CN111151293A - Nitrogen-doped tungsten carbide catalyst and preparation and application thereof - Google Patents

Nitrogen-doped tungsten carbide catalyst and preparation and application thereof Download PDF

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CN111151293A
CN111151293A CN201911378258.4A CN201911378258A CN111151293A CN 111151293 A CN111151293 A CN 111151293A CN 201911378258 A CN201911378258 A CN 201911378258A CN 111151293 A CN111151293 A CN 111151293A
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nitrogen
tungsten carbide
doped tungsten
carbide catalyst
doped
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CN111151293B (en
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马睿
李亚云
杨冠恒
张瑜珑
刘瑞新
卢信清
王宁伟
王雪
彭安娜
许春慧
涂高美
朱伟东
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Zhejiang Normal University CJNU
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    • C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • C07C2529/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract

The invention relates to the technical field of catalysis, particularly relates to a nitrogen-doped tungsten carbide catalyst, and preparation and application thereof, and discloses nitrogen-doped carbonThe tungsten carbide catalyst comprises a nitrogen-doped tungsten carbide active center and a carrier containing a B acid site, wherein the nitrogen-doped tungsten carbide active center is nitrogen-doped tungsten carbide nano-particles with the particle size of less than or equal to 10nm and can react with CO2The product is converted into ethanol and propanol products with high added values, so that the conversion rate and the selectivity of ethanol and propanol are remarkably improved; the preparation method adopts a co-impregnation preparation method, is simple and convenient, does not need to strictly control the concentration of a metal salt solution, and has reasonable C, N content matching of the active center of the prepared catalyst, so that the catalyst has higher activity and stability; regulation of W2Electronic structure in C, thereby effectively regulating and controlling CO2The C-C bond generation rate and the C-O bond breakage rate in the hydrogenation process greatly reduce the selectivity of the C1 product, improve the selectivity of ethanol and propanol products, and have wide application prospects.

Description

Nitrogen-doped tungsten carbide catalyst and preparation and application thereof
Technical Field
The invention relates to the technical field of catalysis, in particular to a nitrogen-doped tungsten carbide catalyst and preparation and application thereof.
Background
Ethanol and propanol are very important organic solvents and basic chemical raw materials, and have very wide application, and the ethanol can be used for preparing chemical raw materials such as acetaldehyde, diethyl ether, ethyl acetate, ethylamine and the like, and can also be blended into gasoline to be used as vehicle fuel; the propanol can be used for synthesizing bulk chemicals such as propyl acetate, glycol ether, propylamine and the like, and can also be used for synthesizing medical and pesticide products such as propyl paraben, perfluoropropionic acid, trifluralin and the like; ethanol and propanol have wide application in national defense industry, medical treatment and health, organic synthesis, food industry, industrial and agricultural production.
The existing methods for preparing ethanol mainly comprise a fermentation method, an ethylene hydration method, a coal chemical industry and a method for directly preparing ethanol by using synthesis gas. However, the traditional fermentation method is long in time consumption and low in efficiency; the method for preparing ethanol directly from ethylene hydration method, coal chemical industry, synthesis gas and the like has higher cost. In addition, the industrial propanol is mostly prepared by hydration reaction of propylene at high temperature and high pressure, but the method has low conversion per pass of propylene and relatively high production cost.
CO2Is a direct product of fossil fuel combustion and is abundant on earth. The continuous development of human society leads to the rapid increase of the use amount of fossil fuels and the CO in the atmosphere2The content is increased day by day, which not only aggravates the greenhouse effect, but also causes huge waste of carbon resources. Introducing CO2The catalytic conversion of ethanol and propanol into high value-added ethanol is CO2One of the important technical means of resource utilization has important significance for solving two new challenges of climate change and energy crisis faced by the present human society.
Heterogeneous catalysis of CO as reported so far2The reaction system for preparing the ethanol and the propanol by hydrogenation is less. King light et al uses CoAlOxAs a catalyst, CO is reacted at 100 ℃ and 4MPa2Conversion to products such as ethanol, propanol, etc., CO2Conversion was 28.9%, selectivity of ethanol in liquid alcohol product was 62.7%, but selectivity in total product was only 2.82% (CN 108380216A); ZHenhong He et al Pt/Co3O4As catalysts in DMI and H2In a mixed solvent of O, reacting CO at 200 ℃ under 8MPa2Conversion to C2+Alcohols, wherein the selectivity of ethanol, propanol in the liquid alcohol product is 29% and 5.2%, respectively, but the selectivity in the total product is less than 11.3% (Angew.Int, ed, 2016, 55, 737- -); shuxing Bai et al use Pd-Cu supported on P25 as a bimetallic catalyst to react CO at 200 deg.C2The selectivity of ethanol to ethanol in the liquid alcohol product is up to 92% (J.Am.chem.Soc., 2017, 139, 6827-6830).
At present, CO is heterogeneously catalyzed2In the process for preparing ethanol and propanol by catalytic hydrogenation, although the selectivity of ethanol and propanol in liquid alcohol products is higher, main products of reaction are still CO and CH4Or C such as methanol1The selectivity of the product, ethanol and propanol in the total product after the reaction is still low (<20%). This is mainly due to the fact that on the one hand CO is present2Is a molecule with extremely stable chemical structure, and is difficult to realize effective activation; on the other hand in CO2During the hydrogenation reaction, the C-OH bond structure is difficult to maintain, and simultaneously, the C-C bond is difficult to be formed controllably to obtain ethanol or propanol, so that the main product after the reaction is a C1 compound or long-chain alkane. The catalytic reaction system developed at present can not realize CO2High conversion and high selectivity of ethanol and propanol products. Thus CO is converted into2Converting into C such as ethanol or propanol with high added value2+Alcohols still present significant challenges.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the CO in the prior art2The process for preparing ethanol and propanol by catalytic hydrogenation has the problems of low conversion rate and low selectivity, and reasonably matches CO2The rate of formation of C-C bonds and the rate of C-OH bond cleavage during hydrogenation, thereby providing a supported tungsten carbide catalyst as CO2The catalyst for preparing ethanol and propanol products with high activity and high selectivity.
The invention discloses a nitrogen-doped tungsten carbide catalyst which comprises a carrier and a nitrogen-doped tungsten carbide active ingredient loaded on the carrier, wherein the carrier contains a B acid site, and the nitrogen-doped tungsten carbide active ingredient is nitrogen-doped tungsten carbide nano-particles with the particle size of less than or equal to 10 nm.
The invention also discloses a raw material composition for preparing the nitrogen-doped tungsten carbide catalyst, which comprises soluble tungsten salt, methylene amine organic matters and B acid site carriers, wherein the molar ratio of the tungsten salt to the methylene amine is 1:0.5-1: 5.
Optionally, the content of tungsten is 5 wt% -50 wt%, and the content of nitrogen is 0.5 wt% -5 wt%.
Optionally, the soluble tungsten salt comprises one of ammonium metatungstate, ammonium paratungstate, sodium tungstate, and phosphotungstic acid.
Optionally, the methylene amine organic compound is one of hexamethylene diamine, hexamethylene tetramine, tetramethylene diamine and trimethyl hexamethylene diamine.
Optionally, the carrier at the acid site B comprises a molecular sieve carrier containing the acid site B, and comprises one of a ZSM-5 type carrier, a Y type carrier, a Beta type carrier and an MOR type carrier.
Optionally, the coating further comprises an auxiliary agent, wherein the auxiliary agent comprises at least one of Cu, Co, In and Fe, and the content of the auxiliary agent is 0.5 wt% -5 wt%.
The invention also discloses a preparation method of the nitrogen-doped tungsten carbide catalyst or the nitrogen-doped tungsten carbide catalyst prepared from the raw material composition for preparing the nitrogen-doped tungsten carbide catalyst, which comprises the following steps:
(1) preparing a mixed solution of soluble tungsten salt, methylene amine organic matters and water, soaking the mixed solution on a carrier containing an acid site B, and drying at 80-120 ℃ to obtain a catalyst precursor;
(2) and placing the precursor in a mixed atmosphere containing hydrogen, and carrying out temperature programming on the precursor to 600-900 ℃ for carbonization for 2-12h to obtain the supported nitrogen-doped tungsten carbide catalyst, wherein the temperature raising rate of the temperature programming is 0.5-2 ℃/min.
Optionally, the mixed gas further includes at least one of nitrogen, argon and helium, and the volume fraction of the hydrogen is 10-50%.
The invention also discloses the application of the nitrogen-doped tungsten carbide catalyst, or the carbon-doped tungsten carbide catalyst prepared from the raw material composition for preparing the nitrogen-doped tungsten carbide catalyst, or the nitrogen-doped tungsten carbide catalyst prepared by the preparation method of the nitrogen-doped tungsten carbide catalyst in the field of alcohol preparation from carbon dioxide hydrogenation gas.
The invention also discloses a method for preparing alcohol by catalyzing carbon dioxide hydrogenation gas, wherein the volume ratio of CO is 1:3-1:42And H2Reacting to generate alcohol under the action of a catalyst, wherein the catalyst is the nitrogen-doped tungsten carbide catalyst as described in claim 1 or 2, or the nitrogen-doped tungsten carbide catalyst prepared by the preparation method of the nitrogen-doped tungsten carbide catalyst as described in claim 8 or 9.
Optionally, the reaction temperature of the catalytic reaction is 200-350 ℃.
Optionally, the reaction pressure of the catalytic reaction is 0.5-10 MPa.
Optionally, the volume space velocity of the catalytic reaction is 1000-10000h-1。
The technical scheme of the invention has the following advantages:
1. the invention discloses a nitrogen-doped tungsten carbide catalyst (N-W2C/B), which comprises a nitrogen-doped tungsten carbide active center and a carrier, wherein the carrier contains a B acid site, the nitrogen-doped tungsten carbide active center is nitrogen-doped tungsten carbide nano-particles, the particle size of the nitrogen-doped tungsten carbide nano-particles is less than or equal to 10nm, and the nitrogen-doped tungsten carbide nano-particles are loaded on the carrier; the nanometer size obviously enhances the activity of the catalyst, and CO can be converted without using noble metal2Converted into ethanol and propanol products with high added values, and the CO is obviously improved2Conversion and selectivity to ethanolpropanol. The carrier is preferably a molecular sieve containing B acid sites, and has a large specific surface area, and nitrogen-doped tungsten carbide active centers are uniformly distributed in pore diameters, so that the catalytic performance is good and stable.
2. The preparation method of the nitrogen-doped tungsten carbide catalyst (N-W2C/B) adopts a co-impregnation preparation method, is simple and convenient, takes the methylene amine as a carbon source and a nitrogen source, and avoids CH in the traditional tungsten carbide synthesis process4The carbon deposition problem of the catalyst caused by the cracking of gas at high temperature leads the catalyst to be in CO2The catalytic hydrogenation reaction has higher activity and stability; the N-W2C/B catalyst provided by the temperature programmed carbonization preparation method provided by the invention regulates and controls W through reasonable matching of the content of the active center C, N2Electronic structure in C, thereby effectively regulating and controlling CO2C-C bond formation rate and C-O bond formation during hydrogenationThe breaking rate greatly reduces the selectivity of the C1 product and improves the selectivity of ethanol and propanol products.
3. The nitrogen-doped tungsten carbide catalyst (N-W2C/B) provided by the invention is applied to CO2The application in the hydrogenation process changes the prior preparation method of ethanol and propanol, and compared with the traditional fermentation method, ethylene hydration method and synthesis gas synthesis method, the carbon dioxide has rich carbon source and is catalyzed and hydrogenated into ethanol and propanol with high added values; can solve the problem of carbon balance unbalance and has wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an electron micrograph of a nitrogen-doped tungsten carbide catalyst according to example 1;
FIG. 2 is an electron micrograph of a nitrogen-doped tungsten carbide catalyst according to example 2;
FIG. 3 is an electron micrograph of a nitrogen-doped tungsten carbide catalyst according to example 3;
FIG. 4 is an electron micrograph of a nitrogen-doped tungsten carbide catalyst according to example 4;
FIG. 5 is an electron micrograph of a nitrogen-doped tungsten carbide catalyst according to example 5;
FIG. 6 is an electron micrograph of a nitrogen-doped tungsten carbide catalyst according to example 6;
FIG. 7 is an electron micrograph of a nitrogen-doped tungsten carbide catalyst according to example 7;
fig. 8 is an electron micrograph of nitrogen-doped tungsten carbide catalyst described in example 8.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
This example discloses a nitrogen-doped tungsten carbide catalyst (N-W)2C/B), comprising the following steps:
adding 10mmol of ammonium metatungstate and 8mmol of hexamethylenediamine into water to obtain a mixed solution, soaking the mixed solution on 5g of HZSM-5 type molecular sieve containing a B acid site in an equal volume, standing at room temperature for 12h, drying in an oven at 100 ℃ for 24h to obtain a precursor of the nitrogen-doped tungsten carbide catalyst, and measuring that the mass fraction of tungsten in the precursor is 27% and the mass fraction of nitrogen is 0.5%;
heating the precursor to 600 ℃ in a mixed gas of hydrogen and nitrogen by a program for carbonization for 4h, wherein the volume fraction of the hydrogen in the mixed gas is 10%, and the temperature programming rate is 1.5 ℃/min, thus obtaining the nitrogen-doped tungsten carbide catalyst (N-W)2C/B), as shown in fig. 1, wherein the particle size of the nitrogen-doped tungsten carbide nano-particles is 5-7 nm.
Example 2
This example discloses a nitrogen-doped tungsten carbide catalyst (N-W)2C/B), comprising the following steps:
adding 6.8mmol of ammonium metatungstate and 20.4mmol of hexamethylenediamine into water to obtain a mixed solution, soaking the mixed solution on 5g of H- β molecular sieve containing a B acid position, standing at room temperature for 12H, and drying in an oven at 80 ℃ for 18H to obtain a precursor of the nitrogen-doped tungsten carbide catalyst, wherein the mass fraction of tungsten in the precursor is 20% and the mass fraction of nitrogen is 1%;
mixing the precursor with hydrogen and heliumThe temperature is increased to 800 ℃ in the body by a program and carbonized for 4h, wherein the volume fraction of hydrogen in the mixed gas is 30 percent, the speed of the temperature increase by the program is 2.0 ℃/min, and the nitrogen-doped tungsten carbide catalyst (N-W) is obtained2C/B), as shown in fig. 2, wherein the particle size of the nitrogen-doped tungsten carbide nanoparticles is 5-9 nm.
Example 3
This example discloses a nitrogen-doped tungsten carbide catalyst (N-W)2C/B), comprising the following steps:
adding 15.3mmol of ammonium metatungstate and 19.2mmol of hexamethylenediamine into water to obtain a mixed solution, soaking the mixed solution on 5g of H-Y type molecular sieve containing a B acid position, standing for 12H at room temperature, drying for 24H in an oven at 120 ℃ to obtain a precursor of the nitrogen-doped tungsten carbide catalyst, wherein the mass fraction of tungsten in the precursor is measured to be 36%, and the mass fraction of nitrogen is measured to be 0.8%;
heating the precursor in a mixed gas of hydrogen and nitrogen to 700 ℃ by a program for carbonization for 2h, wherein the volume fraction of the hydrogen in the mixed gas is 40%, and the temperature programming rate is 1.0 ℃/min, thus obtaining the nitrogen-doped tungsten carbide catalyst (N-W)2C/B), as shown in fig. 3, wherein the particle size of the nitrogen-doped tungsten carbide nanoparticles is 5-8 nm.
Example 4
This example discloses a nitrogen-doped tungsten carbide catalyst (N-W)2C/B), comprising the following steps:
adding 1.4mmol of ammonium metatungstate and 4.0mmol of hexamethylenediamine into water to obtain a mixed solution, soaking the mixed solution on 5g of MOR type molecular sieve containing an acid site B, standing at room temperature for 12h, drying in an oven at 100 ℃ for 24h to obtain a precursor of the nitrogen-doped tungsten carbide catalyst, and measuring that the mass fraction of tungsten in the precursor is 5% and the mass fraction of nitrogen is 0.6%;
heating the precursor to 650 ℃ in a mixed gas of hydrogen and argon by a program for 12h for carbonization, wherein the volume fraction of the hydrogen in the mixed gas is 20%, and the temperature programming rate is 0.5 ℃/min, thus obtaining the nitrogen-doped tungsten carbide catalyst (N-W)2C/B), as shown in FIG. 4, wherein the nitrogen is doped with tungsten carbide nano particlesThe particle size of the particles is 5-7 nm.
Example 5
This example discloses a nitrogen-doped tungsten carbide catalyst (N-W)2C/B), comprising the following steps:
adding 3.7mmol of ammonium metatungstate and 15.6mmol of hexamethylenediamine into water to obtain a mixed solution, soaking the mixed solution on 5g of H- β molecular sieve containing a B acid position, standing at room temperature for 12H, and drying in an oven at 100 ℃ for 30H to obtain a precursor of the nitrogen-doped tungsten carbide catalyst, wherein the mass fraction of tungsten in the precursor is 12% and the mass fraction of nitrogen is 2%;
heating the precursor to 750 ℃ in a mixed gas of hydrogen and argon by a program for carbonization for 4h, wherein the volume fraction of the hydrogen in the mixed gas is 15%, and the temperature programming rate is 2.5 ℃/min, so as to obtain the nitrogen-doped tungsten carbide catalyst (N-W)2C/B), as shown in fig. 5, wherein the particle size of the nitrogen-doped tungsten carbide nanoparticles is 3-5 nm.
Example 6
This example discloses a nitrogen-doped tungsten carbide catalyst (N-W)2C/B), comprising the following steps:
adding 22.3mmol of ammonium metatungstate and 80.1mmol of hexamethylenediamine into water to obtain a mixed solution, soaking the mixed solution on 5g of HZSM-5 type molecular sieve containing an acid B position, standing at room temperature for 12h, and drying in an oven at 100 ℃ for 24h to obtain a precursor of the nitrogen-doped tungsten carbide catalyst, wherein the mass fraction of tungsten in the precursor is 45% and the mass fraction of nitrogen is 5%;
heating the precursor in a mixed gas of hydrogen and argon to 680 ℃ by a program, and carbonizing for 4h, wherein the volume fraction of hydrogen in the mixed gas is 35%, and the temperature programming rate is 3.0 ℃/min, so as to obtain the nitrogen-doped tungsten carbide catalyst (N-W)2C/B), as shown in fig. 6, wherein the particle size of the nitrogen-doped tungsten carbide nanoparticles is 3-5 nm.
Example 7
This example discloses a nitrogen-doped tungsten carbide catalyst (N-W)2C/B), comprising the following steps:
adding 6.0mmol of ammonium metatungstate and 30.0mmol of hexamethylenediamine into water to obtain a mixed solution, soaking the mixed solution on 5g of H-Y molecular sieve containing an acid B position, standing at room temperature for 12H, and drying in an oven at 100 ℃ for 24H to obtain a precursor of the nitrogen-doped tungsten carbide catalyst, wherein the mass fraction of tungsten in the precursor is measured to be 18%, and the mass fraction of nitrogen is measured to be 2.5%;
heating the precursor in a mixed gas of hydrogen and argon by a program to 730 ℃ for carbonization for 4h, wherein the volume fraction of the hydrogen in the mixed gas is 25%, and the temperature programming rate is 2.5 ℃/min, thus obtaining the nitrogen-doped tungsten carbide catalyst (N-W)2C/B), as shown in fig. 7, wherein the particle size of the nitrogen-doped tungsten carbide nanoparticles is 6-10 nm.
Example 8
This example discloses a nitrogen-doped tungsten carbide catalyst (N-W)2C/B), comprising the following steps:
adding 27.2mmol of ammonium metatungstate and 13.6mmol of hexamethylenediamine into water to obtain a mixed solution, soaking the mixed solution on an MOR type molecular sieve containing a B acid position, standing for 12h at room temperature, and drying in an oven at 100 ℃ for 24h to obtain a precursor of the nitrogen-doped tungsten carbide catalyst, wherein the mass fraction of tungsten in the precursor is measured to be 50%, and the mass fraction of nitrogen is measured to be 1.8%;
heating the precursor to 780 ℃ in a mixed gas of hydrogen and argon for 4h of carbonization, wherein the volume fraction of hydrogen in the mixed gas is 50%, and the temperature programming rate is 1.5 ℃/min, thus obtaining the nitrogen-doped tungsten carbide catalyst (N-W)2C/B), as shown in fig. 8, wherein the particle size of the nitrogen-doped tungsten carbide nanoparticles is 6-8 nm.
Example 9
This example discloses a nitrogen-doped tungsten carbide catalyst (Cu-N-W) containing a copper promoter2C/B), comprising the following steps:
adding 16mmol of ammonium metatungstate, 24mmol of hexamethylenediamine and 0.45mmol of copper nitrate into a mixed solution in water, dipping the mixed solution on an HZSM-5 type molecular sieve containing a B acid site, standing for 12h at room temperature, drying for 24h in an oven at 100 ℃ to obtain a precursor of the nitrogen-doped tungsten carbide catalyst, and measuring that the mass fraction of tungsten in the precursor is 36%, the mass fraction of nitrogen is 1.6% and the mass fraction of copper is 0.5%;
heating the precursor to 750 ℃ in a mixed gas of hydrogen and argon by a program for carbonization for 4h, wherein the volume fraction of the hydrogen in the mixed gas is 50%, and the temperature programming rate is 1 ℃/min, thus obtaining the nitrogen-doped tungsten carbide catalyst (Cu-N-W) containing the copper auxiliary agent2C/B)。
Example 10
This example discloses a nitrogen-doped tungsten carbide catalyst (Co-N-W) containing a cobalt promoter2C/B), comprising the following steps:
adding 17mmol of ammonium metatungstate, 41.5mmol of hexamethylenediamine and 1.2mmol of cobalt nitrate into a mixed solution in water, dipping the mixed solution on an MOR type molecular sieve containing a B acid site, standing for 12h at room temperature, drying for 24h in an oven at 100 ℃ to obtain a precursor of the nitrogen-doped tungsten carbide catalyst, wherein the mass fraction of tungsten in the precursor is 38%, the mass fraction of nitrogen is 2.1%, and the mass fraction of cobalt is 2.3%;
heating the precursor in a mixed gas of hydrogen and argon to 700 ℃ by a program, and carbonizing for 6h, wherein the volume fraction of the hydrogen in the mixed gas is 50%, and the temperature programming rate is 1.5 ℃/min, so as to obtain the nitrogen-doped tungsten carbide catalyst (Co-N-W) containing the cobalt auxiliary agent2C/B)。
Example 11
This example discloses a nitrogen-doped tungsten carbide catalyst (In-N-W) containing an indium promoter2C/B), comprising the following steps:
adding 9.5mmol of ammonium metatungstate, 33.5mmol of hexamethylenediamine and 2.4mmol of indium nitrate into a mixed solution in water, dipping the mixed solution on an H- β type molecular sieve containing a B acid site, standing for 12H at room temperature, and drying for 24H in an oven at 100 ℃ to obtain a precursor of the nitrogen-doped tungsten carbide catalyst, wherein the mass fraction of tungsten element in the precursor is 25%, the mass fraction of nitrogen element is 2.5% and the mass fraction of indium element is 5.0%;
the precursor is carbonized for 6 hours at 680 ℃ by programmed temperature rise In mixed gas of hydrogen and argon, wherein the volume fraction of the hydrogen In the mixed gas is 35 percent, and the programmed temperature rise rate is 2.0 ℃/min, and the nitrogen-doped tungsten carbide catalyst (In-N-W) containing the indium auxiliary agent is obtained2C/B)。
Example 12
This example discloses a nitrogen-doped tungsten carbide catalyst (Fe-N-W) containing an iron promoter2C/B), comprising the following steps:
adding 4.8mmol of ammonium metatungstate, 21.5mmol of hexamethylenediamine and 3.2mmol of ferric nitrate into a mixed solution in water, dipping the mixed solution on an H-Y type molecular sieve containing a B acid site, standing for 12H at room temperature, and drying in an oven at 100 ℃ for 24H to obtain a precursor of the nitrogen-doped tungsten carbide catalyst, wherein the mass fraction of tungsten element in the precursor is 14.5%, the mass fraction of nitrogen element is 1.4%, and the mass fraction of iron element is 3.3%;
heating the precursor to 720 ℃ in a mixed gas of hydrogen and argon by a program for carbonization for 4h, wherein the volume fraction of the hydrogen in the mixed gas is 15%, and the temperature programming rate is 2.0 ℃/min, thus obtaining the nitrogen-doped tungsten carbide catalyst (Fe-N-W) containing the indium auxiliary agent2C/B)。
Example 13
This example provides a specific implementation manner of using the nitrogen-doped tungsten carbide catalyst described in example 1 for preparing alcohol by carbon dioxide hydrogenation, which includes the following steps:
granulating the nitrogen-doped tungsten carbide catalyst to 70 meshes, placing the granules in a fixed bed reactor with the inner diameter of 10mm, wherein the raw material gas for catalytic reaction is CO2And H2The volume ratio of the mixed gas is 1:3, and the reaction temperature of the catalytic reaction is 200 ℃; the reaction pressure of the catalytic reaction is 3 MPa; the volume space velocity of the catalytic reaction is 2000h-1；
Two gas chromatographs are introduced into a heat-insulating pipe at 100 ℃ from an outlet pipeline of the reactor, and raw material gas CO is respectively carried out2And H2And the products ethanol and propanolQualitative and quantitative analysis.
Example 14
This example provides a specific implementation manner of using the nitrogen-doped tungsten carbide catalyst described in example 2 for preparing alcohol by carbon dioxide hydrogenation, which includes the following steps:
granulating the nitrogen-doped tungsten carbide catalyst to 60 meshes, placing the granules in a fixed bed reactor with the inner diameter of 10mm, wherein the raw material gas for catalytic reaction is CO2And H2Mixed gas with the volume ratio of 1:3.6, wherein the reaction temperature of the catalytic reaction is 240 ℃; the reaction pressure of the catalytic reaction is 4 MPa; the volume space velocity of the catalytic reaction is 4000h-1；
Two gas chromatographs are introduced into a heat-insulating pipe at 100 ℃ from an outlet pipeline of the reactor, and raw material gas CO is respectively carried out2And H2And qualitative and quantitative analysis of the products ethanol and propanol.
Example 15
This example provides a specific implementation manner of using the nitrogen-doped tungsten carbide catalyst described in example 2 for preparing alcohol by carbon dioxide hydrogenation, which includes the following steps:
granulating the nitrogen-doped tungsten carbide catalyst to 80 meshes, placing the granules in a fixed bed reactor with the inner diameter of 10mm, wherein the raw material gas for catalytic reaction is CO2And H2Mixed gas with the volume ratio of 1:3.2, wherein the reaction temperature of the catalytic reaction is 280 ℃; the reaction pressure of the catalytic reaction is 2.6 MPa; the volume space velocity of the catalytic reaction is 8000h-1；
Two gas chromatographs are introduced into a heat-insulating pipe at 100 ℃ from an outlet pipeline of the reactor, and raw material gas CO is respectively carried out2And H2And qualitative and quantitative analysis of the products ethanol and propanol.
Example 16
This example provides a specific implementation manner of using the nitrogen-doped tungsten carbide catalyst described in example 4 for preparing alcohol by carbon dioxide hydrogenation, which includes the following steps:
granulating the nitrogen-doped tungsten carbide catalyst to 70 meshes, placing the granules in a fixed bed reactor with the inner diameter of 10mm, and carrying out catalytic reactionThe feed gas is CO2And H2Mixed gas with the volume ratio of 1:3.5, wherein the reaction temperature of the catalytic reaction is 300 ℃; the reaction pressure of the catalytic reaction is 3.5 MPa; the volume space velocity of the catalytic reaction is 1000h-1；
Two gas chromatographs are introduced into a heat-insulating pipe at 100 ℃ from an outlet pipeline of the reactor, and raw material gas CO is respectively carried out2And H2And qualitative and quantitative analysis of the products ethanol and propanol.
Example 17
This example provides a specific implementation manner of using the nitrogen-doped tungsten carbide catalyst described in example 3 for preparing alcohol by carbon dioxide hydrogenation, which includes the following steps:
granulating the nitrogen-doped tungsten carbide catalyst to 70 meshes, placing the granules in a fixed bed reactor with the inner diameter of 10mm, wherein the raw material gas for catalytic reaction is CO2And H2The volume ratio of the mixed gas is 1:4, and the reaction temperature of the catalytic reaction is 260 ℃; the reaction pressure of the catalytic reaction is 8.5 MPa; the volume space velocity of the catalytic reaction is 3000h-1；
Two gas chromatographs are introduced into a heat-insulating pipe at 100 ℃ from an outlet pipeline of the reactor, and raw material gas CO is respectively carried out2And H2And qualitative and quantitative analysis of the products ethanol and propanol.
Example 18
This example provides a specific implementation manner of using the nitrogen-doped tungsten carbide catalyst described in example 7 for preparing alcohol by carbon dioxide hydrogenation, which includes the following steps:
granulating the nitrogen-doped tungsten carbide catalyst to 70 meshes, placing the granules in a fixed bed reactor with the inner diameter of 10mm, wherein the raw material gas for catalytic reaction is CO2And H2Mixed gas with the volume ratio of 1:3.5, wherein the reaction temperature of the catalytic reaction is 250 ℃; the reaction pressure of the catalytic reaction is 6.8 MPa; the volume space velocity of the catalytic reaction is 9000h-1；
Two gas chromatographs are introduced into a heat-insulating pipe at 100 ℃ from an outlet pipeline of the reactor, and raw material gas CO is respectively carried out2And H2And characterization of the products ethanol and propanolAnd carrying out quantitative analysis.
Example 19
This example provides a specific implementation manner of using the nitrogen-doped tungsten carbide catalyst described in example 8 for preparing alcohol by carbon dioxide hydrogenation, including the following steps:
granulating the nitrogen-doped tungsten carbide catalyst to 70 meshes, placing the granules in a fixed bed reactor with the inner diameter of 10mm, wherein the raw material gas for catalytic reaction is CO2And H2Mixed gas with the volume ratio of 1:3.6, wherein the reaction temperature of the catalytic reaction is 320 ℃; the reaction pressure of the catalytic reaction is 5.6 MPa; the volume space velocity of the catalytic reaction is 10000h-1；
Two gas chromatographs are introduced into a heat-insulating pipe at 100 ℃ from an outlet pipeline of the reactor, and raw material gas CO is respectively carried out2And H2And qualitative and quantitative analysis of the products ethanol and propanol.
Example 20
This example provides a specific implementation manner of using the nitrogen-doped tungsten carbide catalyst described in example 5 for preparing alcohol by carbon dioxide hydrogenation, which includes the following steps:
granulating the nitrogen-doped tungsten carbide catalyst to 70 meshes, placing the granules in a fixed bed reactor with the inner diameter of 10mm, wherein the raw material gas for catalytic reaction is CO2And H2Mixed gas with the volume ratio of 1:3.4, wherein the reaction temperature of the catalytic reaction is 300 ℃; the reaction pressure of the catalytic reaction is 0.5 MPa; the volume space velocity of the catalytic reaction is 5000h-1；
Two gas chromatographs are introduced into a heat-insulating pipe at 100 ℃ from an outlet pipeline of the reactor, and raw material gas CO is respectively carried out2And H2And qualitative and quantitative analysis of the products ethanol and propanol.
Example 21
This example provides a specific implementation manner of using the nitrogen-doped tungsten carbide catalyst described in example 6 for preparing alcohol by carbon dioxide hydrogenation, including the following steps:
granulating the nitrogen-doped tungsten carbide catalyst to 70 meshes, placing the granules in a fixed bed reactor with the inner diameter of 10mm, and carrying out catalytic reaction on the raw material gasIs CO2And H2Mixed gas with the volume ratio of 1:3.6, wherein the reaction temperature of the catalytic reaction is 330 ℃; the reaction pressure of the catalytic reaction is 6.3 MPa; the volume space velocity of the catalytic reaction is 6000h-1；
Two gas chromatographs are introduced into a heat-insulating pipe at 100 ℃ from an outlet pipeline of the reactor, and raw material gas CO is respectively carried out2And H2And qualitative and quantitative analysis of the products ethanol and propanol.
Example 22
This example provides a specific implementation manner of using the nitrogen-doped tungsten carbide catalyst described in example 3 for preparing alcohol by carbon dioxide hydrogenation, which includes the following steps:
granulating the nitrogen-doped tungsten carbide catalyst to 70 meshes, placing the granules in a fixed bed reactor with the inner diameter of 10mm, wherein the raw material gas for catalytic reaction is CO2And H2Mixed gas with the volume ratio of 1:3.9, wherein the reaction temperature of the catalytic reaction is 350 ℃; the reaction pressure of the catalytic reaction is 4.5 MPa; the volume space velocity of the catalytic reaction is 4800h-1；
Two gas chromatographs are introduced into a heat-insulating pipe at 100 ℃ from an outlet pipeline of the reactor, and raw material gas CO is respectively carried out2And H2And qualitative and quantitative analysis of the products ethanol and propanol.
Example 23
This example provides a specific implementation manner of using the nitrogen-doped tungsten carbide catalyst described in example 4 for preparing alcohol by carbon dioxide hydrogenation, which includes the following steps:
granulating the nitrogen-doped tungsten carbide catalyst to 70 meshes, placing the granules in a fixed bed reactor with the inner diameter of 10mm, wherein the raw material gas for catalytic reaction is CO2And H2Mixed gas with the volume ratio of 1:3.1, wherein the reaction temperature of the catalytic reaction is 320 ℃; the reaction pressure of the catalytic reaction is 1.5 MPa; the volume space velocity of the catalytic reaction is 6400h-1；
Two gas chromatographs are introduced into a heat-insulating pipe at 100 ℃ from an outlet pipeline of the reactor, and raw material gas CO is respectively carried out2And H2And the nature of the products ethanol and propanol,And (4) carrying out quantitative analysis.
Example 24
This example provides a specific implementation manner of using the nitrogen-doped tungsten carbide catalyst described in example 6 for preparing alcohol by carbon dioxide hydrogenation, including the following steps:
granulating the nitrogen-doped tungsten carbide catalyst to 70 meshes, placing the granules in a fixed bed reactor with the inner diameter of 10mm, wherein the raw material gas for catalytic reaction is CO2And H2Mixed gas with the volume ratio of 1:3.8, wherein the reaction temperature of the catalytic reaction is 310 ℃; the reaction pressure of the catalytic reaction is 9.2 MPa; the volume space velocity of the catalytic reaction is 3500h-1；
Two gas chromatographs are introduced into a heat-insulating pipe at 100 ℃ from an outlet pipeline of the reactor, and raw material gas CO is respectively carried out2And H2And qualitative and quantitative analysis of the products ethanol and propanol.
Example 25
This example provides a specific implementation manner of using the nitrogen-doped tungsten carbide catalyst described in example 3 for preparing alcohol by carbon dioxide hydrogenation, which includes the following steps:
granulating the nitrogen-doped tungsten carbide catalyst to 70 meshes, placing the granules in a fixed bed reactor with the inner diameter of 10mm, wherein the raw material gas for catalytic reaction is CO2And H2Mixed gas with the volume ratio of 1:3.2, wherein the reaction temperature of the catalytic reaction is 290 ℃; the reaction pressure of the catalytic reaction is 10 MPa; the volume space velocity of the catalytic reaction is 7200h-1；
Two gas chromatographs are introduced into a heat-insulating pipe at 100 ℃ from an outlet pipeline of the reactor, and raw material gas CO is respectively carried out2And H2And qualitative and quantitative analysis of the products ethanol and propanol.
Example 26
This example provides a specific implementation manner of using the nitrogen-doped tungsten carbide catalyst described in example 5 for preparing alcohol by carbon dioxide hydrogenation, which includes the following steps:
granulating the nitrogen-doped tungsten carbide catalyst to 70 meshes, placing the granules in a fixed bed reactor with the inner diameter of 10mm, wherein the raw material gas for catalytic reaction isCO2And H2Mixed gas with the volume ratio of 1:3.7, wherein the reaction temperature of the catalytic reaction is 340 ℃; the reaction pressure of the catalytic reaction is 7.6 MPa; the volume space velocity of the catalytic reaction is 1800h-1；
Two gas chromatographs are introduced into a heat-insulating pipe at 100 ℃ from an outlet pipeline of the reactor, and raw material gas CO is respectively carried out2And H2And qualitative and quantitative analysis of the products ethanol and propanol.
Example 27
This example provides a specific implementation manner of using the nitrogen-doped tungsten carbide catalyst with a cobalt promoter in alcohol production by carbon dioxide hydrogenation according to example 10, including the following steps:
granulating the nitrogen-doped tungsten carbide catalyst containing the cobalt auxiliary agent to 70 meshes, placing the granules in a fixed bed reactor with the inner diameter of 10mm, wherein the raw material gas for catalytic reaction is CO2And H2Mixed gas with the volume ratio of 1:3.5, wherein the reaction temperature of the catalytic reaction is 330 ℃; the reaction pressure of the catalytic reaction is 3.6 MPa; the volume space velocity of the catalytic reaction is 4800h-1；
Two gas chromatographs are introduced into a heat-insulating pipe at 100 ℃ from an outlet pipeline of the reactor, and raw material gas CO is respectively carried out2And H2And qualitative and quantitative analysis of the products ethanol and propanol.
Example 28
This example provides a specific implementation manner of using the nitrogen-doped tungsten carbide catalyst with an indium promoter in alcohol production by carbon dioxide hydrogenation according to example 11, including the following steps:
granulating the nitrogen-doped tungsten carbide catalyst containing the indium auxiliary agent to 70 meshes, placing the granules in a fixed bed reactor with the inner diameter of 10mm, wherein the raw material gas for catalytic reaction is CO2And H2The volume ratio of the mixed gas is 1:3, and the reaction temperature of the catalytic reaction is 320 ℃; the reaction pressure of the catalytic reaction is 4.6 MPa; the volume space velocity of the catalytic reaction is 6000h-1；
Two gas chromatographs are introduced into the reactor outlet pipeline in a heat-insulating pipe at 100 ℃ for respectively carrying out raw material gas CO2And H2And qualitative and quantitative analysis of the products ethanol and propanol.
Example 29
This example provides a specific implementation manner of using the nitrogen-doped tungsten carbide catalyst with a copper promoter in alcohol production through carbon dioxide hydrogenation according to example 9, including the following steps:
granulating the nitrogen-doped tungsten carbide catalyst containing the copper auxiliary agent to 70 meshes, placing the granules in a fixed bed reactor with the inner diameter of 10mm, wherein the raw material gas for catalytic reaction is CO2And H2Mixed gas with the volume ratio of 1:3.8, wherein the reaction temperature of the catalytic reaction is 280 ℃; the reaction pressure of the catalytic reaction is 5.2 MPa; the volume space velocity of the catalytic reaction is 2500h-1；
Two gas chromatographs are introduced into a heat-insulating pipe at 100 ℃ from an outlet pipeline of the reactor, and raw material gas CO is respectively carried out2And H2And qualitative and quantitative analysis of the products ethanol and propanol.
Example 30
This example provides a specific implementation of the nitrogen-doped tungsten carbide catalyst with an iron promoter used in the carbon dioxide hydrogenation process to produce alcohol as described in example 12, including the following steps:
granulating the nitrogen-doped tungsten carbide catalyst containing the iron auxiliary agent to 70 meshes, placing the granules in a fixed bed reactor with the inner diameter of 10mm, wherein the raw material gas for catalytic reaction is CO2And H2Mixed gas with the volume ratio of 1:3.8, wherein the reaction temperature of the catalytic reaction is 260 ℃; the reaction pressure of the catalytic reaction is 3.8 MPa; the volume space velocity of the catalytic reaction is 5400h-1；
Two gas chromatographs are introduced into a heat-insulating pipe at 100 ℃ from an outlet pipeline of the reactor, and raw material gas CO is respectively carried out2And H2And qualitative and quantitative analysis of the products ethanol and propanol.
Test example 1
Examples 13-30 the reactor outlet line was vented to two gas chromatographs, gas chromatograph 1 using a FID detector for quantitative analysis of ethanol and propanol products in the product, and gas chromatograph 2 using a TCD detector for quantitative analysis of CO2 conversion in the gas mixture, as calculated by the equation given below, with the results shown in table 1:
Figure BDA0002341572620000191
Figure BDA0002341572620000192
TABLE 1 CO from examples 13-3022Comparison of the hydroconversion reaction Performance
Figure BDA0002341572620000193
Figure BDA0002341572620000201
Discussion of the results: the nitrogen-doped tungsten carbide catalyst provided by the invention can obviously improve the conversion rate of carbon dioxide and the selectivity of ethanol, and the tungsten content, the nitrogen content and the H content in the precursor of the catalyst2The volume fraction, the heating rate and the carbonization temperature, and the space velocity, the reaction temperature, the pressure and the raw material gas proportion in the catalytic reaction are all relative to CO2The conversion rate and the selectivity of ethanol and propanol are influenced.
It is to be understood that the above examples are illustrative only for the purpose of clarity of description and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (14)

1. The nitrogen-doped tungsten carbide catalyst is characterized by comprising a carrier and a nitrogen-doped tungsten carbide active ingredient loaded on the carrier, wherein the carrier contains a B acid site, and the nitrogen-doped tungsten carbide active ingredient is nitrogen-doped tungsten carbide nano-particles with the particle size of less than or equal to 10 nm.
2. A raw material composition for preparing the nitrogen-doped tungsten carbide catalyst of claim 1, which comprises a soluble tungsten salt, a methylene amine organic substance and a B acid site carrier, wherein the molar ratio of the tungsten salt to the methylene amine is 1:0.5-1: 5.
3. The feed composition of nitrogen-doped tungsten carbide catalyst according to claim 2, wherein the content of tungsten is 5 wt% to 50 wt% and the content of nitrogen is 0.5 wt% to 5 wt%.
4. The feed composition for the preparation of nitrogen-doped tungsten carbide catalyst according to claim 2 or 3, wherein the soluble tungsten salt comprises one of ammonium metatungstate, ammonium paratungstate, sodium tungstate and phosphotungstic acid.
5. The raw material composition for preparing the nitrogen-doped tungsten carbide catalyst according to any one of claims 2 to 4, wherein the methylene amine organic compound is one of hexamethylenediamine, hexamethylenetetramine, tetramethylenediamine and trimethylhexamethylenediamine.
6. The feedstock composition for preparing nitrogen-doped tungsten carbide catalyst according to any one of claims 2 to 5, wherein the B acid site support comprises a molecular sieve support containing B acid sites, including one of ZSM-5 type support, Y type support, Beta type support and MOR type support.
7. The raw material composition for preparing the nitrogen-doped tungsten carbide catalyst according to any one of claims 2 to 6, further comprising an auxiliary agent, wherein the auxiliary agent comprises at least one of Cu, Co, In and Fe, and the content of the auxiliary agent is 0.5 wt% to 5 wt%.
8. A method for producing a nitrogen-doped tungsten carbide catalyst produced from the nitrogen-doped tungsten carbide catalyst according to claim 1 or the raw material composition for producing a nitrogen-doped tungsten carbide catalyst according to any one of claims 2 to 7, comprising the steps of:
(1) preparing a mixed solution of soluble tungsten salt, methylene amine organic matters and water, soaking the mixed solution on a carrier containing an acid site B, and drying at 80-120 ℃ to obtain a catalyst precursor;
(2) and placing the precursor in a mixed atmosphere containing hydrogen, and carrying out temperature programming on the precursor to 600-900 ℃ for carbonization for 2-12h to obtain the supported nitrogen-doped tungsten carbide catalyst, wherein the temperature raising rate of the temperature programming is 0.5-2 ℃/min.
9. The method of claim 8, wherein the gas mixture further comprises at least one of nitrogen, argon, and helium, and the volume fraction of the hydrogen gas is 10-50%.
10. Use of the nitrogen-doped tungsten carbide catalyst according to claim 1, or the carbon-doped tungsten carbide catalyst prepared from the raw material composition for preparing the nitrogen-doped tungsten carbide catalyst according to any one of claims 2 to 7, or the nitrogen-doped tungsten carbide catalyst prepared by the preparation method of the nitrogen-doped tungsten carbide catalyst according to claim 8 or 9 in the field of alcohol preparation from carbon dioxide hydrogenation gas.
11. The method for preparing alcohol by catalyzing carbon dioxide hydrogenation gas is characterized in that CO with the volume ratio of 1:3-1:42And H2Reacting to generate alcohol under the action of a catalyst, wherein the catalyst is the nitrogen-doped tungsten carbide catalyst as described in claim 1 or 2, or the nitrogen-doped tungsten carbide catalyst prepared by the preparation method of the nitrogen-doped tungsten carbide catalyst as described in claim 8 or 9.
12. The method for producing alcohol from carbon dioxide and hydrogen gas as claimed in claim 11, wherein the reaction temperature of the catalytic reaction is 200-350 ℃.
13. The method for producing alcohol from carbon dioxide and hydrogen gas according to claim 11 or 12, wherein the reaction pressure of the catalytic reaction is 0.5 to 10 MPa.
14. The method for producing alcohol from carbon dioxide and hydrogen gas as claimed in any one of claims 11 to 13, wherein the volume space velocity of the catalytic reaction is 1000--1。
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