 ℃ for 11 hours, placing the dried product into a muffle furnace, calcining at a temperature rising rate of 2 ℃ per minute to 600 ℃, calcining for 2.5 hours, cooling the product to normal temperature, and taking out to obtain cobalt tungstate.
Respectively weighing dinitroso diammine platinum containing 0.024g of platinum and zinc nitrate containing 0.014g of zinc, putting into a beaker, adding 10mL of deionized water, stirring and dissolving uniformly to obtain the required impregnating solution, adding 2g of cobalt tungstate into the impregnating solution, stirring for 10min, putting into a drying oven, drying at 120 ℃ for 11h, putting the dried product into a muffle furnace, calcining at a temperature rising rate of 2 ℃ per min to 600 ℃ for 2.5h, cooling the product to normal temperature after calcining, and taking out to obtain the solid impregnated product.
Loading the solid impregnated product into a tabletting grinding tool, tabletting by a tabletting machine, granulating, and sieving by a 20-40-mesh stainless steel standard sleeve sieve to obtain the platinum-based ethane oxidative dehydrogenation catalyst, which is recorded as 1.2Pt-0.7Zn/CoWO 4.
Example 5
2.91G of cobalt nitrate hexahydrate was weighed into a beaker, 18mL of deionized water was added, 3.085g of sodium tungstate was weighed into another beaker, and 18mL of deionized water was added. The two beakers were placed on a constant temperature magnetic stirrer to dissolve them uniformly at a stirring temperature of 35 ℃. And then dropwise adding the cobalt nitrate solution into the sodium tungstate solution, and stirring for 30min to obtain a cobalt tungstate precursor solution.
Dropwise adding 0.05mol/L sodium hydroxide solution into the cobalt tungstate precursor solution, regulating the pH to 8, stirring for 2.5 hours, closing a magnetic stirrer, standing for 3 hours, filtering to obtain a cobalt tungstate precursor, washing the cobalt tungstate precursor with deionized water for 4 times, placing the product into a drying oven, drying at 80 ℃ for 11 hours, placing the dried product into a muffle furnace, calcining at a temperature rising rate of 2 ℃ per minute to 600 ℃, calcining for 2.5 hours, cooling the product to normal temperature, and taking out to obtain cobalt tungstate.
Respectively weighing dinitroso diammine platinum containing 0.024g of platinum and indium nitrate containing 0.014g of indium, putting into a beaker, adding 10mL of deionized water, stirring and dissolving uniformly to obtain the required impregnating solution, adding 2g of cobalt tungstate into the impregnating solution, stirring for 10min, putting into a drying oven, drying at 120 ℃ for 11h, putting the dried product into a muffle furnace, calcining at a temperature rising rate of 2 ℃ per min to 600 ℃ for 2.5h, cooling the product to normal temperature after calcining, and taking out to obtain the solid impregnated product.
Loading the solid impregnated product into a tabletting grinding tool, tabletting by a tabletting machine, granulating, and sieving by a 20-40-mesh stainless steel standard sleeve sieve to obtain the platinum-based ethane oxidative dehydrogenation catalyst, which is recorded as 1.2Pt-0.7In/CoWO 4.
Example 6
2.91G of cobalt nitrate hexahydrate was weighed into a beaker, 18mL of deionized water was added, 3.085g of sodium tungstate was weighed into another beaker, and 18mL of deionized water was added. The two beakers were placed on a constant temperature magnetic stirrer to dissolve them uniformly at a stirring temperature of 35 ℃. And then dropwise adding the cobalt nitrate solution into the sodium tungstate solution, and stirring for 30min to obtain a cobalt tungstate precursor solution.
Dropwise adding 0.05mol/L sodium hydroxide solution into the cobalt tungstate precursor solution, regulating the pH to 8, stirring for 2.5 hours, closing a magnetic stirrer, standing for 3 hours, filtering to obtain a cobalt tungstate precursor, washing the cobalt tungstate precursor with deionized water for 4 times, placing the product into a drying oven, drying at 80 ℃ for 11 hours, placing the dried product into a muffle furnace, calcining at a temperature rising rate of 2 ℃ per minute to 600 ℃, calcining for 2.5 hours, cooling the product to normal temperature, and taking out to obtain cobalt tungstate.
Respectively weighing dinitroso diammine platinum containing 0.024g of platinum and potassium nitrate containing 0.014g of potassium, putting into a beaker, adding 10mL of deionized water, stirring and dissolving uniformly to obtain the required impregnating solution, adding 2g of prepared cobalt tungstate into the impregnating solution, stirring for 10min, putting into a drying box, drying at 120 ℃ for 11h, putting the dried product into a muffle furnace, calcining for 2.5h at a heating rate of 2 ℃ per min, cooling the product to normal temperature, and taking out to obtain the solid impregnated product.
Loading the solid impregnated product into a tabletting grinding tool, tabletting by a tabletting machine, granulating, and sieving by a 20-40-mesh stainless steel standard sleeve sieve to obtain the platinum-based ethane oxidative dehydrogenation catalyst, which is recorded as 1.2Pt-0.7K/CoWO 4.
Example 7
2.91G of cobalt nitrate hexahydrate was weighed into a beaker, 18mL of deionized water was added, 3.085g of sodium tungstate was weighed into another beaker, and 18mL of deionized water was added. The two beakers were placed on a constant temperature magnetic stirrer to dissolve them uniformly at a stirring temperature of 35 ℃. And then dropwise adding the cobalt nitrate solution into the sodium tungstate solution, and stirring for 30min to obtain a cobalt tungstate precursor solution.
Dropwise adding 0.05mol/L sodium hydroxide solution into the cobalt tungstate precursor solution, regulating the pH to 8, stirring for 2.5 hours, closing a magnetic stirrer, standing for 3 hours, filtering to obtain a cobalt tungstate precursor, washing the cobalt tungstate precursor with deionized water for 4 times, placing the product into a drying oven, drying at 80 ℃ for 11 hours, placing the dried product into a muffle furnace, calcining at a temperature rising rate of 2 ℃ per minute to 600 ℃, calcining for 2.5 hours, cooling the product to normal temperature, and taking out to obtain cobalt tungstate.
Adding 2g of cobalt tungstate into the impregnating solution, stirring for 10min, drying for 11h at 120 ℃, then placing the dried product into a muffle furnace, heating to 600 ℃ at a heating rate of 2 ℃ per min, calcining for 2.5h, cooling to normal temperature, and taking out to obtain the solid impregnated product.
And (3) loading the solid impregnated product into a tabletting grinding tool, tabletting by a tabletting machine, granulating, and sieving by a 20-40-mesh stainless steel standard sleeve sieve to obtain the platinum-based ethane oxidative dehydrogenation catalyst, which is recorded as 1.2Pt/CoWO 4.
Comparative example 1
In comparison with example 1, this comparative example only carries auxiliary Sn.
2.91G of cobalt nitrate hexahydrate was weighed into a beaker, 18mL of deionized water was added, 3.085g of sodium tungstate was weighed into another beaker, and 18mL of deionized water was added. The two beakers were placed on a constant temperature magnetic stirrer to dissolve them uniformly at a stirring temperature of 35 ℃. And then dropwise adding the cobalt nitrate solution into the sodium tungstate solution, and stirring for 30min to obtain a cobalt tungstate precursor solution.
Dropwise adding 0.05mol/L sodium hydroxide solution into the cobalt tungstate precursor solution, regulating the pH to 8, stirring for 2.5 hours, closing a magnetic stirrer, standing for 3 hours, filtering to obtain a cobalt tungstate precursor, washing the cobalt tungstate precursor with deionized water for 4 times, placing the product into a drying oven, drying at 80 ℃ for 11 hours, placing the dried product into a muffle furnace, calcining at a temperature rising rate of 2 ℃ per minute to 600 ℃, calcining for 2.5 hours, cooling the product to normal temperature, and taking out to obtain cobalt tungstate.
Weighing tin nitrate with the weight of 0.014g of tin, putting the tin nitrate into a beaker, adding 10mL of deionized water, stirring and dissolving uniformly to obtain the required impregnating solution, adding 2g of prepared cobalt tungstate into the impregnating solution, stirring for 10min, putting into a drying oven, drying at 120 ℃ for 11h, putting the dried product into a muffle furnace, heating to 600 ℃ at the heating rate of 2 ℃ per min, calcining for 2.5h, cooling to normal temperature, and taking out to obtain the solid impregnated product.
Loading the solid impregnated product into a tabletting grinding tool, tabletting by a tabletting machine, granulating, and sieving by a 20-40-mesh stainless steel standard sleeve sieve to obtain the platinum-based ethane oxidative dehydrogenation catalyst, which is recorded as 0.7Sn/CoWO 4.
Comparative example 2
In comparison with example 1, this comparative example uses a cobalt tungstate carrier as a catalyst.
2.91G of cobalt nitrate hexahydrate was weighed into a beaker, 18mL of deionized water was added, 3.085g of sodium tungstate was weighed into another beaker, and 18mL of deionized water was added. The two beakers were placed on a constant temperature magnetic stirrer to dissolve them uniformly at a stirring temperature of 35 ℃. And then dropwise adding the cobalt nitrate solution into the sodium tungstate solution, and stirring for 30min to obtain a cobalt tungstate precursor solution.
Dropwise adding 0.05mol/L sodium hydroxide solution into the cobalt tungstate precursor solution, regulating the pH to 8, stirring for 2.5 hours, closing a magnetic stirrer, standing for 3 hours, filtering to obtain a cobalt tungstate precursor, washing the cobalt tungstate precursor with deionized water for 4 times, placing the product into a drying oven, drying at 80 ℃ for 11 hours, placing the dried product into a muffle furnace, calcining at a temperature rising rate of 2 ℃ per minute to 600 ℃, calcining for 2.5 hours, cooling the product to normal temperature, and taking out to obtain cobalt tungstate.
Loading cobalt tungstate into a tabletting grinding tool, tabletting by a tabletting machine, granulating, and sieving by a 20-40-mesh stainless steel standard sleeve sieve to obtain the platinum-based ethane oxidative dehydrogenation catalyst which is marked as CoWO 4.
Comparative example 3
The pH of the cobalt tungstate preparation system of this comparative example was 6 compared to example 1.
2.91G of cobalt nitrate hexahydrate was weighed into a beaker, 18mL of deionized water was added, 3.085g of sodium tungstate was weighed into another beaker, and 18mL of deionized water was added. The two beakers were placed on a constant temperature magnetic stirrer to dissolve them uniformly at a stirring temperature of 35 ℃. And then dropwise adding the cobalt nitrate solution into the sodium tungstate solution, and stirring for 30min to obtain a cobalt tungstate precursor solution.
Dropwise adding 0.05mol/L sodium hydroxide solution into the cobalt tungstate precursor solution, regulating the pH to 6, stirring for 2.5 hours, closing a magnetic stirrer, standing for 3 hours, filtering to obtain a cobalt tungstate precursor, washing the cobalt tungstate precursor with deionized water for 4 times, placing the product into a drying oven, drying at 80 ℃ for 11 hours, placing the dried product into a muffle furnace, calcining at a temperature rising rate of 2 ℃ per minute to 600 ℃, calcining for 2.5 hours, cooling the product to normal temperature, and taking out to obtain cobalt tungstate.
Respectively weighing dinitroso diammine platinum containing 0.024g of platinum and tin nitrate containing 0.014g of tin, putting into a beaker, adding 10mL of deionized water, stirring and dissolving uniformly to obtain the required impregnating solution, adding 2g of cobalt tungstate into the impregnating solution, stirring for 10min, putting into a drying oven, drying at 120 ℃ for 11h, putting the dried product into a muffle furnace, calcining at a temperature rising rate of 2 ℃ per min to 600 ℃ for 2.5h, cooling the product to normal temperature after calcining, and taking out to obtain the solid impregnated product.
Loading the solid impregnated product into a tabletting grinding tool, tabletting by a tabletting machine, granulating, and sieving by a 20-40-mesh stainless steel standard sleeve sieve to obtain the platinum-based ethane oxidative dehydrogenation catalyst, which is recorded as 1.2Pt-0.7Sn/CoWO 4 (pH=6).
Comparative example 4
The pH of the cobalt tungstate preparation system of this comparative example was 10 compared to example 1.
2.91G of cobalt nitrate hexahydrate was weighed into a beaker, 18mL of deionized water was added, 3.085g of sodium tungstate was weighed into another beaker, and 18mL of deionized water was added. The two beakers were placed on a constant temperature magnetic stirrer to dissolve them uniformly at a stirring temperature of 35 ℃. And then dropwise adding the cobalt nitrate solution into the sodium tungstate solution, and stirring for 30min to obtain a cobalt tungstate precursor solution.
Dropwise adding 0.05mol/L sodium hydroxide solution into the cobalt tungstate precursor solution, regulating the pH to 10, stirring for 2.5 hours, closing a magnetic stirrer, standing for 3 hours, filtering to obtain a cobalt tungstate precursor, washing the cobalt tungstate precursor with deionized water for 4 times, placing the product into a drying oven, drying at 80 ℃ for 11 hours, placing the dried product into a muffle furnace, calcining for 2.5 hours at a temperature rising rate of 2 ℃ per minute, cooling the product to normal temperature after the calcining is finished, and taking out to obtain cobalt tungstate.
Respectively weighing dinitroso diammine platinum containing 0.024g of platinum and tin nitrate containing 0.014g of tin, putting into a beaker, adding 10mL of deionized water, stirring and dissolving uniformly to obtain the required impregnating solution, adding 2g of cobalt tungstate into the impregnating solution, stirring for 10min, putting into a drying oven, drying at 120 ℃ for 11h, putting the dried product into a muffle furnace, calcining at a temperature rising rate of 2 ℃ per min to 600 ℃ for 2.5h, cooling the product to normal temperature after calcining, and taking out to obtain the solid impregnated product.
Loading the solid impregnated product into a tabletting grinding tool, tabletting by a tabletting machine, granulating, and sieving by a 20-40-mesh stainless steel standard sleeve sieve to obtain the platinum-based ethane oxidative dehydrogenation catalyst, which is recorded as 1.2Pt-0.7Sn/CoWO 4 (pH=10).
Comparative example 5
In this comparative example, HZSM-5 molecular sieve was selected as the carrier as compared with example 1.
Dinitroso diammine platinum containing 0.24g of platinum and tin nitrate containing 0.14g of tin are weighed respectively, put into a beaker, added with 10mL of deionized water, and stirred and dissolved uniformly to prepare the required impregnating solution.
2G of HZSM-5 molecular sieve is weighed and added into impregnating solution, stirring is carried out for 10min, the impregnating solution is put into a drying oven, drying is carried out for 11h at 120 ℃, then the dried product is put into a muffle furnace, the temperature is raised to 600 ℃ at the temperature rising rate of 2 ℃ per min, the calcining is carried out for 2.5h, after the calcining is finished, the product is cooled to normal temperature, and then the solid impregnated product is obtained.
Loading the solid impregnated product into a tabletting grinding tool, tabletting by a tabletting machine, granulating, and sieving by a 20-40-mesh stainless steel standard sleeve sieve to obtain the platinum-based ethane oxidative dehydrogenation catalyst, which is recorded as 1.2Pt-0.7Sn/HZSM-5.
Comparative example 6
The concentration of sodium hydroxide added dropwise in this comparative example was 0.3mol/L as compared with example 1.
2.91G of cobalt nitrate hexahydrate was weighed into a beaker, 18mL of deionized water was added, 3.085g of sodium tungstate was weighed into another beaker, and 18mL of deionized water was added. The two beakers were placed on a constant temperature magnetic stirrer to dissolve them uniformly at a stirring temperature of 35 ℃. And then dropwise adding the cobalt nitrate solution into the sodium tungstate solution, and stirring for 30min to obtain a cobalt tungstate precursor solution.
Dropwise adding 0.3mol/L sodium hydroxide solution into the cobalt tungstate precursor solution, regulating the pH to 8, stirring for 2.5 hours, closing a magnetic stirrer, standing for 3 hours, filtering to obtain a cobalt tungstate precursor, washing the cobalt tungstate precursor with deionized water for 4 times, placing the product into a drying oven, drying at 80 ℃ for 11 hours, placing the dried product into a muffle furnace, calcining at a temperature rising rate of 2 ℃ per minute to 600 ℃, calcining for 2.5 hours, cooling the product to normal temperature, and taking out to obtain cobalt tungstate.
Respectively weighing dinitroso diammine platinum containing 0.024g of platinum and tin nitrate containing 0.014g of tin, putting into a beaker, adding 10mL of deionized water, stirring and dissolving uniformly to obtain the required impregnating solution, adding 2g of cobalt tungstate into the impregnating solution, stirring for 10min, putting into a drying oven, drying at 120 ℃ for 11h, putting the dried product into a muffle furnace, calcining at a temperature rising rate of 2 ℃ per min to 600 ℃ for 2.5h, cooling the product to normal temperature after calcining, and taking out to obtain the solid impregnated product.
Loading the solid impregnated product into a tabletting grinding tool, tabletting by a tabletting machine, granulating, and sieving by a 20-40-mesh stainless steel standard sleeve sieve to obtain the platinum-based ethane oxidative dehydrogenation catalyst, wherein the platinum-based ethane oxidative dehydrogenation catalyst is recorded as 1.2Pt-0.7Sn/CoWO 4（CNaOH =0.3 mol/L.
Application example
The carbon dioxide to ethane dehydrogenation reaction is carried out in a continuous flow fixed bed reactor. Firstly, a small amount of quartz wool is plugged into the middle part of a high-temperature resistant quartz glass tube with the inner diameter of 12mm, 0.2 g of catalyst and 0.5 g of quartz sand are mixed and then filled into the quartz glass tube, and then, a small amount of quartz wool is plugged into the other side of the catalyst to fix the catalyst.
And (3) loading the quartz glass tube filled with the catalyst into a fixed bed reactor, introducing a small amount of nitrogen for purging, replacing air in the reactor, and reducing the catalyst by using 99.99% of hydrogen, wherein the hydrogen gas speed is 40mL/min, the temperature is 400 ℃, and the reduction time is 2h.
After the reduction is finished, the gas is switched to be nitrogen after natural cooling, the temperature is raised to 600 ℃, then the gas is switched to be ethane and CO 2、N2 raw material gas (ethane: CO 2:N2 =20:20:60), the reaction temperature is 600 ℃, the reaction pressure is 0.1MPa, and the space velocity of the raw material gas is 6000 mL/(g cat. H).
Catalyst performance evaluation was performed using the present application scheme, and the reaction results are shown in Table 1
As can be seen from the data of examples 1, 4,5, 6, 7 and comparative examples 1,2 in Table 1, the addition of Sn, zn, in, K promoter to the catalyst can increase ethylene selectivity. Among them, the ethylene selectivity is best up to 52.05% when Sn is used as an auxiliary agent, and the ethylene selectivity can also be up to 48.97% when the catalyst of example 7 is not added with Sn auxiliary agent. The experimental data of the catalyst in comparative example 1 show that Pt is the main active component of the reaction, and has no catalytic effect basically when only Sn is loaded, and the experimental data of the catalyst in comparative example 2 show that the cobalt tungstate carrier has no catalytic effect basically when no active component is loaded.
As can be seen from the data of example 1, comparative example 3 and comparative example 4 in table 1, the pH value of the cobalt tungstate preparation system affects the catalytic performance of the catalyst. Comparative example 3 in the preparation of cobalt tungstate support, pH 6, acidic environment affecting Co 2+ may be hydrolyzed and weakened, possibly resulting in incomplete precipitation of cobalt tungstate, and comparative example 4 in the preparation of cobalt tungstate support, pH 10, too high alkaline environment resulting in agglomeration of cobalt tungstate particles or formation of amorphous structure, because pH level affects the existence morphology of Co 2+ and tungstate radical. At the appropriate pH, co 2+ will hydrolyze to Co (OH) 2, whereas the tungstate exists as WO 4 2-, at which time CoWO 4 is more readily formed. However, at too high a pH, cobalt may form a cobalt hydroxide precipitate, while the tungstate may remain dissolved, resulting in incomplete precipitation, while OH-occupies oxygen vacancies, reducing surface defects, and adversely affecting active metal loading and CO 2 activation. Thus, the catalysts of comparative example 3 and comparative example 4 had reduced adsorption and activation capacity of the carrier for CO 2 during the carbon dioxide-to-ethane dehydrogenation reaction, thereby affecting the catalytic performance and resulting in lower CO 2 conversion.
As can be seen from the data of example 1 and comparative example 6 in table 1, the NaOH concentration for adjusting the pH had an effect on the performance of the catalyst during the cobalt tungstate support preparation. When the concentration of the dropwise added NaOH is more than 0.2mol/L, in the cobalt tungstate preparation process, cobalt tungstate particles are generated too quickly due to the too high local pH value of the system, the morphology of the cobalt tungstate is affected, and the performance of the catalyst is reduced.
As can be seen from the TEM images before and after the catalyst reaction (fig. 1) and the Pt particle size distribution bar graph before and after the catalyst reaction (fig. 2), the catalyst in example 1 (fig. 1a and 1 b) uses cooo 4 as the carrier, the sintering aggregation amount of Pt metal in the reaction process is small, and as can be seen from fig. 2a and 2b, the catalyst particle size becomes insignificant, which indicates that using cooo 4 as the carrier is favorable for generating strong metal-carrier interaction so as to stabilize the metal active species, reduce sintering of the active metal, and improve the sintering resistance of the Pt metal. In comparative example 5 (FIGS. 1c and 1 d), coWO4 was not used as a carrier, HZSM-5 molecules were used as a carrier, and it can be seen from FIGS. 2c and 2d that the particle size of Pt metal after the reaction was significantly increased.

Claims (11)

1.一种铂基乙烷氧化脱氢催化剂的制备方法，其特征在于，包括以下步骤：1. A method for preparing a platinum-based ethane oxidative dehydrogenation catalyst, characterized in that it comprises the following steps: （1）将钴盐水溶液滴加至钨酸钠水溶液中，搅拌均匀，得到前驱体溶液；(1) Add the cobalt salt aqueous solution dropwise into the sodium tungstate aqueous solution and stir evenly to obtain a precursor solution; （2）向前驱体溶液中滴加氢氧化钠溶液，调节前驱体溶液pH值至中性或弱碱性，静置、过滤，得到钨酸钴前驱体；将钨酸钴前驱体洗涤、烘干、煅烧，得到钨酸钴；(2) adding sodium hydroxide solution to the precursor solution, adjusting the pH value of the precursor solution to neutral or weak alkaline, standing and filtering to obtain a cobalt tungstate precursor; washing, drying and calcining the cobalt tungstate precursor to obtain cobalt tungstate; （3）以二亚硝基二氨铂水溶液为浸渍液，将钨酸钴加入浸渍液中，搅拌、烘干、煅烧制得浸渍产物，将浸渍产物进行压片，造粒，过筛得到铂基乙烷氧化脱氢催化剂。(3) Using a dinitrodiammine platinum aqueous solution as an impregnation solution, adding cobalt tungstate into the impregnation solution, stirring, drying, and calcining to obtain an impregnation product, and then tableting, granulating, and sieving the impregnation product to obtain a platinum-based ethane oxidative dehydrogenation catalyst. 2.根据权利要求1所述铂基乙烷氧化脱氢催化剂的制备方法，其特征在于，所述步骤（1）中，钴盐水溶液中的钴离子与钨酸钠水溶液中的钨酸根摩尔比为1:1～1.1；搅拌温度为30～40℃，转速为300r/min，时间为20～30min。2. The method for preparing a platinum-based ethane oxidative dehydrogenation catalyst according to claim 1, characterized in that in the step (1), the molar ratio of cobalt ions in the cobalt salt aqueous solution to tungstate in the sodium tungstate aqueous solution is 1:1-1.1; the stirring temperature is 30-40°C, the rotation speed is 300 r/min, and the time is 20-30 min. 3.根据权利要求1所述铂基乙烷氧化脱氢催化剂的制备方法，其特征在于，所述步骤（2）中，氢氧化钠溶液浓度为0.05～0.2mol/L；搅拌温度为30～40℃，转速为300r/min，时间为2～3h。3. The method for preparing a platinum-based ethane oxidative dehydrogenation catalyst according to claim 1, characterized in that in the step (2), the concentration of the sodium hydroxide solution is 0.05-0.2 mol/L; the stirring temperature is 30-40°C, the rotation speed is 300 r/min, and the time is 2-3 h. 4.根据权利要求1所述铂基乙烷氧化脱氢催化剂的制备方法，其特征在于，所述步骤（2）中，前驱体溶液pH值为7～9。4. The method for preparing a platinum-based ethane oxidative dehydrogenation catalyst according to claim 1, characterized in that in the step (2), the pH value of the precursor solution is 7 to 9. 5.根据权利要求1所述铂基乙烷氧化脱氢催化剂的制备方法，其特征在于，所述步骤（2）中，烘干温度为80～100℃，时间为10～12h；煅烧温度为550～650℃，时间为2～3h，升温速率为2℃/min。5. The method for preparing a platinum-based ethane oxidative dehydrogenation catalyst according to claim 1, characterized in that in the step (2), the drying temperature is 80-100° C., the time is 10-12 h; the calcination temperature is 550-650° C., the time is 2-3 h, and the heating rate is 2° C./min. 6.根据权利要求1所述铂基乙烷氧化脱氢催化剂的制备方法，其特征在于，所述步骤（3）中钨酸钴与二亚硝基二氨铂水溶液中的铂离子的质量比为1g:0.01～0.015g。6. The method for preparing a platinum-based ethane oxidative dehydrogenation catalyst according to claim 1, characterized in that the mass ratio of cobalt tungstate to platinum ions in the dinitrosodiammineplatinum aqueous solution in step (3) is 1g:0.01-0.015g. 7.根据权利要求1所述铂基乙烷氧化脱氢催化剂的制备方法，其特征在于，所述步骤（3）中，所述的浸渍液还含有硝酸盐助剂，硝酸盐助剂为硝酸锡、硝酸铟、硝酸锌、硝酸钾中的任意一种。7. The method for preparing a platinum-based ethane oxidative dehydrogenation catalyst according to claim 1, characterized in that in the step (3), the impregnation solution further contains a nitrate auxiliary agent, and the nitrate auxiliary agent is any one of tin nitrate, indium nitrate, zinc nitrate, and potassium nitrate. 8.根据权利要求7所述铂基乙烷氧化脱氢催化剂的制备方法，其特征在于，所述步骤（3）中，钨酸钴、二亚硝基二氨铂水溶液中的铂离子、硝酸盐助剂中的金属离子的质量比为1g:0.01～0.015g:0.005～0.01g。8. The method for preparing a platinum-based ethane oxidative dehydrogenation catalyst according to claim 7, characterized in that in the step (3), the mass ratio of cobalt tungstate, platinum ions in the dinitrodiammineplatinum aqueous solution, and metal ions in the nitrate additive is 1g:0.01-0.015g:0.005-0.01g. 9.根据权利要求1所述铂基乙烷氧化脱氢催化剂的制备方法，其特征在于，所述步骤（3）中，搅拌温度为30～40℃，转速为300r/min，时间为10min；烘干温度为110～130℃，时间为10～12h；煅烧温度为550～650℃，时间为2～3h，升温速率为2°C/min。9. The method for preparing a platinum-based ethane oxidative dehydrogenation catalyst according to claim 1, characterized in that in the step (3), the stirring temperature is 30-40°C, the rotation speed is 300 r/min, and the time is 10 min; the drying temperature is 110-130°C, and the time is 10-12 h; the calcination temperature is 550-650°C, the time is 2-3 h, and the heating rate is 2°C/min. 10.根据权利要求1所述铂基乙烷氧化脱氢催化剂的制备方法，其特征在于，所述步骤（3）中，所述铂基乙烷氧化脱氢催化剂粒径要求为20～40目。10. The method for preparing a platinum-based ethane oxidative dehydrogenation catalyst according to claim 1, characterized in that in the step (3), the particle size of the platinum-based ethane oxidative dehydrogenation catalyst is required to be 20 to 40 meshes. 11.一种如权利要求1～10中任一项所述制备方法制备的铂基乙烷氧化脱氢催化剂的应用，其特征在于，所述的铂基乙烷氧化脱氢催化剂应用在二氧化碳氧化乙烷脱氢反应中。11. Use of a platinum-based ethane oxidative dehydrogenation catalyst prepared by the preparation method according to any one of claims 1 to 10, characterized in that the platinum-based ethane oxidative dehydrogenation catalyst is used in the carbon dioxide oxidation dehydrogenation reaction of ethane.
CN202510541070.6A 2025-04-28 2025-04-28 Preparation method and application of platinum-based ethane oxidative dehydrogenation catalyst Pending CN120079400A (en)

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