CN113398961A - Method for preparing methanol by carbon dioxide hydrogenation based on molybdenum carbide catalyst - Google Patents
Method for preparing methanol by carbon dioxide hydrogenation based on molybdenum carbide catalyst Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 39
- 229910039444 MoC Inorganic materials 0.000 title claims abstract description 30
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 21
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 2
- 238000002161 passivation Methods 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 208000012839 conversion disease Diseases 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000009467 reduction Effects 0.000 description 27
- 239000007789 gas Substances 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000011068 loading method Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 241000282326 Felis catus Species 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- 238000010494 dissociation reaction Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
- C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a method for preparing methanol by carbon dioxide hydrogenation based on a molybdenum carbide catalyst, wherein the general formula of the molybdenum carbide catalyst is M/MoxCyWherein M is at least one of Cu and Pt, and accounts for 0.02-0.05% of the mass of the catalyst, and MoxCyIs alpha or beta phase molybdenum carbide. The molybdenum carbide catalyst is used for preparing methanol by carbon dioxide hydrogenation, and the reaction conditions are as follows: the reaction temperature is 200 ℃ and 300 ℃, the reaction pressure is 5MPa, and the space velocity of the raw material gas is 12000 mL/g/h. The catalyst of the invention has better catalytic performance at low temperature, and in the reaction, the reaction conversion rate and methanol selection are carried out within the range of 200-300 ℃ by regulating and controlling the reaction temperatureThe selectivity can be respectively regulated, the selectivity of methanol is reduced at high temperature, the selectivity of methane is improved, and the catalyst can realize different functions at different temperatures in industrial production.
Description
Technical Field
The invention relates to CO2A catalyst for preparing methanol by hydrogenation, and preparation and application thereof, belonging to CO2The technical field of hydrocatalysis conversion.
Background
Methanol is an important chemical intermediate raw material and can be used as a fuel for internal combustion engines and fuel cells, and along with the gradual reduction of non-renewable energy sources, methanol as a replaceable chemical raw material can be used for synthesizing various chemicals, gasoline and other fuels. In recent years, with the development of technologies such as a molecular sieve catalyst, Methanol To Olefin (MTO), Methanol to aromatic (MTG), and the like, the Demand of a fuel obtained from Methanol in the international market has been rapidly increasing (Johnson, d.global Methanol Demand Growth; IHS inc., 2016). The traditional industrial preparation of methanol adopts a synthesis gas conversion method, but mainly faces to a catalyst (Cu/ZnO/Al)2O3) The active sites are easy to sinter under the reaction conditions, which causes poor stability, and moreover, the raw material synthesis gas output of the process is often accompanied with the consumption of fossil resources such as coal, natural gas and the like and CO caused by the conversion process2Discharge and environmental pollution.
CO2Are the main components of greenhouse gases in the atmosphere, which result from the combustion of large quantities of fossil fuels and lead to increasingly deeper global climate change over the past decades. Human activity emits CO to the atmosphere every year2Nearly 400 hundred million tons of atmospheric CO in 20192The content is as high as 407ppm, and the growth is 20 percent in the last 40 years. Reduction of CO2The amount of discharge is certainly a pressing issue. If mixing CO with2By converting renewable energy into chemical raw materials, not only can CO be solved2Excess emission problem, and CO generation2Becomes a novel carbon source for replacing the traditional fossil fuel. CO22The molecules being chemically inert but incorporating H having a high free energy2The molecule as a reactant makes the reaction thermodynamically easy, while H2If the water is obtained by a renewable mode such as electrolytic water or photolytic water, the whole process has wide prospects in environment and economy. Thus, using CO2Catalytic hydrogenation to methanol is an attractive means of reducing CO2Discharge and create a new carbon cycle process scenario.
At present, CO2The hydrogenation for preparing methanol mainly adopts a supported metal or metal oxide catalyst, but because of CO2The chemical stability of (2) is high, and the activation temperature is generally 250 ℃ or above. For example, conventional Cu/ZnO/Al2O3(Science 352 2016 969–974),Cu/ZrO2(J.Am.chem.Soc.138201612440-12450), Pd/ZnO (J.Catal.3432016133-146), and the like. GmbH&Lurgi GmbH adopted catalyst Cu/ZnO/Al in 20102O3A methanol yield of 0.6kg CH at 40% conversion per pass was achieved in a commercial pilot plant3OH/L cat h, the catalytic performance of this type is often affected by changes in the surface chemistry of Cu and is easily deactivated by agglomeration under conditions where the reaction generates large amounts of water. At slightly higher temperatures, the selectivity of methanol in the product decreases, which in turn produces CO as a by-product. In recent years, Cu-Zn materials modified with transition metals have also been studied extensively, e.g., CuZnGa-hydrotalcite in CO2At a conversion of 20%, a methanol yield of 0.59kg CH was achieved3OH/L cat h, but the methanol selectivity was only around 50% (ACS Catal.2018,8, 4390-4401). And adopts noble metal loaded Pd/CeO2The methanol selectivity of the catalyst reaches 92 percent, but CO2Conversion is not ideal (J.Catal.,1994,150, 217-220). In view of the characteristic that the reaction is thermodynamically favorable at low temperature, the CO can be efficiently activated at lower temperature2And H2And has a higher CO2The catalyst for conversion rate and methanol selectivity is to realize CO2The industrial application of hydrogenation to prepare methanol is an urgent problem. It is stated that CO2Molecules are in a bent configuration when adsorbed on the surface of MoC, so that the activation of the MoC is facilitated, but the generated CO is not easy to desorb and can be continuously dissociated to generate methane through hydrogenation. The surface structure of the material is modified by doping metal atoms and the like, so that the characteristic of strong capability of inhibiting the carbon-oxygen bond dissociation of the materialAnd moderately increase dissociation H2The ability to increase low temperature CO2An effective way for preparing methanol by hydrogenation.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a method for efficiently activating CO at a lower temperature2And H2And has a higher CO2A catalyst for conversion and methanol selectivity.
In order to solve the technical problems, the technical scheme of the invention is realized by the following technical scheme:
a molybdenum carbide catalyst, characterized in that the general formula of the molybdenum carbide catalyst is M/MoxCyWherein M is at least one of Cu and Pt, and accounts for 0.02-0.05% of the mass of the catalyst, and MoxCyIs alpha or beta phase molybdenum carbide.
The invention also provides a preparation method of the molybdenum carbide catalyst, which is characterized in that chloroplatinic acid or copper nitrate is respectively dissolved in deionized water and is mixed with MoO3Mixing the powders, rotary steaming, and drying to obtain powder CH4And H2Purging in the mixed gas, carbonizing to obtain molybdenum carbide catalyst, and adding into O2And N2The mixed gas is passivated and then stored.
Preferably, the CH4And H2Mixed gas of (2) CH4Is 20% by volume, and the flow rate during purging is 150 mL/min.
Preferably, the carbonization process parameters are as follows: the temperature was raised from room temperature to 400 ℃ at a rate of 5 ℃/min, then to 700 ℃ at a rate of 0.5 ℃/min, and held for 1 hour.
Preferably, said O is2And N2O in the mixed gas of2Is 0.5 percent, and the passivation time is 220 min.
Preferably, the catalyst is Pt/alpha-MoxCyWhen in use, chloroplatinic acid is adopted as a precursor; the catalyst is Cu/beta-MoxCyWhen the precursor is copper nitrate.
The catalyst is reduced in situ before the evaluation of reaction performance, the reduction temperature is 500 ℃, the reduction time is 1h, the space velocity of hydrogen is 30000mL/g/h, and the reduction pressure is 0.1 MPa.
The invention also provides a method for preparing methanol by carbon dioxide hydrogenation based on the molybdenum carbide catalyst, which is used for preparing methanol by carbon dioxide hydrogenation under the following reaction conditions: the reaction temperature is 200 ℃ and 300 ℃, the reaction pressure is 5MPa, and the space velocity of the raw material gas is 12000 mL/g/h.
Preferably, the feed gas is made of CO2And H2Is prepared according to the volume ratio of 1: 3.
The invention provides a preparation scheme of a novel metal supported catalyst based on molybdenum carbide, and the preparation scheme is used for evaluating the reaction performance in a fixed bed reactor, and has the characteristics of low reaction temperature and high methanol space-time yield, wherein the platinum-based catalyst is prepared by using CO at the temperature of 200 ℃, the pressure of 5MPa and the space velocity of 12000mL/g cat h2The conversion rate is 9.8%, and the space-time yield of methanol can reach 72.6g CH under the same conditions of the copper-based catalyst3Compared with the results reported by the prior patent, the OH/kg cat h can realize the same performance at lower temperature, and the invention of the series of catalysts provides wide prospect for subsequent low-temperature industrial application.
Compared with the prior art, the method for preparing CO provided by the invention2The catalyst for preparing methanol by hydrogenation mainly has the following beneficial effects:
(1) according to the invention, metal Pd and Cu are doped into the traditional molybdenum carbide catalyst, so that the characteristic of strong adsorption and dissociation capability of the molybdenum carbide material CO2 is kept, excessive dissociation of carbon-oxygen bonds is inhibited to generate methane, and the selectivity of methanol is improved. The purpose of synthesizing the methanol at low temperature is achieved.
(2) The catalyst of the invention has better catalytic performance at low temperature, and the prepared catalyst Pt/alpha-MoxCyThe content of Pt in the Cu/beta-Mo alloy is 2 percentxCyThe content of Cu in the alloy is 5%, and the Cu can realize CO at 200 DEG C2The conversion was 10%, whereas the space-time yield of methanol at 200 ℃ was 72.6g CH3OH/kg cat·h。
(3) In the reaction of the catalyst, the reaction temperature is regulated, the reaction conversion rate and the methanol selectivity can be respectively regulated and controlled within the range of 200-300 ℃, the methanol selectivity is reduced and the methane selectivity is improved at high temperature, and the catalyst is favorable for realizing different functions of the catalyst at different temperatures in industrial production.
(4) The preparation process of the catalyst is simple and easy to repeat, and the catalyst can be prepared in a large scale.
Drawings
FIG. 1 is a graph of Cu/β -Mo loading of 5% for Cu obtained in examples 1-3xCyCatalyst and beta-MoxCyAnd the phase-pure alpha-Mo of examples 4 to 6xCyXRD spectrum of (1).
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Mo prepared by the inventionxCyIn the present invention, the ratio of x and y is not considered, and both the ratio and the numerical value may be any natural number or a positive number of an unnatural number, as is known in the art. The proportion between the two products can be known through testing, but the data does not influence the implementation of the technical scheme of the invention, so that relevant proportion data are not provided in the invention. The invention only researches the performance of the molybdenum carbide catalyst in the preparation of methanol.
Example 1
Weighing 1g of MoO3Mixing with 40mL of deionized water, ultrasonically dispersing, weighing 190mg of copper nitrate, and dissolving in MoO3In a dispersion of (2), after rotary evaporation and drying, the powder is transferred into a tube furnace at 20% CH4/H2Blowing at 150mL/min in atmosphere, starting temperature programming carbonization (room temperature → 400 ℃, 5 ℃/min, 400 → 700 ℃, 0.5 ℃/min, keeping for 1 hour), and finally passivating for 220min in mixed gas atmosphere containing 0.5% by volume of oxygen and the balance of nitrogen to obtain Cu/beta-Mo with mass concentration of 5%xCy。
The obtained catalyst is in-situ before the reaction performance evaluationAnd (3) reducing at 500 ℃ for 1h at a hydrogen airspeed of 30000mL/g/h under a reduction pressure of 0.1 MPa. Reducing the furnace temperature to 200 ℃ after reduction, wherein the reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction pressure is 5MPa, the catalyst loading is 100mg, the space velocity of the raw material gas is 12000mL/g/h, and the raw material gas for reaction is CO2And H2Composition of CO2And H2Is 1: 3. The results of the activity evaluation are shown in Table 1.
Example 2
Weighing 1g of MoO3Mixing with 40mL of deionized water, ultrasonically dispersing, weighing 190mg of copper nitrate, and dissolving in MoO3In a dispersion of (2), after rotary evaporation and drying, the powder is transferred into a tube furnace at 20% CH4/H2Blowing at 150mL/min in atmosphere, starting temperature programming carbonization (room temperature → 400 ℃, 5 ℃/min, 400 → 700 ℃, 0.5 ℃/min, keeping for 1 hour), and finally passivating for 220min in mixed gas atmosphere containing 0.5% by volume of oxygen and the balance of nitrogen to obtain Cu/beta-Mo with mass concentration of 5%xCy。
The obtained catalyst is reduced in situ before the reaction performance evaluation, the reduction temperature is 500 ℃, the reduction time is 1h, the air speed of hydrogen is 30000mL/g/h, and the reduction pressure is 0.1 MPa. Reducing the furnace temperature to 260 ℃ after reduction, wherein the reaction conditions are as follows: the reaction temperature is 260 ℃, the reaction pressure is 5MPa, the catalyst loading is 100mg, the space velocity of the raw material gas is 12000mL/g/h, and the raw material gas for reaction is CO2And H2Composition of CO2And H2Is 1: 3. The results of the activity evaluation are shown in Table 1.
Example 3
Weighing 1g of MoO3Mixing with 40mL of deionized water, ultrasonically dispersing, weighing 190mg of copper nitrate, and dissolving in MoO3In a dispersion of (2), after rotary evaporation and drying, the powder is transferred into a tube furnace at 20% CH4/H2Blowing at 150mL/min in atmosphere, starting temperature programming carbonization (room temperature → 400 ℃, 5 ℃/min, 400 → 700 ℃, 0.5 ℃/min, keeping for 1 hour), and finally passivating for 220min in mixed gas atmosphere containing 0.5% by volume of oxygen and the balance of nitrogen to obtain Cu/beta-Mo with mass concentration of 5%xCy。
The obtained catalyst is reduced in situ before the reaction performance evaluation, the reduction temperature is 500 ℃, the reduction time is 1h, the air speed of hydrogen is 30000mL/g/h, and the reduction pressure is 0.1 MPa. Reducing the furnace temperature to 300 ℃ after reduction, wherein the reaction conditions are as follows: the reaction temperature is 300 ℃, the reaction pressure is 5MPa, the catalyst loading is 100mg, the space velocity of the raw material gas is 12000mL/g/h, and the raw material gas for reaction is CO2And H2Composition of CO2And H2Is 1: 3. The results of the activity evaluation are shown in Table 1.
Example 4
Weighing 1g of MoO3Mixing with 40mL of deionized water, ultrasonic dispersing, and removing 5.6mL of chloroplatinic acid solution (1.834X 10)- 2mol/L) and dissolved in MoO3In a dispersion of (2), after rotary evaporation and drying, the powder is transferred into a tube furnace at 20% CH4/H2Blowing at 150mL/min in atmosphere, starting temperature programming carbonization (room temperature → 400 ℃, 5 ℃/min, 400 → 700 ℃, 0.5 ℃/min, keeping for 1 hour), and finally passivating for 220min in mixed gas atmosphere containing 0.5% by volume of oxygen and the balance of nitrogen to obtain Pt/alpha-Mo with mass concentration of 2%xCy。
The obtained catalyst is reduced in situ before the reaction performance evaluation, the reduction temperature is 500 ℃, the reduction time is 1h, the air speed of hydrogen is 30000mL/g/h, and the reduction pressure is 0.1 MPa. Reducing the furnace temperature to 200 ℃ after reduction, wherein the reaction conditions are as follows: the reaction temperature is 200 ℃, the reaction pressure is 5MPa, the catalyst loading is 100mg, the space velocity of the raw material gas is 12000mL/g/h, and the raw material gas for reaction is CO2And H2Composition of CO2And H2Is 1: 3. The results of the activity evaluation are shown in Table 1.
Example 5
Weighing 1g of MoO3Mixing with 40mL of deionized water, ultrasonic dispersing, and removing 5.6mL of chloroplatinic acid solution (1.834X 10)- 2mol/L) and dissolved in MoO3In a dispersion of (2), after rotary evaporation and drying, the powder is transferred into a tube furnace at 20% CH4/H2Purging in atmosphere at flow rate of 150mL/min, and starting temperature programmed carbonization (room temperature → 400 deg.C, 5 deg.C/min, 400 → 700 deg.C, 0.5 deg.C)Min, keeping for 1 hour), finally passivating for 220min in the mixed gas atmosphere containing 0.5 volume percent of oxygen and the balance of nitrogen to obtain Pt/alpha-Mo with the mass concentration of 2 percentxCy。
The obtained catalyst is reduced in situ before the reaction performance evaluation, the reduction temperature is 500 ℃, the reduction time is 1h, the air speed of hydrogen is 30000mL/g/h, and the reduction pressure is 0.1 MPa. Reducing the furnace temperature to 260 ℃ after reduction, wherein the reaction conditions are as follows: the reaction temperature is 260 ℃, the reaction pressure is 5MPa, the catalyst loading is 100mg, the space velocity of the raw material gas is 12000mL/g/h, and the raw material gas for reaction is CO2And H2Composition of CO2And H2Is 1: 3. The results of the activity evaluation are shown in Table 1.
Example 6
Weighing 1g of MoO3Mixing with 40mL of deionized water, ultrasonic dispersing, and removing 5.6mL of chloroplatinic acid solution (1.834X 10)- 2mol/L) and dissolved in MoO3In a dispersion of (2), after rotary evaporation and drying, the powder is transferred into a tube furnace at 20% CH4/H2Blowing at 150mL/min in atmosphere, starting temperature programming carbonization (room temperature → 400 ℃, 5 ℃/min, 400 → 700 ℃, 0.5 ℃/min, keeping for 1 hour), and finally passivating for 220min in mixed gas atmosphere containing 0.5% by volume of oxygen and the balance of nitrogen to obtain Pt/alpha-Mo with mass concentration of 2%xCy。
The obtained catalyst is reduced in situ before the reaction performance evaluation, the reduction temperature is 500 ℃, the reduction time is 1h, the air speed of hydrogen is 30000mL/g/h, and the reduction pressure is 0.1 MPa. Reducing the furnace temperature to 300 ℃ after reduction, wherein the reaction conditions are as follows: the reaction temperature is 300 ℃, the reaction pressure is 5MPa, the catalyst loading is 100mg, the space velocity of the raw material gas is 12000mL/g/h, and the raw material gas for reaction is CO2And H2Composition of CO2And H2Is 1: 3. The results of the activity evaluation are shown in Table 1.
TABLE 1 catalytic Performance data for the examples
FIG. 1 is a graph of Cu/β -Mo loading of 5% for Cu obtained in examples 1-3xCyCatalyst and beta-MoxCyAnd the phase-pure alpha-Mo of examples 4 to 6xCyXRD spectrum of (1).
Claims (8)
1. A molybdenum carbide catalyst, characterized in that the general formula of the molybdenum carbide catalyst is M/MoxCyWherein M is at least one of Cu and Pt, and accounts for 0.02-0.05% of the mass of the catalyst, and MoxCyIs alpha or beta phase molybdenum carbide.
2. The method for preparing a molybdenum carbide catalyst according to claim 1, wherein chloroplatinic acid or copper nitrate is dissolved in deionized water and MoO3Mixing the powders, rotary steaming, and drying to obtain powder CH4And H2Purging in the mixed gas, carbonizing to obtain molybdenum carbide catalyst, and adding into O2And N2The mixed gas is passivated and then stored.
3. The method of preparing the molybdenum carbide catalyst according to claim 2, wherein the CH is4And H2Mixed gas of (2) CH4Is 20% by volume, and the flow rate during purging is 150 mL/min.
4. The method for preparing the molybdenum carbide catalyst according to claim 2, wherein the carbonization process parameters are as follows: the temperature was raised from room temperature to 400 ℃ at a rate of 5 ℃/min, then to 700 ℃ at a rate of 0.5 ℃/min, and held for 1 hour.
5. The method for preparing a molybdenum carbide catalyst according to claim 2, wherein O is O2And N2O in the mixed gas of2Is 0.5 percent, and the passivation time is 220 min.
6. The method of preparing the molybdenum carbide catalyst of claim 2, wherein the catalyst is Pt/α -MoxCyWhen in use, chloroplatinic acid is adopted as a precursor; the catalyst is Cu/beta-MoxCyWhen the precursor is copper nitrate.
7. A method for preparing methanol by carbon dioxide hydrogenation based on a molybdenum carbide catalyst, which is characterized in that the molybdenum carbide catalyst in claim 1 is used for preparing methanol by carbon dioxide hydrogenation, and the reaction conditions are as follows: the reaction temperature is 200 ℃ and 300 ℃, the reaction pressure is 5MPa, and the space velocity of the raw material gas is 12000 mL/g/h.
8. The molybdenum carbide catalyst-based method for preparing methanol by hydrogenating carbon dioxide according to claim 7, wherein the raw material gas is CO2And H2Is prepared according to the volume ratio of 1: 3.
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