CN111185209A - Preparation of molybdenum carbide supported nickel-based catalyst and application of catalyst in preparation of ethanol by hydrogenation of carbon dioxide - Google Patents
Preparation of molybdenum carbide supported nickel-based catalyst and application of catalyst in preparation of ethanol by hydrogenation of carbon dioxide Download PDFInfo
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Abstract
The invention provides a nickel modified molybdenum carbide catalyst, a preparation method thereof and application thereof in the reaction of preparing ethanol by carbon dioxide hydrogenation, wherein the nickel has good hydrogenation capability and the molybdenum carbide has good capability of activating carbon dioxide, so that the nickel carbide composite bimetallic catalyst has the characteristics of high selectivity and high activity compared with a non-noble metal catalyst, and compared with a noble metal catalyst, the nickel molybdenum carbide catalyst has the characteristics of low price and simple preparation.
Description
Technical Field
The invention belongs to the field of petrochemical industry, and particularly relates to a molybdenum carbide supported nickel-based catalyst, preparation thereof and application thereof in preparation of ethanol by carbon dioxide hydrogenation.
Background
Carbon dioxide is common greenhouse gas, waste gas generated in industrial production belongs to cheap, nontoxic and renewable carbon-resource, and low-carbon fuel with high added value such as methane, alcohol, formic acid and the like can be produced after enrichment. Therefore, the problem of global warming can be solved, and the utilization rate of carbon resources can be improved, so that the comprehensive utilization of carbon dioxide is more and more concerned by people. Carbon dioxide is a thermodynamically extremely stable molecule, and how to break carbon-oxygen bonds under mild conditions is extremely challengingThe subject of scientific research. In a common carbon dioxide activating mode, CO can be effectively improved by a catalytic hydrogenation reduction mode2The activation efficiency of (3). Thus, CO2The hydrogenation of alcohols is one of the important ways of carbon dioxide utilization.
Ethanol is used as a common solvent in a wide range of organic synthesis applications, and is used as a solvent for adhesives, nitrolacquers, varnishes, cosmetics, inks, paint removers, and the like, as a raw material for producing agricultural chemicals, medicines, rubbers, plastics, rayon, detergents, and the like, and as an antifreeze, a fuel, a disinfectant, and the like. Meanwhile, ethanol gasoline consumes a large amount of ethanol, so that the role of ethanol in future chemical production and national production is more and more important.
At present, by CO2The hydrogenation for synthesizing ethanol mainly adopts a homogeneous catalyst. Although the activity of the homogeneous catalyst is relatively high, an expensive organic ligand is required in the synthesis process, and the organic ligand is easy to oxidize and deteriorate in a reaction system, so that the stability of the homogeneous catalyst in the application process is worth worrying. In view of the problems of homogeneous catalysts, in recent years, efforts have been made to apply heterogeneous metal catalysts to CO2Hydrogenation to synthesize the ethanol. In this reaction, as for heterogeneous catalysts, Ir and Rh are the main noble metals, and these noble metals have not only high reaction temperature but also low catalytic activity, and therefore, the reaction temperature is 250 ℃. Meanwhile, the reaction solvent used in the system is often expensive and seriously polluted, so that the search for a proper catalyst for the application in carbon dioxide hydrogenation is very important.
In the art of synthesizing alcohols by hydrogenation of carbon dioxide, et al disclose a method for synthesizing ethanol and higher alcohols thereof by hydrogenation of carbon dioxide. Researchers take ruthenium and rhodium complex as catalyst, iodide as cocatalyst and solvent, and take CO2Hydrogenation and reaction are carried out to obtain ethanol and higher alcohol thereof. However, the catalyst is a homogeneous catalyst, a large amount of ligand is needed, and the air sensitivity causes that the service life of the catalyst is difficult to guarantee; meanwhile, the reaction pressure is up to 12MPa, and the product ethanol has low selectivity and low activity.
Chinese patent CN 104995161 a discloses a name: from CO or CO2Producing methanol and ethanol. The technology uses a ruthenium compound and a compound containing chlorine or bromine dissolved in tetraorganic phosphorus chloride salt or tetraorganic phosphorus bromide salt with low melting point as catalyst systems to catalyze CO2The mixture of (a) synthesizes methanol and ethanol. However, the service life of such homogeneous catalysts is difficult to guarantee; meanwhile, the reaction pressure is up to 25MPa, and the selectivity of the product ethanol is low.
Chinese patent CN 103191747A discloses a method for synthesizing low carbon alcohol catalyst by carbon dioxide hydrogenation. This technique utilizes Cu (N good)3)2、Zn(N〇3)2And Zr (N good)3)4Is a precursor of the catalyst and is added with Na2CO3The catalyst is a precipitator, CuZnZrO2 catalysts with different metal ratios are prepared by a coprecipitation method, and CO is reacted in a gas-solid reaction mode2Hydrogenation to alcohols. But the reaction temperature is high and is above 250 ℃, and the activity and the selectivity of ethanol are both low. The catalyst of the CoAlOx) composite oxide prepared by the coprecipitation method in Shaofeng is applied to the synthesis of carbon dioxide, the selectivity of the reaction is high and can reach more than 90%, but the yield of ethanol is only about 2%.
US patent US 8912240B2 discloses a product named: patented technology OF PRODUCTION OF Methanol andethanoflrom CO OR C02 (METHANOL and ethanol synthesis via CO OR C02). The technology uses organic phosphine chloride or bromide with homogeneous ruthenium complex highly dispersed in low melting point as catalyst, and CO can be obtained2And (3) catalytically hydrogenating to synthesize methanol and ethanol. But the reaction pressure is up to 25MPa, and the selectivity of the product ethanol is low. The application of gold catalysts in ethanol synthesis is continuously reported, the selectivity of the catalysts is very high and basically reaches one hundred percent, but the conversion rate of the catalysts is very low.
In summary, various types of catalytic CO are currently available2The homogeneous catalyst for synthesizing the ethanol by hydrogenation has strict requirements on reaction conditions and poor stability; the heterogeneous catalyst has high reaction temperature, high reaction energy consumption and low activity. Therefore, suitable cheap catalysts are searched for application in ethanol synthesisIs in need of much attention.
Disclosure of Invention
The method mainly solves two problems in the ethanol synthesis process, wherein the first is the activation of carbon dioxide, and the second is the activation of hydrogen, so that a nickel-modified molybdenum carbide catalyst is designed, and a bifunctional catalyst is constructed by utilizing the very good hydrogen activation capability of nickel and the good activation of carbon dioxide by molybdenum carbide, and is applied to the ethanol synthesis process.
Therefore, the invention relates to a nickel modified molybdenum carbide catalyst applied to the reaction of preparing ethanol by carbon dioxide hydrogenation, and the catalyst has the characteristics of high selectivity and high activity compared with a non-noble metal catalyst, and has the characteristics of low price and simple preparation compared with a noble metal catalyst.
The invention provides a nickel molybdenum carbide bifunctional catalyst with high catalytic efficiency and no noble metal and a preparation method thereof. According to the invention, by regulating the proportion of nickel and combining the stabilizing effect of the molybdenum carbide carrier on the nickel, the stability of the catalyst is improved, the loading amount of nickel metal in the catalyst is reduced, and the molybdenum carbide activates carbon dioxide, so that the catalyst prepared by the method is low in price, high in catalytic reaction activity, durable in stability and extremely high in market application value for preparing ethanol by hydrogenating carbon dioxide.
The invention provides a nano nickel supported catalyst on one hand, which is characterized in that the active component of the catalyst is metallic nickel, and the carrier is molybdenum carbide; the mass ratio of the metal nickel to the carrier molybdenum carbide is (0.001:1) - (0.5: 1).
On the other hand, the invention provides a preparation method of the nano nickel modified load molybdenum carbide catalyst, which comprises the following steps:
(1) dissolving soluble nickel salt in deionized water, adding molybdenum salt, heating and stirring at a certain temperature for 1-24 h, and evaporating water to obtain a solid, wherein the preferable temperature is 60-80 ℃;
(2) roasting the solid in the step (1) at 500-1000 ℃ for 1-600 minutes to obtain a composite oxide NiMoOx;
(3) roasting the composite oxide NiMoOx in a mixed atmosphere of hydrogen and methane for 0.5-12 h in 1% of O2Cooling and passivating for 10-24 hours in a/Ar atmosphere to obtain the catalyst Ni/Mo2C。
Based on the technical scheme, preferably, the soluble nickel salt is at least one of nickel acetate, nickel nitrate, nickel chloride, nickel sulfate and nickel acetylacetonate.
Based on the above technical solution, the volume ratio of the hydrogen gas to the methane is preferably (2:1) to (4:1), and more preferably 4: 1.
Based on the above technical scheme, preferably, the molybdenum salt is at least one of molybdic acid, paramolybdic acid, molybdate and paramolybdate.
The invention also provides an application of the nano nickel-loaded molybdenum carbide catalyst in preparation of ethanol by carbon dioxide hydrogenation.
Based on the above technical solution, preferably, the application comprises the following steps: firstly, weighing a certain amount of catalyst, adding the catalyst into a reaction kettle, adding a certain amount of solvent, replacing air in the reaction kettle by using carbon dioxide, filling the carbon dioxide to a certain pressure, then filling hydrogen, and reacting for 10 min-25 h at 100-300 ℃; the volume ratio of the carbon dioxide to the hydrogen is 1-30% to 99-70%.
Based on the technical scheme, preferably, the solvent is one or more of methanol, DMF, water, cyclohexane, dichloromethane and acetone chloroform dimethyl sulfoxide.
Based on the technical scheme, preferably, the mass ratio of the catalyst to the solvent is 0.001-1: 1; the gas pressure is 0.5-15 Mpa.
Advantageous effects
(1) The carbide has the catalytic property of noble-like metals, non-noble metals can be used to achieve the same catalytic effect as noble metals by introducing the carbide as a carrier, and meanwhile, nickel is added to regulate the content of metallic nickel and the valence state of the nickel, so that the activation capability of hydrogen is improved, and the nickel-molybdenum carbide bimetallic catalyst can have good catalytic property in the carbon dioxide hydrogenation reaction.
(2) The catalyst preparation method is simple, high in catalysis efficiency, simple in method operation, easy to control and suitable for industrial production.
(3) The catalyst improves the stability of the catalyst through strong interaction between carbide and nickel, particularly the stabilization of carbide crystal lattices on nickel, so that the supported nickel carbide bifunctional catalyst is used for synthesizing ethanol, has the advantages of simple, convenient and feasible synthesis method, environmental protection, safety, no toxicity, wide development space and great market application value, and better meets the requirements of sustainable development.
Drawings
FIG. 1 is a scanning electron micrograph of the catalyst prepared in example 1.
Detailed Description
Example 1
Preparation of 5% Ni/Mo2Sample C: separately weighing Ni (NO)3)2·nH2O 0.0662g、1.039g(NH4)6Mo7O24·4H2And dissolving the O in deionized water respectively to prepare solutions. Stirring for 2-3 hours at room temperature, standing for 2 hours, drying at 110 ℃, and roasting for 4 hours at 550 ℃ in air atmosphere to obtain NiMoOxA composite oxide.
Molding the prepared composite oxide (20-40 meshes), weighing the catalyst amount required by the reaction, placing the catalyst amount in a quartz reactor, and reacting in CH4-H2(CH4/H21:4), the temperature rising rate is 5 ℃/min when the temperature is between room temperature and 300 ℃, the temperature rising rate is 1 ℃/min when the temperature is between 300 ℃ and the carbonization final temperature (700 ℃), the temperature is kept for 120min at the carbonization final temperature, the temperature is reduced to the room temperature in the argon atmosphere, and 1 percent O containing trace oxygen is used2Passivating the/Ar for 12h to finally obtain NiMo2C catalyst (labeled a 1). It can be seen from FIG. 1 that the nickel molybdenum carbide synthesized by the patent has a very rough surface, thus having a high specific surface area and being beneficial to catalytic reactionThe process is carried out.
Example 2
Preparation of 5% Ni/Mo2Sample C: an experiment was conducted in a similar manner to example 1, except that the content of nickel prepared was changed to 1%, and Ni (NO) was added3)2·6H2The mass of O was changed to 0.01324g, and the product A2 was obtained by referring to example 1 for other specific steps.
Example 3
An experiment was conducted in a similar manner to example 1 except that ammonium molybdate was changed to molybdenum oxide, and example 1 was followed to obtain a product B.
Example 4
An experiment was carried out in a similar manner to example 1, except that the amount of nickel nitrate was changed to 0.10424g of nickel acetate, and example 1 was followed, to obtain product C.
Example 5
An experiment was conducted in a similar manner to example 1 except that the calcination temperature was changed to 800 degrees centigrade and the other specific steps were carried out with reference to example 1 to obtain product D.
Example 6
An experiment was carried out in a similar manner to example 1 except that the ratio of methane to hydrogen in the calcination atmosphere was changed to 1, and the product E was obtained by referring to example 1 for other specific steps.
Examples 7 to 17
Weighing 20mg of catalyst, adding 20ml of solvent, firstly filling carbon dioxide into a 100ml reaction kettle, replacing for three times, and then filling a certain amount of CO2Gas is filled with a certain amount of H2And (3) keeping the reaction kettle at a constant temperature for a certain time by using gas, and starting a mechanical stirrer at a stirring speed of 1500 rpm. The gas after the reaction is analyzed by gas chromatography, the types of the catalyst, the types of the solvent, the reaction time and the proportion of the reaction gas (carbon dioxide and hydrogen) are changed to obtain different embodiments, and specific experimental results are shown in the following table, wherein the catalyst has the optimal reaction activity when the proportion of the carbon dioxide and the hydrogen in the DMF solvent is 1:1 and the reaction is carried out at 150 ℃, and compared with the general reaction temperature in the patent which is more than 200 ℃, the reaction temperature is greatly higherThe reaction temperature is reduced, and the method has the potential of large-scale industrial application.
Claims (10)
1. A nano nickel supported catalyst is characterized in that the active component of the catalyst is metallic nickel, and the carrier is molybdenum carbide; the mass ratio of the metallic nickel to the carrier molybdenum carbide is 0.001: 1-0.5: 1; the method of loading metallic nickel on the carrier includes impregnation, coprecipitation or precipitation.
2. A method for preparing the catalyst of claim 1, comprising the steps of:
(1) dissolving soluble nickel salt in deionized water, adding molybdenum salt, heating and stirring at 60-100 ℃ for 1-24 h, and evaporating to obtain a solid;
(2) roasting the solid in the step (1) at 500-1000 ℃ for 1-600 minutes, preferably 60-120 minutes to obtain a composite oxide NiMoOx；
(3) Mixing the composite oxide NiMoO obtained in the step (2)xRoasting at the temperature of 700 ℃ in the mixed atmosphere of hydrogen and methane, wherein the roasting time is 0.5-12 h and is 1% of O2Cooling and passivating for 10-24 hours in a/Ar atmosphere to obtain the catalyst Ni/Mo2C。
3. The method according to claim 2, wherein the soluble nickel salt is at least one of nickel acetate, nickel nitrate, nickel chloride, nickel sulfate, and nickel acetylacetonate.
4. The production method according to claim 2, wherein the volume ratio of hydrogen to methane in the step (2) is 2:1 to 4: 1.
5. The method according to claim 2, wherein the molybdenum salt is at least one of molybdic acid, paramolybdic acid, molybdate salt and paramolybdate salt.
6. The preparation method according to claim 2, wherein in the step (3), the roasting adopts a temperature programming method, the temperature rising rate is firstly 5 ℃/min to rise to a certain temperature, and then the temperature is continuously raised to the roasting temperature by 1 ℃/min.
7. Use of the catalyst of claim 1 in the hydrogenation of carbon dioxide to ethanol.
8. Use according to claim 7, characterized in that it comprises the following steps:
(1) firstly, adding a catalyst into a reaction kettle, and then adding a solvent, wherein the mass ratio of the catalyst to the solvent is 0.001-0.1;
(2) replacing air in the reaction kettle by using carbon dioxide, and then continuously filling the carbon dioxide to a certain pressure;
(3) filling hydrogen, and reacting at 100-300 ℃ for 10 min-25 h; the volume ratio of the carbon dioxide to the hydrogen is 1-30% to 99-70%.
9. Use according to claim 8, characterized in that the solvent is at least one of methanol, DMF, water, cyclohexane, dichloromethane, acetone chloroform dimethyl sulfoxide.
10. The use according to claim 8, wherein the mass ratio of the catalyst to the carbon dioxide is 0.001-1: 1; the pressure is 0.5-15 MPa.
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Cited By (4)
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| CN113145147A (en) * | 2021-04-30 | 2021-07-23 | 华东理工大学 | Supported molybdenum carbide catalyst, preparation method thereof and application of catalyst in selective production of phenol monomers by depolymerizing lignin |
| CN115121116A (en) * | 2022-07-14 | 2022-09-30 | 李永生 | Process method for converting carbon dioxide into ethanol |
| CN115228491A (en) * | 2021-04-23 | 2022-10-25 | 中国科学院大连化学物理研究所 | High-dispersion rhodium-based catalyst, preparation method thereof and application thereof in preparation of ethanol from carbon dioxide |
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| CN112808286A (en) * | 2021-01-27 | 2021-05-18 | 常州工学院 | Cobalt/molybdenum carbide nano catalyst and preparation method and application thereof |
| CN115228491A (en) * | 2021-04-23 | 2022-10-25 | 中国科学院大连化学物理研究所 | High-dispersion rhodium-based catalyst, preparation method thereof and application thereof in preparation of ethanol from carbon dioxide |
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| CN115121116A (en) * | 2022-07-14 | 2022-09-30 | 李永生 | Process method for converting carbon dioxide into ethanol |
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