CN114570423A - Catalyst for preparing ethanol and propanol from synthesis gas and preparation method and application thereof - Google Patents

Catalyst for preparing ethanol and propanol from synthesis gas and preparation method and application thereof Download PDF

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CN114570423A
CN114570423A CN202111607885.8A CN202111607885A CN114570423A CN 114570423 A CN114570423 A CN 114570423A CN 202111607885 A CN202111607885 A CN 202111607885A CN 114570423 A CN114570423 A CN 114570423A
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catalyst
solution
synthesis gas
propanol
solid solution
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CN114570423B (en
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房克功
张明伟
穆晓亮
***
赵璐
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

The invention belongs to the technical field of synthesis gas conversion, and relates to a catalyst for preparing ethanol and propanol from synthesis gas, which comprises three components of a structural solid solution, a metal boride and a hydrophobic modified layer, wherein the structural solid solution is one of ZnCr, ZnZr, ZnAl, MgAl, MnAl, CeZr, LaZr, MnZr and MnCe, the weight percentage of the structural solid solution in the catalyst is 49-85%, the weight percentage of the metal boride in the catalyst is 10-50%, and the weight percentage of the hydrophobic modified layer in the catalyst is 0.5-10%. The invention also relates to a preparation method and application of the catalyst.

Description

Catalyst for preparing ethanol and propanol from synthesis gas and preparation method and application thereof
Technical Field
The invention belongs to the technical field of synthesis gas conversion, and particularly relates to a catalyst for efficiently synthesizing ethanol and propanol by taking synthesis gas (mixed gas of CO and hydrogen) as a raw material, a preparation method and application.
Background
Ethanol and propanol are basic chemical raw materials with high added values, and have wide application in the fields of producing high-octane oxygen-containing fuel oil, additives, organic solvents, polyester and other fuels and chemicals. The traditional ethanol and propanol production technology relates to the routes of grain fermentation, petroleum-based ethylene hydration or hydroformylation and the like, and the requirements of fuel oil and chemical markets on ethanol and propanol are difficult to meet. Therefore, the development of the technology for preparing ethanol and propanol by taking the low-cost synthesis gas as the raw material has important strategic and practical significance for reducing the industrial consumption of food in China, relieving the shortage of petroleum resources, improving the multi-element development level and quality of the energy and chemical industry and the like.
The reaction of preparing ethanol and propanol (C2-C3 alcohol) from synthesis gas is that under the action of heterogeneous catalyst, CO and hydrogen are adsorbed, dissociated and hydrogenated on the surface of the catalyst to form intermediate species containing C, O, H and other elements, and further carbon chain growth (C-C coupling) and oxidation group (CO) are carried out*) The insertion reaction is carried out to obtain the final product. In the process, the reasonable regulation and control of the surface active components of the catalyst and the synergistic effect thereof are the key points for synthesizing ethanol and propanol with high selectivity. The catalysts for preparing C2-C3 low-carbon alcohol from synthesis gas, which are found at present, can be roughly divided into the following types:a modified methanol synthesis catalyst mainly comprising a low-pressure Cu-Zn and high-pressure Zn-Cr catalyst modified by an alkaline assistant (such as Cs, K and the like), a copper-modified Fe-Co-based Fischer-Tropsch synthesis catalyst, a precious metal Rh-based catalyst, a molybdenum sulfide-based catalyst and the like. Chinese patent CN 104128186B discloses a catalyst for preparing low carbon alcohol by synthesis gas and a preparation method thereof, the catalyst is prepared by mechanically mixing and grinding AlOOH and an industrial methanol CuZnAl catalyst, and is used for synthesis reaction of low carbon alcohol prepared by fixed bed synthesis gas, the selectivity of the low carbon alcohol is 50%, wherein the selectivity of C2+ alcohol is more than 20%. Chinese patent CN 104056629B discloses a low carbon alcohol synthesis catalyst using graphite or graphene as a carrier to load CuCo alloy components, wherein the selectivity of synthesizing low carbon alcohol by converting synthesis gas reaches 56.8% under the reaction conditions of 260-290 ℃ and 6.0MPa, but the distribution of alcohol products is wider. Chinese patent CN 103764277A discloses an alkali metal modified RhMn-based catalyst, which is used for catalytic conversion of synthesis gas to generate more organic oxygen-containing compounds such as acetic acid, ethanol, methyl formate, methyl acetate and the like, and the gaseous product is mainly methane. Chinese patent CN 108325548A discloses a catalyst for grinding and mixing potassium carbonate and molybdenum sulfide, which obtains over 70 percent of low-carbon alcohol selectivity (CO) under the conditions of 10MPa of pressure and 300-350 ℃ of reaction temperature2Not counted in), but a large amount of CO is present in the gaseous product2Greatly reduces the carbon utilization rate in the alcohol synthesis process.
From the above published reports, the modified methanol synthesis catalyst and the copper modified fischer-tropsch synthesis catalyst respectively cause the generation of a large amount of byproducts such as hydrocarbons and methanol, and the content of C2-C3 alcohol is low; the noble metal catalyst is easy to generate more methane and C2 acid/aldehyde/ester products, and the cost of the catalyst is higher, so the catalyst is not suitable for large-scale industrial application. The reaction conditions suitable for the molybdenum sulfide-based catalyst are harsh, the conversion rate of raw material gas is high only under the conditions of high pressure (8.0-12 MPa) and high temperature (320-2Resulting in low carbon utilization and pollution of ecological environment. In addition, on each of the catalysts disclosed above, the C2-C3 alcohols tend not to be the major products and are difficult to pass through for subsequent separationsAnd obtaining a large amount of the target product C2-C3 alcohol. At present, no catalyst for one-step directional conversion and high-efficiency synthesis of ethanol and propanol products by taking synthesis gas as a raw material, a preparation method and application thereof are found in China.
Disclosure of Invention
The invention aims to provide a catalyst for synthesizing ethanol and propanol directionally by catalytic conversion of synthesis gas, and a preparation method and application thereof, aiming at the defects of the existing technology for preparing low-carbon alcohol from synthesis gas.
The technical scheme adopted by the invention is as follows: the catalyst for preparing ethanol and propanol from synthesis gas comprises three components of a structural solid solution, a metal boride and a hydrophobic modification layer, wherein the structural solid solution is one of ZnCr, ZnZr, ZnAl, MgAl, MnAl, CeZr, LaZr, MnZr and MnCe, the weight percentage content of the structural solid solution in the catalyst is 49-85%, the weight percentage content of the metal boride in the catalyst is 10-50%, and the weight percentage content of the hydrophobic modification layer in the catalyst is 0.5-10%.
The metal boride is a boride formed by reacting one or more of Rh, Pd, Ir, Co, Mo, Cu, Ni or Fe with boron element.
The hydrophobic modification layer is one of trimethylchlorosilane TMCS, dimethyldiethoxysilane DMDES, methyltriethoxysilane MTES, hexadecyltrichlorosilane HTCS and octyltrichlorosilane OTCS.
A preparation method of a catalyst for preparing ethanol and propanol from synthesis gas is characterized by comprising the following steps: the method comprises the following steps
Step one, preparing a structural solid solution precursor
Step 11, dissolving soluble metal salt of any structural solid solution in deionized water to prepare a bimetal mixed salt solution, and marking as A solution;
step 12, dissolving a precipitator in deionized water to obtain a solution B;
step 13, adding deionized water into a beaker, heating to 40-95 ℃, dripping the solution A and the solution B into the beaker under the stirring condition, keeping the pH value at 6.5-9, carrying out coprecipitation reaction, continuing stirring for 1-4h after precipitation is finished, naturally cooling to room temperature, filtering, washing the obtained solid with deionized water for 3-6 times, and removing surface residual impurities to obtain a structural solid solution precursor;
step two, introduction of active metal boride component
Step 21, placing soluble metal salt of metal boride, ammonium fluoride NH4F and urea in a polytetrafluoroethylene lined hydrothermal synthesis kettle, stirring at room temperature, dissolving to obtain a clear and transparent solution C, adding the structural solid solution precursor prepared in step 13 into the solution C, sealing the polytetrafluoroethylene lined hydrothermal synthesis kettle, carrying out constant-temperature hydrothermal treatment at 120 ℃ for 4-12h, cooling to room temperature, carrying out centrifugal separation, washing the obtained solid with deionized water for 3-6 times, removing surface residual impurities, and then drying and roasting to obtain solid powder containing the structural solid solution;
step 22, preparing 8-25% of sodium borohydride aqueous solution or 0-35% of boric acid aqueous solution, wherein the mass concentration of sodium hydroxide in the sodium borohydride aqueous solution is 3%, soaking the solid powder containing the structural solid solution prepared in the step 21 in the sodium borohydride aqueous solution or the boric acid aqueous solution, stirring for 30-90 minutes at room temperature, filtering, and vacuum-drying for 2-8 hours at 40-150 ℃ to obtain solid powder containing the structural solid solution and the metal boride;
step three, introducing a hydrophobic modification layer
And 31, transferring the solid powder containing the structural solid solution and the metal boride prepared in the step 22 into a conical flask, sequentially adding toluene and a hydrophobic modification component, carrying out ultrasonic oscillation treatment, washing an obtained sample with toluene, and further carrying out vacuum drying to obtain the catalyst for preparing ethanol and propanol from synthesis gas.
The total metal ion concentration of the solution A is 0.3-0.8mol/L, and the molar ratio of two metal ions is (0.1-0.6): 1; the precipitator in the preparation process of the solution B is one of ammonia water, ammonium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide, and the molar concentration of the precipitator in the solution B is 0.4-2 mol/L.
In the clear and transparent solution C obtained in the step 21, the concentration of total metal ions is 0.2-0.7mol/L, the concentration of ammonium fluoride is 0.5-2.0 mol/L, and the concentration of urea is 0.9-3.0 mol/L.
In the sodium borohydride aqueous solution prepared in the step 22, the mass concentration of the sodium borohydride is 10-15%, and in the boric acid aqueous solution prepared in the step 22, the mass concentration of the boric acid is 15-25%.
In step 31, 8-30ml of toluene is added per 1g of solid powder containing the structural solid solution and the metal boride, and 1-2ml of the hydrophobic modification component is added per 1g of solid powder containing the structural solid solution and the metal boride.
In step 31, 10 to 15ml of toluene is added per 1g of solid powder containing the structural solid solution and the metal boride, and 0.5 to 6ml of the hydrophobic modification component is added per 1g of solid powder containing the structural solid solution and the metal boride.
The application of the catalyst for preparing ethanol and propanol from synthesis gas is characterized in that: the process adopts a fixed bed process or a slurry bed process, the catalyst is firstly subjected to reduction pretreatment in a reducing atmosphere at 400 ℃ under 300--1The reduction pressure is 0.2-0.5MPa, and the reduction time is 6-12 h; then, the synthesis gas raw material is sent to a reactor to perform catalytic reaction with the reduced catalyst, and products after the reaction are condensed and separated to obtain ethanol and propanol products.
In a reducing atmosphere is H2And N2Formed mixed gas of H2Accounting for 10 percent of the total volume of the mixed gas, and the space velocity of the reducing gas is 1200-1600 h-1The reduction pressure is 0.3-0.4MPa, and the reduction time is 8-10 h.
H in the raw material synthesis gas is fed into a reactor to perform catalytic reaction with the reduced catalyst2The mol ratio of the carbon dioxide to CO is 1-3: 1; the reaction temperature is 220 ℃ and 280 ℃; the reaction pressure is 4.0-7.0 MPa; raw material synthesis gas air speed of 1000-6000h-1。
H in the raw material synthesis gas is fed into a reactor to perform catalytic reaction with the reduced catalyst2The mol ratio of the carbon dioxide to CO is 1.5-2.5: 1; the reaction temperature is 240 ℃ and 260 ℃; the reaction pressure is 5.0-6.5 MPa; the space velocity of the raw material synthesis gas is 3000--1
The invention has the following advantages and beneficial effects:
(1) the preparation method of the catalyst integrates the advantages of coprecipitation and hydrothermal synthesis of the catalyst, so that the structural carrier of the catalyst and the active metal component have stronger synergistic effect, and the obtained catalyst has smaller particle size and uniform composition distribution;
(2) according to the invention, the boronizing treatment of the active metal of the catalyst can improve the metal dispersion degree and the structural stability, and simultaneously can reduce the active sites of the hydrocarbon by-products generated by further carbon chain growth due to complete dissociation and adsorption of part of carbon monoxide on the surface of the metal, and inhibit the generation of the hydrocarbon by-products;
(3) the surface of the catalyst has hydrophobic property, water generated in the reaction process can be quickly removed, the oxidation of water to active metal on the surface of the catalyst and the water gas shift reaction are inhibited, and CO is greatly reduced2The generation of the reaction reduces the emission of greenhouse gases at the outlet of the reactor, and is a green and environment-friendly reaction process for synthesizing alcohol;
(4) the catalyst product is distributed intensively, the total alcohol selectivity is more than 70 percent, the content of ethanol and propanol in the total alcohol is up to 75 percent, and the catalyst is far higher than the reported performance of the traditional low-carbon alcohol synthesis catalyst, and the high-efficiency selective control synthesis of preparing C2-C3 alcohol by converting synthesis gas can be realized;
(5) the catalyst has the advantages of low price of raw materials for preparation, easy engineering amplification of the preparation method, mild reaction conditions, short process engineering, realization of one-step direct conversion of the synthesis gas into the ethanol and the propanol, great reduction of the construction cost of production devices and good industrial application prospect.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
Example 1
Catalyst preparation
Preparation of (I) solid solution precursor
(1) Weighing 7.5g Al (NO)3)3∙9H2O、15.36g Mg(NO3)2∙6H2Dissolving O in 200mL of deionized water to prepare a solution A;
(2) weighing 6.21g K2CO310.08g KOH in 200mL deionized waterPreparing a solution B;
(3) adding 100mL of deionized water into a beaker, heating to 60 ℃, dripping the solution A and the solution B into the solution in the beaker in a parallel flow manner through a peristaltic pump for coprecipitation reaction at a stirring speed of 100 r/min, keeping the pH value of the solution at 9, continuing stirring for 2h after the precipitation is finished, naturally cooling the precipitated solution to room temperature, filtering, washing the obtained solid for 3 times by using the deionized water, and removing residual impurities on the surface.
Introduction of (di) active metal boride component
(4) 2.91g Cu (NO) was weighed3)2∙3H2O、1.62g Fe(NO3)3∙9H2Placing O and 4.32g of urea in a polytetrafluoroethylene-lined hydrothermal synthesis kettle, adding 80mL of deionized water, stirring at room temperature, dissolving to obtain a clear and transparent uniform solution, transferring the structural solid solution precursor obtained in the step (3) into a metal component solution in the polytetrafluoroethylene-lined hydrothermal synthesis kettle, stirring, sealing the polytetrafluoroethylene-lined hydrothermal synthesis kettle, carrying out constant-temperature hydrothermal treatment at 120 ℃ for 12 hours, cooling to room temperature, carrying out centrifugal separation, washing the obtained solid with deionized water for 3 times, removing residual impurities on the surface, drying at 100 ℃ for 12 hours, and roasting at 350 ℃ for 3 hours;
(5) preparing 10% sodium borohydride (containing 3% sodium hydroxide) by mass concentration, soaking the solid obtained in the step (4) in 50mL of the sodium borohydride solution, stirring for 30 minutes at room temperature, filtering, and drying for 4 hours in vacuum at 100 ℃.
(III) hydrophobic modification treatment
(6) And (3) transferring 5g of the solid powder obtained in the step (II) into a conical flask, sequentially adding 50mL of toluene and 5mL of methyltriethoxysilane hydrophobic modification component, carrying out ultrasonic oscillation treatment for 2h, washing the obtained sample with toluene, and further carrying out vacuum drying at 100 ℃ for 12h to obtain the catalyst required by the invention.
Catalyst application
2g of the catalyst prepared according to the method of the above example was charged into a fixed bed reactor. The method is carried out by using the following application steps, wherein the catalyst is firstly reduced at 300 ℃ in 10% H atmosphere before being used2/N2In the mixed gasCarrying out reduction pretreatment, wherein the space velocity of the reduction gas is 1000h-1The reduction pressure is 0.2MPa, and the reduction time is 6 h; then, the synthesis gas raw material is sent to a reactor to perform catalytic reaction with the reduced catalyst, and products after the reaction are condensed and separated to obtain ethanol and propanol products.
The catalytic reaction condition is H in the raw material synthesis gas2The mol ratio of/CO is 2: 1; the reaction temperature is 220 ℃; the reaction pressure is 4.0 MPa; air speed of raw material synthesis gas is 4000h-1。
Example 2
Catalyst preparation
Preparation of (I) solid solution precursor
(1) Weighing 7.5g Al (NO)3)3∙9H2O、28.63g Mn(NO3)2Dissolving (50 wt.% aqueous solution) in 200mL of deionized water to obtain solution A;
(2) weighing 13.55g of KOH and dissolving in 200mL of deionized water to prepare a solution B;
(3) adding 100mL of deionized water into a beaker, heating to 70 ℃, dripping the solution A and the solution B into the beaker solution through a peristaltic pump in a parallel flow manner at a stirring speed of 100 revolutions per minute for coprecipitation reaction, keeping the pH value of the solution at 8.5, continuing stirring for 1h after the precipitation is finished, naturally cooling the precipitated solution to room temperature, filtering, washing the obtained solid for 3 times by using the deionized water, and removing residual impurities on the surface.
Introduction of (di) active metal boride component
(4) Weigh 5.81g Cu (NO)3)2∙3H2O、6.98g Co(NO3)2·6H2O and 2.88g of urea are placed in a polytetrafluoroethylene-lined hydrothermal synthesis kettle, 160mL of deionized water is added, stirring is carried out at room temperature, a clear and transparent uniform solution is obtained by dissolution, the structural solid solution precursor obtained in the step (3) is transferred into a metal component solution in the polytetrafluoroethylene-lined hydrothermal synthesis kettle, stirring is carried out, the polytetrafluoroethylene-lined hydrothermal synthesis kettle is sealed, the constant-temperature hydrothermal treatment is carried out at 120 ℃ for 12h, cooling is carried out to the room temperature, centrifugal separation is carried out, the obtained solid is washed for 3 times by the deionized water, residual impurities on the surface are removed, drying is carried out at 100 ℃ for 12h, and roasting is carried out at 350 ℃ for 12h3h；
(5) Preparing sodium borohydride (containing 3% of sodium hydroxide) with the mass concentration of 15%, soaking the solid obtained in the step (4) in 50mL of the sodium borohydride solution, stirring for 30 minutes at room temperature, filtering, and drying for 4 hours in vacuum at 100 ℃.
(III) hydrophobic modification treatment
(6) And (3) transferring 5g of the solid powder obtained in the step (II) into a conical flask, sequentially adding 50mL of toluene and 5mL of dimethyl diethoxy silane hydrophobic modification component, carrying out ultrasonic oscillation treatment for 2h, washing the obtained sample with toluene, and further carrying out vacuum drying at 100 ℃ for 12h to obtain the catalyst required by the invention.
Catalyst application
2g of the catalyst prepared according to the method of the above example was charged into a fixed bed reactor. The method is carried out by using the following application steps that before the catalyst is used, the catalyst is firstly reduced at 350 ℃ in 10% H atmosphere2/N2Carrying out reduction pretreatment in the mixed gas, wherein the space velocity of the reduction gas is 2000h-1The reduction pressure is 0.5MPa, and the reduction time is 12 h; then, the synthesis gas raw material is sent to a reactor to perform catalytic reaction with the reduced catalyst, and products after the reaction are condensed and separated to obtain ethanol and propanol products.
The catalytic reaction conditions are as follows: h in raw syngas2The mol ratio of/CO is 2:1, the reaction temperature is 240 ℃, and the reaction pressure is 5.0 MPa; raw material synthesis gas space velocity 3000h-1。
Example 3
Catalyst preparation
Preparation of (I) solid solution precursor
(1) Weighing 7.5g Al (NO)3)3∙9H2O、23.8g Zn(NO3)2·6H2Dissolving O in 200mL of deionized water to prepare a solution A;
(2) weighing 16.05g of KOH and dissolving in 200mL of deionized water to prepare a solution B;
(3) adding 100mL of deionized water into a beaker, heating to 70 ℃, dripping the solution A and the solution B into the beaker solution through a peristaltic pump in a parallel flow manner at a stirring speed of 100 revolutions per minute for coprecipitation reaction, keeping the pH value of the solution at 8.5, continuing stirring for 1h after the precipitation is finished, naturally cooling the precipitated solution to room temperature, filtering, washing the obtained solid for 3 times by using the deionized water, and removing residual impurities on the surface.
Introduction of (di) active metal boride component
(4) Weigh 7.26g Cu (NO)3)2∙3H2O、8.73g Ni(NO3)2·6H2Placing O and 3.6g of urea in a polytetrafluoroethylene-lined hydrothermal synthesis kettle, adding 150mL of deionized water, stirring at room temperature, dissolving to obtain a clear and transparent uniform solution, transferring the structural solid solution precursor obtained in the step (3) into a metal component solution in the polytetrafluoroethylene-lined hydrothermal synthesis kettle, stirring, sealing the polytetrafluoroethylene-lined hydrothermal synthesis kettle, carrying out constant-temperature hydrothermal treatment at 120 ℃ for 12 hours, cooling to room temperature, carrying out centrifugal separation, washing the obtained solid with deionized water for 3 times, removing residual impurities on the surface, drying at 100 ℃ for 12 hours, and roasting at 350 ℃ for 3 hours;
(5) preparing sodium borohydride (containing 3% of sodium hydroxide) with the mass concentration of 15%, soaking the solid obtained in the step (4) in 50mL of the sodium borohydride solution, stirring for 30 minutes at room temperature, filtering, and drying for 4 hours in vacuum at 100 ℃.
(III) hydrophobic modification treatment
(6) And (3) transferring 5g of the solid powder obtained in the step (II) to a conical flask, sequentially adding 50mL of toluene and 5mL of octyl trichlorosilane hydrophobic modification component, carrying out ultrasonic oscillation treatment for 2h, washing the obtained sample with toluene, and further carrying out vacuum drying at 100 ℃ for 12h to obtain the catalyst required by the invention.
Catalyst application
5g of the catalyst prepared according to the method of the above example was charged into a slurry bed reactor. The method is carried out by using the following application steps, wherein the catalyst is firstly reduced at 300 ℃ in 10% H atmosphere before being used2/N2Carrying out reduction pretreatment in the mixed gas, wherein the space velocity of the reduction gas is 1000h-1The reduction pressure is 0.2MPa, and the reduction time is 6 h; then, the synthesis gas raw material is sent to a reactor to perform catalytic reaction with the reduced catalyst, and products after the reaction are condensed and separated to obtain ethanol and propanol products.
The catalytic reaction conditions are as follows: h in raw syngas2The mol ratio of/CO is 1.5:1, the reaction temperature is 220 ℃, the reaction pressure is 5.0MPa, and the air speed of the raw material synthesis gas is 1000h-1。
Example 4
Catalyst preparation
Preparation of (I) solid solution precursor
(1) 25.76g Zr (NO) were weighed3)4·5H2O、5.95g Zn(NO3)2·6H2Dissolving O in 200mL of deionized water to prepare a solution A;
(2) weighing 42.5g K2CO3Dissolving in 200mL of deionized water to prepare a solution B;
(3) adding 100mL of deionized water into a beaker, heating to 70 ℃, dripping the solution A and the solution B into the beaker solution through a peristaltic pump in a parallel flow manner at a stirring speed of 100 revolutions per minute for coprecipitation reaction, keeping the pH value of the solution at 8, continuing stirring for 1h after the precipitation is finished, naturally cooling the precipitated solution to room temperature, filtering, washing the obtained solid for 3 times by using the deionized water, and removing residual impurities on the surface.
Introduction of (di) active metal boride component
(4) Weigh 7.26g Cu (NO)3)2∙3H2O、37.08g H24Mo7N6O24·4H2Placing O and 5.4g of urea in a polytetrafluoroethylene-lined hydrothermal synthesis kettle, adding 150mL of deionized water, stirring at room temperature, dissolving to obtain a clear and transparent uniform solution, transferring the structural solid solution precursor obtained in the step (3) into a metal component solution in the polytetrafluoroethylene-lined hydrothermal synthesis kettle, stirring, sealing the polytetrafluoroethylene-lined hydrothermal synthesis kettle, carrying out constant-temperature hydrothermal treatment at 120 ℃ for 12 hours, cooling to room temperature, carrying out centrifugal separation, washing the obtained solid with deionized water for 3 times, removing residual impurities on the surface, drying at 100 ℃ for 12 hours, and roasting at 350 ℃ for 3 hours;
(5) preparing a boric acid aqueous solution with the mass concentration of 10%, soaking the solid obtained in the step (4) in the boric acid aqueous solution, stirring for 60 minutes at room temperature, filtering, and vacuum-drying for 8 hours at 150 ℃.
(III) hydrophobic modification treatment
(6) And (3) transferring 5g of the solid powder obtained in the step (II) into a conical flask, sequentially adding 50mL of toluene and 5mL of hexadecyl trichlorosilane hydrophobic modification component, carrying out ultrasonic oscillation treatment for 2h, washing the obtained sample with toluene, and further carrying out vacuum drying at 100 ℃ for 12h to obtain the catalyst required by the invention.
Catalyst application
3g of the catalyst prepared according to the method of the above example was charged into a fixed bed reactor. The method is carried out by using the following application steps, wherein the catalyst is firstly reduced in atmosphere of 10% H at 400 ℃ before being used2/N2Carrying out reduction pretreatment in the mixed gas, wherein the space velocity of the reduction gas is 2000h-1The reduction pressure is 0.5MPa, and the reduction time is 12 h; then, the synthesis gas raw material is sent to a reactor to perform catalytic reaction with the reduced catalyst, and products after the reaction are condensed and separated to obtain ethanol and propanol products.
The catalytic reaction conditions are as follows: h in raw syngas2The mol ratio of/CO is 2.5:1, preferably 1.5-2.5:1, the reaction temperature is 280 ℃, the reaction pressure is 7.0MPa, and the air speed of the raw material synthesis gas is 2000h-1。
Example 5
Catalyst preparation
Preparation of (I) solid solution precursor
(1) 25.76g Zr (NO) were weighed3)4·5H2O、10.74g Mn(NO3)2Dissolving (50 wt.% aqueous solution) in 200mL of deionized water to obtain solution A;
(2) 38.16g of Na were weighed2CO3Dissolving in 200mL of deionized water to prepare a solution B;
(3) adding 100mL of deionized water into a beaker, heating to 70 ℃, dripping the solution A and the solution B into the beaker solution through a peristaltic pump in a parallel flow manner at a stirring speed of 100 revolutions per minute for coprecipitation reaction, keeping the pH value of the solution at 8, continuing stirring for 1h after the precipitation is finished, naturally cooling the precipitated solution to room temperature, filtering, washing the obtained solid for 3 times by using the deionized water, and removing residual impurities on the surface.
Introduction of (di) active metal boride component
(4) 14.52g of Cu (NO) was weighed3)2∙3H2O、3.14g RhCl3·3H2Placing O hydrate (Rh 40%) and 4.32g of urea in a polytetrafluoroethylene lined hydrothermal synthesis kettle, adding 150mL of deionized water, stirring at room temperature, dissolving to obtain a clear and transparent uniform solution, transferring the structural solid solution precursor obtained in the step (3) into a metal component solution in the polytetrafluoroethylene lined hydrothermal synthesis kettle, stirring, sealing the polytetrafluoroethylene lined hydrothermal synthesis kettle, carrying out constant-temperature hydrothermal treatment at 120 ℃ for 12 hours, cooling to room temperature, carrying out centrifugal separation, washing the obtained solid with deionized water for 3 times, removing surface residual impurities, drying at 100 ℃ for 12 hours, and roasting at 350 ℃ for 3 hours;
(5) preparing a boric acid aqueous solution with the mass concentration of 10%, soaking the solid obtained in the step (4) in the boric acid aqueous solution, stirring for 60 minutes at room temperature, filtering, and vacuum-drying for 8 hours at 150 ℃.
(III) hydrophobic modification treatment
(6) And (3) transferring 5g of the solid powder obtained in the step (II) into a conical flask, sequentially adding 50mL of toluene and 10mL of trimethylchlorosilane hydrophobic modification component, carrying out ultrasonic oscillation treatment for 2h, washing the obtained sample with toluene, and further carrying out vacuum drying at 100 ℃ for 12h to obtain the catalyst required by the invention.
Catalyst application
2g of the catalyst prepared according to the method of the above example was charged into a fixed bed reactor. The method is carried out by using the following application steps, wherein the catalyst is firstly reduced at 300 ℃ in 10% H atmosphere before being used2/N2Carrying out reduction pretreatment in the mixed gas, wherein the space velocity of the reduction gas is 1500h-1The reduction pressure is 0.3MPa, and the reduction time is 8 h; then, the synthesis gas raw material is sent to a reactor to perform catalytic reaction with the reduced catalyst, and products after the reaction are condensed and separated to obtain ethanol and propanol products.
The catalytic reaction conditions are as follows: h in raw syngas2The mol ratio of/CO is 2.5: 1; the reaction temperature is 230 ℃, the reaction pressure is 5.0MPa, and the air speed of the raw material synthesis gas is 4000h-1。
Example 6
Catalyst preparation
Preparation of (I) solid solution precursor
(1) 8.59g Zr (NO) were weighed3)4·5H2O、34.74g Ce(NO3)3·6H2Dissolving O in 200mL of deionized water to prepare a solution A;
(2) weighing 23.94g of ammonia water (25%) and dissolving the ammonia water in 200mL of deionized water to prepare a solution B;
(3) adding 100mL of deionized water into a beaker, heating to 70 ℃, dripping the solution A and the solution B into the beaker solution through a peristaltic pump in a parallel flow manner at a stirring speed of 100 revolutions per minute for coprecipitation reaction, keeping the pH value of the solution at 8, continuing stirring for 1h after the precipitation is finished, naturally cooling the precipitated solution to room temperature, filtering, washing the obtained solid for 3 times by using the deionized water, and removing residual impurities on the surface.
Introduction of (di) active metal boride component
(4) 14.52g of Cu (NO) was weighed3)2∙3H2O、3.14g Pd(NO3)2Putting the aqueous solution (Pd 18%) and 4.32g of urea into a polytetrafluoroethylene lining hydrothermal synthesis kettle, adding 150mL of deionized water, stirring at room temperature, dissolving to obtain a clear and transparent uniform solution, transferring the structural solid solution precursor obtained in the step (3) into a metal component solution in the polytetrafluoroethylene lining hydrothermal synthesis kettle, stirring, sealing the polytetrafluoroethylene lining hydrothermal synthesis kettle, carrying out constant-temperature hydrothermal treatment at 120 ℃ for 12 hours, cooling to room temperature, carrying out centrifugal separation, washing the obtained solid with deionized water for 3 times, removing surface residual impurities, drying at 100 ℃ for 12 hours, and roasting at 350 ℃ for 3 hours;
(5) preparing a boric acid aqueous solution with the mass concentration of 10%, soaking the solid obtained in the step (4) in the boric acid aqueous solution, stirring for 60 minutes at room temperature, filtering, and vacuum-drying for 8 hours at 150 ℃.
(III) hydrophobic modification treatment
(6) And (3) transferring 5g of the solid powder obtained in the step (II) into a conical flask, sequentially adding 50mL of toluene and 10mL of a dimethyl diethoxy silane hydrophobic modification component, carrying out ultrasonic oscillation treatment for 2h, washing the obtained sample with toluene, and further carrying out vacuum drying at 100 ℃ for 12h to obtain the catalyst required by the invention.
Catalyst application
4g of the catalyst prepared according to the method of the above example was charged into a fixed bed reactor. The method is carried out by using the following application steps that before the catalyst is used, 10% H is firstly carried out in a reducing atmosphere at 340 DEG C2/N2The mixed gas is subjected to reduction pretreatment, and the space velocity of the reduction gas is 1700h-1The reduction pressure is 0.2MPa, and the reduction time is 8 h; then, the synthesis gas raw material is sent to a reactor to perform catalytic reaction with the reduced catalyst, and products after the reaction are condensed and separated to obtain ethanol and propanol products.
The catalytic reaction conditions are as follows: h in raw syngas2The mol ratio of/CO is 2: 1; the reaction temperature is 250 ℃, the reaction pressure is 7.0MPa, and the air speed of the raw material synthesis gas is 4000h-1。
Example 7
Catalyst preparation
Preparation of (I) solid solution precursor
(1) Weighing 8.59g Zr (NO)3)4·5H2O、34.64g La(NO3)3·6H2Dissolving O in 200mL of deionized water to prepare a solution A;
(2) weighing 26g of ammonia water (25%) and dissolving the ammonia water in 200mL of deionized water to prepare a solution B;
(3) adding 100mL of deionized water into a beaker, heating to 70 ℃, dripping the solution A and the solution B into the beaker solution through a peristaltic pump in a parallel flow manner at a stirring speed of 100 revolutions per minute for coprecipitation reaction, keeping the pH value of the solution at 8, continuing stirring for 1h after the precipitation is finished, naturally cooling the precipitated solution to room temperature, filtering, washing the obtained solid for 3 times by using the deionized water, and removing residual impurities on the surface.
Introduction of (di) active metal boride component
(4) 14.52g of Cu (NO) was weighed3)2∙3H2O、1g IrCl45.4g of urea, put into a polytetrafluoroethylene hydrothermal synthesis kettle, added with 150mL of deionized water,stirring at room temperature, dissolving to obtain a clear and transparent uniform solution, transferring the structural solid solution precursor obtained in the step (3) into a metal component solution in the lining polytetrafluoroethylene hydrothermal synthesis kettle, stirring, sealing the lining polytetrafluoroethylene hydrothermal synthesis kettle, carrying out constant-temperature hydrothermal treatment at 120 ℃ for 12h, cooling to room temperature, carrying out centrifugal separation, washing the obtained solid with deionized water for 3 times, removing residual impurities on the surface, drying at 100 ℃ for 12h, and roasting at 350 ℃ for 3 h;
(5) preparing a boric acid aqueous solution with the mass concentration of 10%, soaking the solid obtained in the step (4) in the boric acid aqueous solution, stirring for 60 minutes at room temperature, filtering, and vacuum-drying for 8 hours at 150 ℃.
(III) hydrophobic modification treatment
(6) And (3) transferring 5g of the solid powder obtained in the step (II) into a conical flask, sequentially adding 50mL of toluene and 10mL of octyl trichlorosilane hydrophobic modification component, carrying out ultrasonic oscillation treatment for 2h, washing the obtained sample with toluene, and further carrying out vacuum drying at 100 ℃ for 12h to obtain the catalyst required by the invention.
Catalyst application
4g of the catalyst prepared according to the method of the above example was charged into a fixed bed reactor. The method is carried out by using the following application steps, wherein the catalyst is firstly reduced at 380 ℃ in 10% H atmosphere before being used2/N2Carrying out reduction pretreatment in the mixed gas, wherein the space velocity of the reduction gas is 1600h-1The reduction pressure is 0.3MPa, and the reduction time is 7 h; then, the synthesis gas raw material is sent to a reactor to perform catalytic reaction with the reduced catalyst, and products after the reaction are condensed and separated to obtain ethanol and propanol products.
The catalytic reaction conditions are as follows: h in raw syngas2The mol ratio of/CO is 1.5:1, the reaction temperature is 240 ℃, the reaction pressure is 5.0MPa, and the air speed of the raw material synthetic gas is 5500h-1。
Example 8
Catalyst preparation
Preparation of (I) solid solution precursor
(1) Weighing 7.2g Mn (NO)3)2(50% aqueous solution), 26.04g Ce (NO)3)3·6H2Dissolving O in 200mL of deionized water to prepare a solution A;
(2) weighing 18g of ammonium bicarbonate, and dissolving in 200mL of deionized water to obtain a solution B;
(3) adding 100mL of deionized water into a beaker, heating to 70 ℃, dripping the solution A and the solution B into the beaker solution through a peristaltic pump in a parallel flow manner at a stirring speed of 100 revolutions per minute for coprecipitation reaction, keeping the pH value of the solution at 7.5, continuing stirring for 1h after the precipitation is finished, naturally cooling the precipitated solution to room temperature, filtering, washing the obtained solid for 3 times by using the deionized water, and removing residual impurities on the surface.
Introduction of (di) reactive metal boride component
(4) Weigh 7.25g Cu (NO)3)2∙3H2O、14.6g Co(NO3)2·6H2O、6.18g H24Mo7N6O24·4H2Placing O and 5.28g of urea into a polytetrafluoroethylene hydrothermal synthesis kettle as a lining, adding 150mL of deionized water, stirring at room temperature, dissolving to obtain a clear and transparent uniform solution, transferring the structural solid solution precursor obtained in the step (3) into a metal component solution in the polytetrafluoroethylene hydrothermal synthesis kettle as the lining, stirring, sealing the polytetrafluoroethylene hydrothermal synthesis kettle as the lining, carrying out constant-temperature hydrothermal treatment at 120 ℃ for 12 hours, cooling to room temperature, carrying out centrifugal separation, washing the obtained solid with deionized water for 3 times, removing surface residual impurities, drying at 100 ℃ for 12 hours, and roasting at 350 ℃ for 3 hours;
(5) preparing sodium borohydride (containing 3% sodium hydroxide) with the mass concentration of 10%, soaking the solid obtained in the step (4) in the boric acid solution, stirring at room temperature for 60 minutes, filtering, and drying in vacuum at 150 ℃ for 8 hours.
(III) hydrophobic modification treatment
(6) And (3) transferring 5g of the solid powder obtained in the step (II) into a conical flask, sequentially adding 50mL of toluene and 8mL of dimethyl diethoxy silane hydrophobic modification component, carrying out ultrasonic oscillation treatment for 2h, washing the obtained sample with toluene, and further carrying out vacuum drying at 100 ℃ for 12h to obtain the catalyst required by the invention.
Catalyst application
5g of the catalyst prepared according to the method of the above example was charged into a fixed bed reactor. The method is carried out by using the following application steps that before the catalyst is used, the catalyst is firstly reduced at 300 ℃ in 10% H atmosphere2/N2Carrying out reduction pretreatment in the mixed gas, wherein the space velocity of the reduction gas is 1300h-1The reduction pressure is 0.4MPa, and the reduction time is 9 h; then, the synthesis gas raw material is sent to a reactor to perform catalytic reaction with the reduced catalyst, and products after the reaction are condensed and separated to obtain ethanol and propanol products.
The catalytic reaction conditions are as follows: h in raw syngas2The mol ratio of/CO is 3:1, the reaction temperature is 270 ℃, the reaction pressure is 5.5MPa, and the air speed of the raw material synthesis gas is 3600h-1。
Example 9
Catalyst preparation
Preparation of (I) solid solution precursor
(1) 20.82 g Zn (NO) are weighed out3)2·6H2O、8 g Cr(NO3)3·9H2Dissolving O in 200mL of deionized water to prepare a solution A;
(2) weighing 19g of ammonium bicarbonate, and dissolving in 200mL of deionized water to obtain a solution B;
(3) adding 100mL of deionized water into a beaker, heating to 70 ℃, dripping the solution A and the solution B into the beaker solution through a peristaltic pump in a parallel flow manner at a stirring speed of 100 revolutions per minute for coprecipitation reaction, keeping the pH value of the solution at 8, continuing stirring for 1h after the precipitation is finished, naturally cooling the precipitated solution to room temperature, filtering, washing the obtained solid for 3 times by using the deionized water, and removing residual impurities on the surface.
Introduction of (di) active metal boride component
(4) 9.7g of Cu (NO) was weighed3)2∙3H2O、14.6g Co(NO3)2·6H2O、4.04g Fe (NO3)3•9H2O and 6.9g of urea are placed in a polytetrafluoroethylene-lined hydrothermal synthesis kettle, 150mL of deionized water is added, stirring is carried out at room temperature, a clear and transparent uniform solution is obtained by dissolution, and the structural solid solution precursor obtained in the step (3) is transferred to the liningStirring in a metal component solution in a polytetrafluoroethylene hydrothermal synthesis kettle, sealing the polytetrafluoroethylene hydrothermal synthesis kettle with the lining, carrying out constant-temperature hydrothermal treatment at 120 ℃ for 12 hours, cooling to room temperature, carrying out centrifugal separation, washing the obtained solid with deionized water for 3 times, removing residual impurities on the surface, drying at 100 ℃ for 12 hours, and roasting at 350 ℃ for 3 hours;
(5) preparing sodium borohydride (containing 3% of sodium hydroxide) with the mass concentration of 8%, soaking the solid obtained in the step (4) in the boric acid solution, stirring at room temperature for 60 minutes, filtering, and drying in vacuum at 150 ℃ for 8 hours.
(III) hydrophobic modification treatment
(6) And (3) transferring 5g of the solid powder obtained in the step (II) into a conical flask, sequentially adding 50mL of toluene and 5mL of methyltriethoxysilane hydrophobic modification component, carrying out ultrasonic oscillation treatment for 2h, washing the obtained sample with toluene, and further carrying out vacuum drying at 100 ℃ for 12h to obtain the catalyst required by the invention.
Catalyst application
3g of the catalyst prepared according to the method of the above example was charged into a fixed bed reactor. The method is carried out by using the following application steps that before the catalyst is used, the catalyst is firstly reduced at 340 ℃ in 10% H atmosphere2/N2Carrying out reduction pretreatment in the mixed gas, wherein the space velocity of the reduction gas is 1300h-1The reduction pressure is 0.2MPa, and the reduction time is 7 h; then, the synthesis gas raw material is sent to a reactor to perform catalytic reaction with the reduced catalyst, and products after the reaction are condensed and separated to obtain ethanol and propanol products.
The catalytic reaction conditions are as follows: h in raw syngas2The mol ratio of/CO is 2:1, the reaction temperature is 240 ℃, the reaction pressure is 5.0MPa, and the air speed of the raw material synthesis gas is 4000h-1。

Claims (13)

1. A catalyst for preparing ethanol and propanol from synthesis gas is characterized in that: the catalyst comprises three components of a structural solid solution, a metal boride and a hydrophobic modification layer, wherein the structural solid solution is one of ZnCr, ZnZr, ZnAl, MgAl, MnAl, CeZr, LaZr, MnZr and MnCe, the weight percentage of the structural solid solution in the catalyst is 49-85%, the weight percentage of the metal boride in the catalyst is 10-50%, and the weight percentage of the hydrophobic modification layer in the catalyst is 0.5-10%.
2. The catalyst for preparing ethanol and propanol from synthesis gas according to claim 1, wherein the catalyst comprises: the metal boride is a boride formed by reacting one or more of Rh, Pd, Ir, Co, Mo, Cu, Ni or Fe with boron element.
3. The catalyst for preparing ethanol and propanol from synthesis gas according to claim 1, wherein the catalyst comprises: the hydrophobic modification layer is one of trimethylchlorosilane TMCS, dimethyldiethoxysilane DMDES, methyltriethoxysilane MTES, hexadecyltrichlorosilane HTCS and octyltrichlorosilane OTCS.
4. The preparation method of the catalyst for preparing ethanol and propanol from synthesis gas according to claim 1, which is characterized by comprising the following steps: the method comprises the following steps
Step one, preparing a structural solid solution precursor
Step 11, dissolving soluble metal salt of any structural solid solution in deionized water to prepare a bimetal mixed salt solution, and marking as A solution;
step 12, dissolving a precipitator in deionized water to obtain a solution B;
step 13, adding deionized water into a beaker, heating to 40-95 ℃, dripping the solution A and the solution B into the beaker under the stirring condition, keeping the pH value at 6.5-9, carrying out coprecipitation reaction, continuing stirring for 1-4h after precipitation is finished, naturally cooling to room temperature, filtering, washing the obtained solid with deionized water for 3-6 times, and removing surface residual impurities to obtain a structural solid solution precursor;
step two, introduction of active metal boride component
Step 21, placing soluble metal salt of metal boride, ammonium fluoride NH4F and urea in a polytetrafluoroethylene lined hydrothermal synthesis kettle, stirring at room temperature, dissolving to obtain a clear and transparent solution C, adding the structural solid solution precursor prepared in step 13 into the solution C, sealing the polytetrafluoroethylene lined hydrothermal synthesis kettle, carrying out constant-temperature hydrothermal treatment at 120 ℃ for 4-12h, cooling to room temperature, carrying out centrifugal separation, washing the obtained solid with deionized water for 3-6 times, removing surface residual impurities, and then drying and roasting to obtain solid powder containing the structural solid solution;
step 22, preparing 8-25% of sodium borohydride aqueous solution or 0-35% of boric acid aqueous solution, wherein the mass concentration of sodium hydroxide in the sodium borohydride aqueous solution is 3%, soaking the solid powder containing the structural solid solution prepared in the step 21 in the sodium borohydride aqueous solution or the boric acid aqueous solution, stirring for 30-90 minutes at room temperature, filtering, and vacuum-drying for 2-8 hours at 40-150 ℃ to obtain solid powder containing the structural solid solution and the metal boride;
step three, introducing a hydrophobic modification layer
And 31, transferring the solid powder containing the structural solid solution and the metal boride prepared in the step 22 into a conical flask, sequentially adding toluene and a hydrophobic modification component, carrying out ultrasonic oscillation treatment, washing an obtained sample with toluene, and further carrying out vacuum drying to obtain the catalyst for preparing ethanol and propanol from synthesis gas.
5. The preparation method of the catalyst for preparing ethanol and propanol from synthesis gas according to claim 4, wherein the catalyst comprises the following steps: the total metal ion concentration of the solution A is 0.3-0.8mol/L, and the molar ratio of two metal ions is (0.1-0.6): 1; the precipitator in the preparation process of the solution B is one of ammonia water, ammonium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide, and the molar concentration of the precipitator in the solution B is 0.4-2 mol/L.
6. The preparation method of the catalyst for preparing ethanol and propanol from synthesis gas according to claim 4, wherein the catalyst comprises the following steps: in the clear and transparent solution C obtained in the step 21, the concentration of total metal ions is 0.2-0.7mol/L, the concentration of ammonium fluoride is 0.5-2.0 mol/L, and the concentration of urea is 0.9-3.0 mol/L.
7. The preparation method of the catalyst for preparing ethanol and propanol from synthesis gas according to claim 4, wherein the catalyst comprises the following steps: in the sodium borohydride aqueous solution prepared in the step 22, the mass concentration of the sodium borohydride is 10-15%, and in the boric acid aqueous solution prepared in the step 22, the mass concentration of the boric acid is 15-25%.
8. The preparation method of the catalyst for preparing ethanol and propanol from synthesis gas according to claim 4, wherein the catalyst comprises the following steps: in step 31, 8-30ml of toluene is added per 1g of solid powder containing the structural solid solution and the metal boride, and 1-2ml of the hydrophobic modification component is added per 1g of solid powder containing the structural solid solution and the metal boride.
9. The method for preparing the catalyst for preparing ethanol and propanol from the synthesis gas according to claim 8, wherein the method comprises the following steps: in step 31, 10 to 15ml of toluene is added per 1g of solid powder containing the structural solid solution and the metal boride, and 0.5 to 6ml of the hydrophobic modification component is added per 1g of solid powder containing the structural solid solution and the metal boride.
10. The application of the catalyst for preparing ethanol and propanol from synthesis gas as claimed in claim 1, is characterized in that: the process adopts a fixed bed process or a slurry bed process, the catalyst is firstly subjected to reduction pretreatment in a reducing atmosphere at 400 ℃ under 300--1The reduction pressure is 0.2-0.5MPa, and the reduction time is 6-12 h; then, the synthesis gas raw material is sent to a reactor to perform catalytic reaction with the reduced catalyst, and products after the reaction are condensed and separated to obtain ethanol and propanol products.
11. The application of the catalyst for preparing ethanol and propanol from synthesis gas according to claim 11 is characterized in that: in a reducing atmosphere is H2And N2Formed mixed gas of H2Accounting for 10 percent of the total volume of the mixed gas, and the space velocity of the reducing gas is 1200-1600 h-1The reduction pressure is 0.3-0.4MPa, and the reduction time is 8-10 h.
12. According to the claimsThe application of the catalyst for preparing ethanol and propanol from the synthesis gas is characterized in that: the raw material of the synthesis gas is sent to a reactor to perform catalytic reaction with the reduced catalyst, and H in the raw material synthesis gas2The mol ratio of the carbon dioxide to CO is 1-3: 1; the reaction temperature is 220 ℃ and 280 ℃; the reaction pressure is 4.0-7.0 MPa; raw material synthesis gas air speed of 1000-6000h-1。
13. The application of the catalyst for preparing ethanol and propanol from synthesis gas according to claim 12 is characterized in that: h in the raw material synthesis gas is fed into a reactor to perform catalytic reaction with the reduced catalyst2The mol ratio of the carbon dioxide to CO is 1.5-2.5: 1; the reaction temperature is 240-260 ℃; the reaction pressure is 5.0-6.5 MPa; the space velocity of the raw material synthesis gas is 3000--1。
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Citations (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20011519A0 (en) * 2001-07-17 2001-07-17 Uni Degli Studi Di L Aquila SOLID SOLUTIONS WITH PEROVSKITIC STRUCTURE INCLUDING NOBLE METALS USEFUL AS CATALYST
CN1440925A (en) * 2003-03-27 2003-09-10 武汉大学 Catalyst and its prepn process and use
CN1554484A (en) * 2003-12-26 2004-12-15 中国科学院山西煤炭化学研究所 Method for surface hydrophobic modification of metal loaded catalyst
US20080020137A1 (en) * 2006-07-24 2008-01-24 Venkataramani Venkat Subramani Doped magnesium diboride powders and methods for making the same
CN101224430A (en) * 2008-01-30 2008-07-23 中国科学院山西煤炭化学研究所 Hydrophobic organic modification of Co group Fischer-Tropsch synthesized catalyst, preparing and applications thereof
CN101279272A (en) * 2008-05-13 2008-10-08 北京理工大学 Double-activity composite catalyst and preparation method and application thereof
CN101628237A (en) * 2008-07-16 2010-01-20 中国科学院大连化学物理研究所 Egg-shell catalyst for preparing heavy hydrocarbon from synthesis gas, and preparation method and application thereof
CN102728372A (en) * 2011-04-14 2012-10-17 中国石油化工股份有限公司 Preparation method of hydrofining catalyst
CN103464134A (en) * 2013-09-03 2013-12-25 中国科学院山西煤炭化学研究所 Catalyst for preparing carbon monoxide by decomposing carbon dioxide, as well as preparation method and application thereof
CN103691442A (en) * 2013-12-03 2014-04-02 辽宁石油化工大学 Catalyst for synthesis of isobutanol from synthesis gas and preparation method of catalyst
CN103872314A (en) * 2014-03-21 2014-06-18 个旧圣比和实业有限公司 Pre-oxidization method of high-nickel ternary positive electrode active substance precursor of lithium ion battery
KR101469183B1 (en) * 2013-08-23 2014-12-10 한국화학연구원 method of prepering supported catalyst
CN104263317A (en) * 2014-09-26 2015-01-07 厦门大学 Method for synthesizing cobalt oxide/graphene composite wave-absorbing material
CN104918882A (en) * 2012-12-21 2015-09-16 巴斯夫欧洲公司 Parallel preparation of hydrogen, carbon monoxide and carbon-comprising product
EP2926904A1 (en) * 2014-04-01 2015-10-07 Kemijski Institut Catalyst support, a methof for producing thereof, a catalyst comprising said support and the process for converting gas mixtures of methane and carbon dioxide into syngas using said catalyst
CN105457641A (en) * 2014-09-09 2016-04-06 中国石油化工股份有限公司 Preparation of copper, zinc and aluminum methanol synthesizing catalyst by virtue of reduction deposition method
CN106268856A (en) * 2015-05-22 2017-01-04 中国科学院大连化学物理研究所 Rhodium base catalyst of one-step method from syngas ethanol and its preparation method and application
CN106622196A (en) * 2017-01-04 2017-05-10 中国矿业大学 Ethylene catalyst prepared through ethanol delydration and preparation method and application of ethylene catalyst
CN106881102A (en) * 2015-12-16 2017-06-23 长春工业大学 A kind of method by cobalt base amorphous state catalyst ethyl lactate hydrogenation synthesis 1,2- propane diols
CN107486234A (en) * 2017-07-23 2017-12-19 复旦大学 Catalyst of light aromatics and preparation method thereof is prepared for synthesis gas directly conversion
CN107519883A (en) * 2017-09-01 2017-12-29 太原理工大学 A kind of hydrophobicity copper-based catalysts and preparation method and application
CN108579744A (en) * 2018-04-26 2018-09-28 东南大学 It is a kind of load ruthenium cerium Zirconium-base catalyst preparation and application process
CN108889302A (en) * 2018-07-20 2018-11-27 太原理工大学 CO and CO2Cu base catalyst of synthesizing methanol by hydrogenating and its preparation method and application
CN109289865A (en) * 2018-09-30 2019-02-01 中国科学院山西煤炭化学研究所 The silicon-containing catalyst and preparation method of a kind of preparing low-carbon mixed alcohol by synthetic gas and application
CN109317130A (en) * 2018-09-29 2019-02-12 中国科学院山西煤炭化学研究所 One kind being used for thermochemical cycle decomposition CO2And/or H2The catalyst and preparation method of O and application
CN109590010A (en) * 2018-11-22 2019-04-09 东北石油大学 For adjusting the mesoporous hydrophobic surface modification method of core-shell catalyst shell
CN110467517A (en) * 2019-08-07 2019-11-19 青岛科技大学 A kind of hydrogenation of acetophenone prepares the method and catalyst of alpha-phenyl ethyl alcohol
CN110586147A (en) * 2019-09-11 2019-12-20 天津大学 Hydrotalcite-structured nickel phosphide catalyst and preparation method thereof
CN110699701A (en) * 2019-09-06 2020-01-17 华东理工大学 Foam nickel loaded with metal nickel and vanadium trioxide compound and preparation method and application thereof
CN110841623A (en) * 2019-10-12 2020-02-28 山东国瓷功能材料股份有限公司 Cerium-zirconium composite oxide with stable high-temperature structure and preparation method thereof
CN110841651A (en) * 2019-11-27 2020-02-28 浙江石油化工有限公司 Boron-containing residual oil hydrotreating catalyst and preparation method thereof
CN111495417A (en) * 2020-05-26 2020-08-07 盐城工学院 Foam nickel loaded iron-cobalt-nickel metal nano catalyst and preparation method and application thereof
CN111822014A (en) * 2020-07-01 2020-10-27 南昌航空大学 Titanium foil loaded Fe-CoP nano-array structure catalyst and preparation method and application thereof
CN112495393A (en) * 2020-11-27 2021-03-16 华南理工大学 Fine-regulation and control supported alloy catalyst and preparation method and application thereof
CN112495384A (en) * 2020-11-26 2021-03-16 中国科学院山西煤炭化学研究所 CuCo-based composite catalyst for preparing low-carbon alcohol from synthesis gas and preparation method and application thereof
CN112619653A (en) * 2020-04-01 2021-04-09 中国科学院山西煤炭化学研究所 High-carbon alcohol catalyst for preparing detergent from synthetic gas and preparation method and application thereof
CN113430553A (en) * 2021-07-23 2021-09-24 华北电力大学 Bifunctional catalytic electrode based on transition metal heterogeneous layered structure and preparation method thereof
CN113617343A (en) * 2021-08-31 2021-11-09 福州大学 Biomass oil deoxidation catalyst and preparation method and application thereof
CN113649032A (en) * 2021-08-18 2021-11-16 金华永和氟化工有限公司 Vinylidene fluoride catalyst and preparation method thereof
CN113813953A (en) * 2021-07-21 2021-12-21 浙江大学 Preparation and application methods of cerium-zirconium composite oxide solid solution catalyst
CN113842942A (en) * 2021-11-01 2021-12-28 北京工业大学 Preparation and application of Fe-Ce-LDH/13X granular catalyst for heterogeneous electro-Fenton system

Patent Citations (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20011519A0 (en) * 2001-07-17 2001-07-17 Uni Degli Studi Di L Aquila SOLID SOLUTIONS WITH PEROVSKITIC STRUCTURE INCLUDING NOBLE METALS USEFUL AS CATALYST
CN1440925A (en) * 2003-03-27 2003-09-10 武汉大学 Catalyst and its prepn process and use
CN1554484A (en) * 2003-12-26 2004-12-15 中国科学院山西煤炭化学研究所 Method for surface hydrophobic modification of metal loaded catalyst
US20080020137A1 (en) * 2006-07-24 2008-01-24 Venkataramani Venkat Subramani Doped magnesium diboride powders and methods for making the same
CN101224430A (en) * 2008-01-30 2008-07-23 中国科学院山西煤炭化学研究所 Hydrophobic organic modification of Co group Fischer-Tropsch synthesized catalyst, preparing and applications thereof
CN101279272A (en) * 2008-05-13 2008-10-08 北京理工大学 Double-activity composite catalyst and preparation method and application thereof
CN101628237A (en) * 2008-07-16 2010-01-20 中国科学院大连化学物理研究所 Egg-shell catalyst for preparing heavy hydrocarbon from synthesis gas, and preparation method and application thereof
CN102728372A (en) * 2011-04-14 2012-10-17 中国石油化工股份有限公司 Preparation method of hydrofining catalyst
CN104918882A (en) * 2012-12-21 2015-09-16 巴斯夫欧洲公司 Parallel preparation of hydrogen, carbon monoxide and carbon-comprising product
KR101469183B1 (en) * 2013-08-23 2014-12-10 한국화학연구원 method of prepering supported catalyst
CN103464134A (en) * 2013-09-03 2013-12-25 中国科学院山西煤炭化学研究所 Catalyst for preparing carbon monoxide by decomposing carbon dioxide, as well as preparation method and application thereof
CN103691442A (en) * 2013-12-03 2014-04-02 辽宁石油化工大学 Catalyst for synthesis of isobutanol from synthesis gas and preparation method of catalyst
CN103872314A (en) * 2014-03-21 2014-06-18 个旧圣比和实业有限公司 Pre-oxidization method of high-nickel ternary positive electrode active substance precursor of lithium ion battery
EP2926904A1 (en) * 2014-04-01 2015-10-07 Kemijski Institut Catalyst support, a methof for producing thereof, a catalyst comprising said support and the process for converting gas mixtures of methane and carbon dioxide into syngas using said catalyst
CN105457641A (en) * 2014-09-09 2016-04-06 中国石油化工股份有限公司 Preparation of copper, zinc and aluminum methanol synthesizing catalyst by virtue of reduction deposition method
CN104263317A (en) * 2014-09-26 2015-01-07 厦门大学 Method for synthesizing cobalt oxide/graphene composite wave-absorbing material
CN106268856A (en) * 2015-05-22 2017-01-04 中国科学院大连化学物理研究所 Rhodium base catalyst of one-step method from syngas ethanol and its preparation method and application
CN106881102A (en) * 2015-12-16 2017-06-23 长春工业大学 A kind of method by cobalt base amorphous state catalyst ethyl lactate hydrogenation synthesis 1,2- propane diols
CN106622196A (en) * 2017-01-04 2017-05-10 中国矿业大学 Ethylene catalyst prepared through ethanol delydration and preparation method and application of ethylene catalyst
CN107486234A (en) * 2017-07-23 2017-12-19 复旦大学 Catalyst of light aromatics and preparation method thereof is prepared for synthesis gas directly conversion
CN107519883A (en) * 2017-09-01 2017-12-29 太原理工大学 A kind of hydrophobicity copper-based catalysts and preparation method and application
CN108579744A (en) * 2018-04-26 2018-09-28 东南大学 It is a kind of load ruthenium cerium Zirconium-base catalyst preparation and application process
CN108889302A (en) * 2018-07-20 2018-11-27 太原理工大学 CO and CO2Cu base catalyst of synthesizing methanol by hydrogenating and its preparation method and application
CN109317130A (en) * 2018-09-29 2019-02-12 中国科学院山西煤炭化学研究所 One kind being used for thermochemical cycle decomposition CO2And/or H2The catalyst and preparation method of O and application
CN109289865A (en) * 2018-09-30 2019-02-01 中国科学院山西煤炭化学研究所 The silicon-containing catalyst and preparation method of a kind of preparing low-carbon mixed alcohol by synthetic gas and application
CN109590010A (en) * 2018-11-22 2019-04-09 东北石油大学 For adjusting the mesoporous hydrophobic surface modification method of core-shell catalyst shell
CN110467517A (en) * 2019-08-07 2019-11-19 青岛科技大学 A kind of hydrogenation of acetophenone prepares the method and catalyst of alpha-phenyl ethyl alcohol
CN110699701A (en) * 2019-09-06 2020-01-17 华东理工大学 Foam nickel loaded with metal nickel and vanadium trioxide compound and preparation method and application thereof
CN110586147A (en) * 2019-09-11 2019-12-20 天津大学 Hydrotalcite-structured nickel phosphide catalyst and preparation method thereof
CN110841623A (en) * 2019-10-12 2020-02-28 山东国瓷功能材料股份有限公司 Cerium-zirconium composite oxide with stable high-temperature structure and preparation method thereof
CN110841651A (en) * 2019-11-27 2020-02-28 浙江石油化工有限公司 Boron-containing residual oil hydrotreating catalyst and preparation method thereof
CN112619653A (en) * 2020-04-01 2021-04-09 中国科学院山西煤炭化学研究所 High-carbon alcohol catalyst for preparing detergent from synthetic gas and preparation method and application thereof
CN111495417A (en) * 2020-05-26 2020-08-07 盐城工学院 Foam nickel loaded iron-cobalt-nickel metal nano catalyst and preparation method and application thereof
CN111822014A (en) * 2020-07-01 2020-10-27 南昌航空大学 Titanium foil loaded Fe-CoP nano-array structure catalyst and preparation method and application thereof
CN112495384A (en) * 2020-11-26 2021-03-16 中国科学院山西煤炭化学研究所 CuCo-based composite catalyst for preparing low-carbon alcohol from synthesis gas and preparation method and application thereof
CN112495393A (en) * 2020-11-27 2021-03-16 华南理工大学 Fine-regulation and control supported alloy catalyst and preparation method and application thereof
CN113813953A (en) * 2021-07-21 2021-12-21 浙江大学 Preparation and application methods of cerium-zirconium composite oxide solid solution catalyst
CN113430553A (en) * 2021-07-23 2021-09-24 华北电力大学 Bifunctional catalytic electrode based on transition metal heterogeneous layered structure and preparation method thereof
CN113649032A (en) * 2021-08-18 2021-11-16 金华永和氟化工有限公司 Vinylidene fluoride catalyst and preparation method thereof
CN113617343A (en) * 2021-08-31 2021-11-09 福州大学 Biomass oil deoxidation catalyst and preparation method and application thereof
CN113842942A (en) * 2021-11-01 2021-12-28 北京工业大学 Preparation and application of Fe-Ce-LDH/13X granular catalyst for heterogeneous electro-Fenton system

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
YONG-ZHEN WANG ET AL.: "High resistance to aerial oxidation of an", 《JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY》 *
YONG-ZHEN WANG ET AL.: "High resistance to aerial oxidation of an", 《JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY》, 6 April 2004 (2004-04-06), pages 549 - 553 *
刘竞舸等: "合成气制混合醇催化剂研究进展", 《化学试剂》 *
刘竞舸等: "合成气制混合醇催化剂研究进展", 《化学试剂》, 27 July 2021 (2021-07-27), pages 1369 - 1375 *
林明桂等: "Zn、Mn 助剂对CuFe 合成低碳醇催化剂的影响", 《物理化学学报》 *
林明桂等: "Zn、Mn 助剂对CuFe 合成低碳醇催化剂的影响", 《物理化学学报》, 31 May 2008 (2008-05-31), pages 833 - 838 *
程萌: "由亲水和疏水硅胶制备的Ｃｏ/Ｒｕ/ＳｉＯ2 催化剂的表征及催化性能研究", 《燃料化学学报》 *
程萌: "由亲水和疏水硅胶制备的Ｃｏ/Ｒｕ/ＳｉＯ2 催化剂的表征及催化性能研究", 《燃料化学学报》, 30 June 2006 (2006-06-30), pages 343 - 347 *

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