CN110665510A - Preparation method of copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas - Google Patents

Preparation method of copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas Download PDF

Info

Publication number
CN110665510A
CN110665510A CN201910887262.7A CN201910887262A CN110665510A CN 110665510 A CN110665510 A CN 110665510A CN 201910887262 A CN201910887262 A CN 201910887262A CN 110665510 A CN110665510 A CN 110665510A
Authority
CN
China
Prior art keywords
cobalt
copper
based catalyst
carbon
electrode material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910887262.7A
Other languages
Chinese (zh)
Other versions
CN110665510B (en
Inventor
王亮
李亚斐
郑长征
刘斌
丁涛
惠盼婷
南柯媚
黄志刚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Polytechnic University
Original Assignee
Xian Polytechnic University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian Polytechnic University filed Critical Xian Polytechnic University
Priority to CN201910887262.7A priority Critical patent/CN110665510B/en
Publication of CN110665510A publication Critical patent/CN110665510A/en
Application granted granted Critical
Publication of CN110665510B publication Critical patent/CN110665510B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method of a copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas, which is implemented according to the following steps: step 1, placing carbon nanotubes in concentrated nitric acid for treatment, then steaming and coating the carbon nanotubes on carbon paper, and naturally airing to obtain a cathode electrode material; step 2, adding anhydrous copper sulfate, cobalt sulfate heptahydrate, sodium citrate and sodium sulfate into ionized water, uniformly stirring to obtain a solution a, adjusting the pH value, and placing the solution in a constant-temperature water bath kettle to obtain an electrolyte; step 3, placing the cathode electrode material and the anode electrode material in an electrolyte, connecting the cathode electrode material and the anode electrode material by adopting a numerical control constant current electroplating power supply, and electrolyzing to obtain a copper-cobalt-based catalyst sample; and 4, washing the copper-cobalt-based catalyst sample into a container, drying, roasting, tabletting, grinding and screening to obtain the copper-cobalt-based catalyst. The catalyst prepared by the method has loose and porous surface, large specific surface area, highly dispersed active components and good catalytic effect.

Description

Preparation method of copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas
Technical Field
The invention belongs to the technical field of chemical catalyst preparation, and particularly relates to a preparation method of a copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas.
Background
Because of the characteristics of energy structure 'rich coal, poor oil and less gas' in China, the strategy of 'coal replacing petroleum' is greatly promoted by the government of China in recent years, and synthesis gas (CO + H)2) Synthesized by using C as raw material under the action of catalyst1～C5The low-carbon mixed alcohol mainly containing alcohols has wide application prospect. The low carbon alcohol can be used as chemical raw material and chemical product, and can also be used as substitute fuel and clean gasoline additive.
The catalysts for preparing low-carbon alcohol from synthesis gas reported at present can be generally divided into ① modified Cu-based methanol catalysts, ② modified Fischer-Tropsch (F-T) synthesis catalysts, ③ Mo-based catalysts and ④ precious metal Rh-based catalysts, wherein the Cu-Co-based catalysts in the modified Fischer-Tropsch catalysts can react under mild reaction conditions (general reaction pressure is 3-6 MPa, reaction temperature is 220-330 ℃), and have relatively high low-carbon alcohol selectivity and catalytic activity, and are considered to have the greatest industrial prospect.
The coprecipitation method, the impregnation method and the sol-gel method, which are reported in the literature and the patents, cause the defects to a great extent, and show that different preparation methods have great influence on the reaction activity of the catalyst for preparing the low-carbon alcohol from the synthesis gas.
Disclosure of Invention
The invention aims to provide a preparation method of a copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas, which solves the problems of low activity and low alcohol selectivity of the copper-cobalt-based catalyst for preparing low-carbon alcohol in the prior art.
The technical scheme adopted by the invention is that the preparation method of the copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas is implemented according to the following steps:
step 1, placing carbon nanotubes in concentrated nitric acid for treatment, then steaming and coating the carbon nanotubes on carbon paper, and naturally airing to obtain a cathode electrode material;
step 2, adding anhydrous copper sulfate, cobalt sulfate heptahydrate, sodium citrate and sodium sulfate into deionized water, uniformly stirring to obtain a solution a, adjusting the pH value of the solution a, and placing the solution a into a constant-temperature water bath kettle to obtain an electrolyte;
step 3, placing the cathode electrode material and the anode electrode material obtained in the step 1 into the electrolyte obtained in the step 2, connecting the cathode electrode material and the anode electrode material by adopting a numerical control constant current electroplating power supply, and electrolyzing to obtain a copper-cobalt-based catalyst sample;
and 4, washing the copper-cobalt-based catalyst sample obtained in the step 3 into a container, drying and roasting, tabletting and grinding after the drying, and screening by using a 40-60-mesh sieve to obtain the copper-cobalt-based catalyst.
The invention is also characterized in that:
the treatment process of the carbon nano tube in the step 1 comprises the following steps: heating the carbon nano tube in concentrated nitric acid to 80-100 ℃, refluxing for 4-6 h, filtering and washing to be neutral after the end, drying overnight in a drying oven at 110 ℃ for 10h, grinding, and screening by using a 200-mesh sieve for later use.
The steam coating process in the step 1 comprises the following steps: weighing 0.05-0.06 g of phenolic resin and 0.06-0.07 g of polyvinylidene fluoride, adding the phenolic resin and the polyvinylidene fluoride into 20-25 ml of N, N-dimethylacetamide, carrying out ultrasonic oscillation for 15-25 min, adding 0.25-0.3 g of treated carbon nano tube, continuing the ultrasonic oscillation for 8-12 min to obtain a mixed solution, using a 12 x 12cm titanium plate to be placed above a 80 ℃ constant-temperature water bath kettle in an overhead manner, and then placing 100-144 cm in size2The carbon paper is placed on a titanium plate, the mixed solution is uniformly dripped on the surface of the carbon paper by a layer by a burette and is evaporated to dryness, the dripping and evaporating processes of the mixed solution are circulated until the dripping of the mixed solution is finished, and the mixed solution is naturally dried, so that the evaporation coating is finished.
The volume of the deionized water in the step 2 is 1L; the concentration of anhydrous copper sulfate in the solution a is 5-10 g/L, the concentration of cobalt sulfate heptahydrate is 30-50 g/L, the concentration of sodium citrate is 40-60 g/L and the concentration of sodium sulfate is 20 g/L; adjusting the pH value to 3.5-5.5, wherein a sulfuric acid solution or a sodium hydroxide solution is adopted as a solution for adjusting the pH value; the temperature of the water bath is 45-55 ℃.
The current density of electrolysis in the step 3 is 2.1-3.7A/dm2The electrolysis time is 20-40 min.
And 3, taking the anode electrode material as a graphite plate.
The thickness of the carbon paper and the graphite plate is 2 mm.
The drying temperature in the step 4 is 85-120 ℃, and the drying time is 8-10 h; calcined in N2The reaction is carried out under the atmosphere, the temperature is 350-450 ℃, and the time is 3.5-4.5 h.
The specific surface area of the carbon nano tube in the step 1 is 100-120 m2G, pipe diameter of 30 &50nm, tube length<10 μm, and a bulk density of 0.12-0.25 g/cm3The carbon content is more than or equal to 98 percent.
The invention has the beneficial effects that: the prepared copper-cobalt-based catalyst has a stable structure, the active components are uniformly loaded and highly dispersed, the activity of the catalyst on the preparation of low-carbon alcohol from synthesis gas is high, the CO conversion rate can reach 38%, and the total alcohol selectivity can reach 47%. The electrodeposition preparation method adopted by the invention has the advantages of simple process, easily controlled deposition conditions and environmental protection.
Drawings
Fig. 1 is an SEM image of a manufacturing method of the present invention, in which fig. 1(a) is an SEM image of example 1, fig. 1(b) is an SEM image of example 2, fig. 1(c) is an SEM image of example 3, fig. 1(d) is an SEM image of example 4, fig. 1(e) is an SEM image of example 5, fig. 1(f) is an SEM image of example 6, and fig. 1(g) is an SEM image of example 7.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention relates to a preparation method of a copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas, which is implemented according to the following steps:
step 1, placing a carbon nano tube in concentrated nitric acid, heating to 80-100 ℃, refluxing for 4-6 hours, filtering and washing to be neutral after the completion, drying overnight in an oven at 110 ℃ for 10 hours, grinding, sieving by using a 200-mesh sieve, then coating on carbon paper by evaporation, and naturally airing to obtain a cathode electrode material;
wherein, the process of steaming and coating is as follows: weighing 0.05-0.06 g of phenolic resin and 0.06-0.07 g of polyvinylidene fluoride, adding the phenolic resin and the polyvinylidene fluoride into 20-25 ml of N, N-dimethylacetamide, carrying out ultrasonic oscillation for 15-25 min, adding 0.25-0.3 g of treated carbon nano tube, continuing the ultrasonic oscillation for 8-12 min to obtain a mixed solution, using a 12 x 12cm titanium plate to be placed above a 80 ℃ constant-temperature water bath kettle in an overhead manner, and then placing 100-144 cm in size2The carbon paper is placed on a titanium plate, the mixed solution is uniformly dripped on the surface of the carbon paper by a dropper to be evaporated to dryness, and the processes of dripping and evaporating to dryness of the mixed solution are circulatedAnd naturally airing until the mixed solution is dripped, and finishing the coating by steaming.
The specific surface area of the carbon nano tube is 100-120 m2A pipe diameter of 30 to 50nm and a pipe length of g<10 μm, and a bulk density of 0.12-0.25 g/cm3The carbon content is more than or equal to 98 percent;
step 2, adding anhydrous copper sulfate, cobalt sulfate heptahydrate, sodium citrate and sodium sulfate into 1L of deionized water, uniformly stirring to obtain a solution a, adjusting the pH value of the solution a to 3.5-5.5 by adopting a sulfuric acid solution or a sodium hydroxide solution, and placing the solution a in a constant-temperature water bath kettle at the temperature of 45-55 ℃ after adjustment to obtain electrolyte;
wherein the concentration of anhydrous copper sulfate in the solution a is 5-10 g/L, the concentration of cobalt sulfate heptahydrate is 30-50 g/L, the concentration of sodium citrate is 40-60 g/L and the concentration of sodium sulfate is 20 g/L;
step 3, placing the cathode electrode material and the anode electrode material obtained in the step 1 into the electrolyte obtained in the step 2, connecting the cathode electrode material and the anode electrode material by adopting a numerical control constant current electroplating power supply, and setting the current density of electrolysis to be 2.1-3.7A/dm2Electrifying to electrolyze for 20-40 min to obtain a copper-cobalt-based catalyst sample;
wherein, the anode electrode material is a graphite plate; the carbon paper and the graphite plate are both 2mm in thickness, the graphite plate is a commercially available graphite plate, and the carbon paper and the graphite plate are used after being soaked in a dilute alkali solution for 30min and washed clean by deionized water before use;
step 4, washing the copper-cobalt-based catalyst sample obtained in the step 3 into a container, drying the sample at 85-120 ℃ for 8-10 h, and heating at the temperature of 5 ℃/min under N2Roasting for 3.5-4.5 hours in an atmospheric tubular furnace at the roasting temperature of 350-450 ℃, tabletting and grinding by using a table type tablet machine after the roasting is finished, and screening by using a 40-60-mesh screen to obtain the copper-cobalt-based catalyst.
The specific process of the performance test of the copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas is as follows:
the performance test of the copper-cobalt-based catalyst for preparing the low-carbon alcohol from the synthesis gas is carried out on an experimental device for synthesizing the low-carbon alcohol by controlling coal gasification through DCS (distributed control System)The tubular reactor with the inner diameter of phi 12mm multiplied by 600mm is filled with 0.5g of copper-cobalt-based catalyst, and the volume ratio of the copper-cobalt-based catalyst is 6: 1H2/N2Reducing the mixed gas at 470 ℃ for 6h, then reducing the temperature of the reactor to 450 ℃, and switching to a gas-liquid separator with the volume ratio of 2: 1H2The synthesis gas of/CO is reacted after the temperature and the gas pressure are stabilized, the reaction tail gas discharged from the outlet of the reactor is immediately unloaded to the normal pressure, the reaction tail gas is directly sent to a six-way valve of a gas chromatograph of Tianmei GC-7890 II for sampling through a heat insulation pipeline, a Thermal Conductivity Detector (TCD) is used for on-line detection, a liquid phase product is sampled once every 6 hours until no liquid is generated, the liquid phase product is injected into the gas chromatograph of Tianmei GC-7890 II after being sampled by an injector, and the analysis is carried out by a hydrogen flame detector (FID).
Example 1
The invention relates to a preparation method of a copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas, which is implemented according to the following steps:
step 1, placing carbon nanotubes in concentrated nitric acid, heating to 80 ℃, refluxing for 5h, filtering and washing to be neutral after the completion, drying overnight for 10h in a drying oven at 110 ℃, grinding, screening by using a 200-mesh sieve, then steaming and coating on carbon paper, and naturally airing to obtain a cathode electrode material;
wherein, the process of steaming and coating is as follows: weighing 0.053g of phenolic resin and 0.064g of polyvinylidene fluoride, adding the phenolic resin and 0.064g of polyvinylidene fluoride into 22ml of N, N-dimethylacetamide, carrying out ultrasonic oscillation in a water bath at 40 ℃ for 20min, adding 0.3g of treated carbon nano tube, continuing the ultrasonic oscillation for 10min to obtain a mixed solution, using a titanium plate with the size of 12 x 12cm to be arranged above a constant-temperature water bath kettle at 80 ℃, placing carbon paper with the size of 10 x 10cm on the titanium plate, uniformly dripping a layer of the mixed solution on the surface of the carbon paper by using a dropper, evaporating to dryness, circulating the processes of dripping and evaporating to dryness of the mixed solution until the dripping of the mixed solution is finished, naturally airing, and finishing the evaporation;
the specific surface area of the carbon nano tube is 100-120 m2A pipe diameter of 30 to 50nm and a pipe length of g<10 μm, and a bulk density of 0.12-0.25 g/cm3The carbon content is more than or equal to 98 percent;
step 2, adding anhydrous copper sulfate, cobalt sulfate heptahydrate, sodium citrate and sodium sulfate into 1L of deionized water, uniformly stirring to obtain a solution a, adjusting the pH value of the solution a to 4.5 by adopting a sulfuric acid solution or a sodium hydroxide solution, and placing the solution a into a constant-temperature water bath kettle at the temperature of 50 ℃ after adjustment to obtain electrolyte;
wherein the concentration of anhydrous copper sulfate in the solution a is 5g/L, the concentration of cobalt sulfate heptahydrate is 30g/L, the concentration of sodium citrate is 50g/L and the concentration of sodium sulfate is 20 g/L;
step 3, placing the cathode electrode material and the anode electrode material obtained in the step 1 into the electrolyte obtained in the step 2, connecting the cathode electrode material and the anode electrode material by adopting a numerical control constant current electroplating power supply, and setting the current density of electrolysis to be 2.9A/dm2Electrifying to electrolyze for 30min to obtain a copper-cobalt-based catalyst sample;
wherein, the anode electrode material is a graphite plate; the thickness of the carbon paper and the graphite plate is 2 mm;
step 4, washing the copper-cobalt-based catalyst sample obtained in the step 3 into a container, drying the sample at 110 ℃ for 8 hours, and then heating the sample at the temperature of 5 ℃/min at N2Roasting for 4 hours in a tubular furnace in the atmosphere at the roasting temperature of 400 ℃, tabletting and grinding by using a table type tablet machine after the roasting is finished, and screening by using a 40-60-mesh screen to obtain the copper-cobalt-based catalyst.
SEM and N are carried out on the obtained copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas2Physical adsorption-desorption characterization, the obtained results are shown in figure 1(a) and table 1;
the specific process of the performance test of the copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas is as follows:
the performance test of the copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas is carried out on a DCS control coal gasification synthesis low-carbon alcohol experimental device, 0.5g of catalyst is filled in a tubular reactor with the inner diameter of phi 12mm multiplied by 600mm, and the volume ratio of the catalyst is 6: 1H2/N2Reducing the mixed gas at 470 ℃ for 6h, then reducing the temperature of the reactor to 450 ℃, and switching to a gas-liquid separator with the volume ratio of 2: 1H2The synthesis gas of/CO is adjusted to 4.0MPa, the reaction is carried out after the temperature and the gas pressure are stable, and then the reaction is carried out from the outlet of the reactorThe discharged reaction tail gas is immediately unloaded to the normal pressure, and is directly sent to a six-way valve of a gas chromatograph of Tianmei GC-7890 II for sampling through a heat insulation pipeline, a Thermal Conductivity Detector (TCD) is used for on-line detection, a liquid phase product is sampled once every 6 hours until no liquid is generated, the liquid phase product is injected into the gas chromatograph of Tianmei GC-7890 II after being sampled by an injector, and the analysis result is analyzed by a hydrogen flame detector (FID), and is shown in table 2.
Example 2
The invention relates to a preparation method of a copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas, which is implemented according to the following steps:
step 1 is the same as in example 1;
step 2, adding anhydrous copper sulfate, cobalt sulfate heptahydrate, sodium citrate and sodium sulfate into 1L of deionized water, uniformly stirring to obtain a solution a, adjusting the pH value of the solution a to 4.5 by adopting a sulfuric acid solution or a sodium hydroxide solution, and placing the solution a into a constant-temperature water bath kettle at the temperature of 50 ℃ after adjustment to obtain electrolyte;
wherein the concentration of anhydrous copper sulfate in the solution a is 5g/L, the concentration of cobalt sulfate heptahydrate is 40g/L, the concentration of sodium citrate is 50g/L and the concentration of sodium sulfate is 20 g/L;
step 3, placing the cathode electrode material and the anode electrode material obtained in the step 1 into the electrolyte obtained in the step 2, connecting the cathode electrode material and the anode electrode material by adopting a numerical control constant current electroplating power supply, and setting the current density of electrolysis to be 2.9A/dm2Electrifying to electrolyze for 30min to obtain a copper-cobalt-based catalyst sample;
wherein, the anode electrode material is a graphite plate; the thickness of the carbon paper and the graphite plate is 2 mm;
step 4, washing the copper-cobalt-based catalyst sample obtained in the step 3 into a container, drying the sample at 110 ℃ for 8 hours, and then heating the sample at the temperature of 5 ℃/min at N2Roasting for 4 hours in a tubular furnace in the atmosphere at the roasting temperature of 400 ℃, tabletting and grinding by using a table type tablet machine after the roasting is finished, and screening by using a 40-60-mesh screen to obtain the copper-cobalt-based catalyst.
SEM and N are carried out on the obtained copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas2Physical adsorption-desorption characterization, the obtained results are shown in fig. 1(b) and table 1;
the specific process of the performance test of the copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas is the same as that of example 1, and the analysis results are shown in table 2.
Example 3
The invention relates to a preparation method of a copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas, which is implemented according to the following steps:
step 1 is the same as in example 1;
step 2, adding anhydrous copper sulfate, cobalt sulfate heptahydrate, sodium citrate and sodium sulfate into 1L of deionized water, uniformly stirring to obtain a solution a, adjusting the pH value of the solution a to 4.5 by adopting a sulfuric acid solution or a sodium hydroxide solution, and placing the solution a into a constant-temperature water bath kettle at the temperature of 50 ℃ after adjustment to obtain electrolyte;
wherein the concentration of anhydrous copper sulfate in the solution a is 5g/L, the concentration of cobalt sulfate heptahydrate is 40g/L, the concentration of sodium citrate is 40g/L and the concentration of sodium sulfate is 20 g/L;
step 3, placing the cathode electrode material and the anode electrode material obtained in the step 1 into the electrolyte obtained in the step 2, connecting the cathode electrode material and the anode electrode material by adopting a numerical control constant current electroplating power supply, and setting the current density of electrolysis to be 2.9A/dm2Electrifying to electrolyze for 30min to obtain a copper-cobalt-based catalyst sample;
wherein, the anode electrode material is a graphite plate; the thickness of the carbon paper and the graphite plate is 2 mm;
step 4, washing the copper-cobalt-based catalyst sample obtained in the step 3 into a container, drying the sample at 110 ℃ for 8 hours, and then heating the sample at the temperature of 5 ℃/min at N2Roasting for 4 hours in a tubular furnace in the atmosphere at the roasting temperature of 400 ℃, tabletting and grinding by using a table type tablet machine after the roasting is finished, and screening by using a 40-60-mesh screen to obtain the copper-cobalt-based catalyst.
SEM and N are carried out on the obtained copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas2Physical adsorption-desorption characterization, the obtained results are shown in fig. 1(c) and table 1;
the specific process of the performance test of the copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas is the same as that of example 1, and the analysis results are shown in table 2.
Example 4
The invention relates to a preparation method of a copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas, which is implemented according to the following steps:
step 1 is the same as in example 1;
step 2, adding anhydrous copper sulfate, cobalt sulfate heptahydrate, sodium citrate and sodium sulfate into 1L of deionized water, uniformly stirring to obtain a solution a, adjusting the pH value of the solution a to 4.5 by adopting a sulfuric acid solution or a sodium hydroxide solution, and placing the solution a into a constant-temperature water bath kettle at the temperature of 50 ℃ after adjustment to obtain electrolyte;
wherein the concentration of anhydrous copper sulfate in the solution a is 5g/L, the concentration of cobalt sulfate heptahydrate is 40g/L, the concentration of sodium citrate is 50g/L and the concentration of sodium sulfate is 20 g/L;
step 3, placing the cathode electrode material and the anode electrode material obtained in the step 1 into the electrolyte obtained in the step 2, connecting the cathode electrode material and the anode electrode material by adopting a numerical control constant current electroplating power supply, and setting the current density of electrolysis to be 2.1A/dm2Electrifying to electrolyze for 30min to obtain a copper-cobalt-based catalyst sample;
wherein, the anode electrode material is a graphite plate; the thickness of the carbon paper and the graphite plate is 2 mm;
step 4, washing the copper-cobalt-based catalyst sample obtained in the step 3 into a container, drying the sample at 110 ℃ for 8 hours, and then heating the sample at the temperature of 5 ℃/min at N2Roasting for 4 hours in a tubular furnace in the atmosphere at the roasting temperature of 400 ℃, tabletting and grinding by using a table type tablet machine after the roasting is finished, and screening by using a 40-60-mesh screen to obtain the copper-cobalt-based catalyst.
SEM and N are carried out on the obtained copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas2Physical adsorption-desorption characterization, the obtained results are shown in fig. 1(d) and table 1;
the specific process of the performance test of the copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas is the same as that of example 1, and the analysis results are shown in table 2.
Example 5
The invention relates to a preparation method of a copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas, which is implemented according to the following steps:
step 1 is the same as in example 1;
step 2, adding anhydrous copper sulfate, cobalt sulfate heptahydrate, sodium citrate and sodium sulfate into 1L of deionized water, uniformly stirring to obtain a solution a, adjusting the pH value of the solution a to 4.5 by adopting a sulfuric acid solution or a sodium hydroxide solution, and placing the solution a into a constant-temperature water bath kettle at the temperature of 50 ℃ after adjustment to obtain electrolyte;
wherein the concentration of anhydrous copper sulfate in the solution a is 5g/L, the concentration of cobalt sulfate heptahydrate is 40g/L, the concentration of sodium citrate is 50g/L and the concentration of sodium sulfate is 20 g/L;
step 3, placing the cathode electrode material and the anode electrode material obtained in the step 1 into the electrolyte obtained in the step 2, connecting the cathode electrode material and the anode electrode material by adopting a numerical control constant current electroplating power supply, and setting the current density of electrolysis to be 2.9A/dm2Electrifying to electrolyze for 40min to obtain a copper-cobalt-based catalyst sample;
wherein, the anode electrode material is a graphite plate; the thickness of the carbon paper and the graphite plate is 2 mm;
step 4, washing the copper-cobalt-based catalyst sample obtained in the step 3 into a container, drying the sample at 110 ℃ for 8 hours, and then heating the sample at the temperature of 5 ℃/min at N2Roasting for 4 hours in a tubular furnace in the atmosphere at the roasting temperature of 400 ℃, tabletting and grinding by using a table type tablet machine after the roasting is finished, and screening by using a 40-60-mesh screen to obtain the copper-cobalt-based catalyst.
SEM and N are carried out on the obtained copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas2Physical adsorption-desorption characterization, the obtained results are shown in figure 1(e) and table 1;
the specific process of the performance test of the copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas is the same as that of example 1, and the analysis results are shown in table 2.
Example 6
The invention relates to a preparation method of a copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas, which is implemented according to the following steps:
step 1, placing carbon nanotubes in concentrated nitric acid, heating to 90 ℃, refluxing for 6h, filtering and washing to be neutral after the completion, drying overnight for 10h in a drying oven at 110 ℃, grinding, screening by using a 200-mesh sieve, then steaming and coating on carbon paper, and naturally airing to obtain a cathode electrode material;
wherein, the process of steaming and coating is as follows: weighing 0.05g of phenolic resin and 0.06g of polyvinylidene fluoride, adding the phenolic resin and the polyvinylidene fluoride into 20ml of N, N-dimethylacetamide, carrying out ultrasonic oscillation for 15min, adding 0.25g of treated carbon nano tube, continuing the ultrasonic oscillation for 8min to obtain a mixed solution, using a 12 x 12cm titanium plate to be placed above a 80 ℃ constant-temperature water bath kettle in an overhead manner, placing 10 x 10cm carbon paper on the titanium plate, uniformly dripping a layer of the mixed solution on the surface of the carbon paper by a dropper, carrying out evaporation, circulating the processes of dripping the mixed solution and evaporation until the dripping of the mixed solution is finished, and naturally airing to finish the evaporation;
the specific surface area of the carbon nano tube is 100-120 m2A pipe diameter of 30 to 50nm and a pipe length of g<10 μm, and a bulk density of 0.12-0.25 g/cm3The carbon content is more than or equal to 98 percent;
step 2, adding anhydrous copper sulfate, cobalt sulfate heptahydrate, sodium citrate and sodium sulfate into 1L of deionized water, uniformly stirring to obtain a solution a, adjusting the pH value of the solution a to 5.5 by adopting a sulfuric acid solution or a sodium hydroxide solution, and placing the solution a in a constant-temperature water bath kettle at the temperature of 45 ℃ after adjustment to obtain electrolyte;
wherein the concentration of anhydrous copper sulfate in the solution a is 7g/L, the concentration of cobaltous sulfate heptahydrate is 50g/L, the concentration of sodium citrate is 60g/L and the concentration of sodium sulfate is 20 g/L;
step 3, placing the cathode electrode material and the anode electrode material obtained in the step 1 into the electrolyte obtained in the step 2, connecting the cathode electrode material and the anode electrode material by adopting a numerical control constant current electroplating power supply, and setting the current density of electrolysis to be 3.7A/dm2Electrifying to electrolyze for 20min to obtain a copper-cobalt-based catalyst sample;
wherein, the anode electrode material is a graphite plate; the carbon paper and the graphite plate are both 2mm in thickness, the graphite plate is a commercially available graphite plate, and the carbon paper and the graphite plate are used after being soaked in a dilute alkali solution for 30min and washed clean by deionized water before use;
step 4, washing the copper-cobalt-based catalyst sample obtained in the step 3 into a container, drying the sample at 85 ℃ for 10 hours, and then heating the sample at the temperature of 5 ℃/min under the condition of N2Roasting for 4.5 hours in a tubular furnace in the atmosphere at the roasting temperature of 350 ℃, tabletting and grinding by using a table type tablet machine after the roasting is finished, and screening by using a 40-60-mesh screen to obtain the copper-cobalt-based catalyst.
SEM and N are carried out on the obtained copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas2Physical adsorption-desorption characterization, the obtained results are shown in figure 1(f) and table 1;
the specific process of the performance test of the copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas is the same as that of example 1, and the analysis results are shown in table 2.
Example 7
The invention relates to a preparation method of a copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas, which is implemented according to the following steps:
step 1, placing carbon nanotubes in concentrated nitric acid, heating to 100 ℃, refluxing for 4h, filtering and washing to be neutral after the completion, drying overnight for 10h in a drying oven at 110 ℃, grinding, screening by using a 200-mesh sieve, then steaming and coating on carbon paper, and naturally airing to obtain a cathode electrode material;
wherein, the process of steaming and coating is as follows: weighing 0.06g of phenolic resin and 0.07g of polyvinylidene fluoride, adding the phenolic resin and the polyvinylidene fluoride into 25ml of N, N-dimethylacetamide, performing ultrasonic oscillation for 25min, adding 0.28g of treated carbon nano tube, continuing the ultrasonic oscillation for 12min to obtain a mixed solution, using a 12 x 12cm titanium plate to be placed above a 80 ℃ constant-temperature water bath kettle in an overhead manner, placing 12 x 12cm carbon paper on the titanium plate, uniformly dripping a layer of the mixed solution on the surface of the carbon paper by using a dropper, performing evaporation, circulating the processes of dripping the mixed solution and evaporation until the mixed solution is dripped, and naturally drying, thus finishing the evaporation;
the specific surface area of the carbon nano tube is 100-120 m2A pipe diameter of 30 to 50nm and a pipe length of g<10 μm, and a bulk density of 0.12-0.25 g/cm3The carbon content is more than or equal to 98 percent;
step 2, adding anhydrous copper sulfate, cobalt sulfate heptahydrate, sodium citrate and sodium sulfate into 1L of deionized water, uniformly stirring to obtain a solution a, adjusting the pH value of the solution a to 3.5 by adopting a sulfuric acid solution or a sodium hydroxide solution, and placing the solution a into a constant-temperature water bath kettle at the temperature of 55 ℃ after adjustment to obtain electrolyte;
wherein the concentration of anhydrous copper sulfate in the solution a is 10g/L, the concentration of cobalt sulfate heptahydrate is 30g/L, the concentration of sodium citrate is 40g/L and the concentration of sodium sulfate is 20 g/L;
step 3, placing the cathode electrode material and the anode electrode material obtained in the step 1 into the electrolyte obtained in the step 2, connecting the cathode electrode material and the anode electrode material by adopting a numerical control constant current electroplating power supply, and setting the current density of electrolysis to be 3.7A/dm2Electrifying to electrolyze for 40min to obtain a copper-cobalt-based catalyst sample;
wherein, the anode electrode material is a graphite plate; the carbon paper and the graphite plate are both 2mm in thickness, the graphite plate is a commercially available graphite plate, and the carbon paper and the graphite plate are used after being soaked in a dilute alkali solution for 30min and washed clean by deionized water before use;
step 4, washing the copper-cobalt-based catalyst sample obtained in the step 3 into a container, drying the sample at 120 ℃ for 9 hours, and then heating the sample at the temperature of 5 ℃/min under the condition of N2Roasting for 3.5 hours in a tubular furnace in the atmosphere at the roasting temperature of 350 ℃, tabletting and grinding by using a table type tablet machine after the roasting is finished, and screening by using a 40-60-mesh screen to obtain the copper-cobalt-based catalyst.
SEM and N are carried out on the obtained copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas2Physical adsorption-desorption characterization, the results are shown in FIG. 1(g) and Table 1;
the specific process of the performance test of the copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas is the same as that of example 1, and the analysis results are shown in table 2.
TABLE 1 structural parameters of copper-cobalt based catalysts prepared in different examples
Examples BET specific surface area/cm2·g-1 Pore size/nm Pore volume/cm3·g-1
1 23.14 29.58 0.147
2 34.41 25.45 0.219
3 33.51 27.31 0.206
4 30.31 29.42 0.211
5 25.67 29.51 0.157
6 32.45 26.32 0.204
7 28.73 27.68 0.245
Fig. 1 and table 1 are SEM images and structural parameters of copper cobalt-based catalysts prepared in different examples, respectively. As can be seen from fig. 1, the surface of the copper-cobalt-based catalyst prepared by the electrodeposition method under different conditions is loose and porous, and the copper-cobalt active component is effectively dispersed on the surface of the carbon nanotube. As can be seen from Table 1, the copper-cobalt based catalyst has a large specific surface area, which is favorable for the adsorption and diffusion of reactants on the surface thereof. In particular, in example 2, the surface of the prepared catalyst is petal-shaped and is more loose, and the specific surface area can reach 34.41cm2·g-1More contribute to CO and H2The reaction is carried out at the active center of the catalyst, so that the conversion rate of CO and the yield of low-carbon alcohol are improved.
TABLE 2 application Properties of copper-cobalt based catalysts prepared in different examples
Figure BDA0002207692100000151
Table 2 shows the performance of the copper cobalt-based catalyst prepared in different examples in the application of the process for preparing lower alcohols from synthesis gas. As can be seen from table 2, the catalyst prepared by electrodeposition was good in catalytic performance. The catalyst prepared in the example 2 has a CO conversion rate of over 37 percent, the total alcohol selectivity of 42 percent and C in the product distribution3+The alcohol content can reach 47%.
The invention relates to a preparation method of a copper-cobalt catalyst used in preparation of low-carbon alcohol from synthesis gas. The catalyst prepared by the method has loose and porous surface, large specific surface area and highly dispersed active components, is favorable for adsorbing CO and H2 on the surface, and has good catalytic effect on preparing low-carbon alcohol from synthetic gas. The CO conversion rate can reach 38 percent, and the total alcohol selectivity can reach 42 percent. The electrodeposition preparation method adopted by the invention has the advantages of simple process, easily controlled deposition conditions and environmental protection.

Claims (9)

1. A preparation method of a copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas is characterized by comprising the following steps:
step 1, placing carbon nanotubes in concentrated nitric acid for treatment, then steaming and coating the carbon nanotubes on carbon paper, and naturally airing to obtain a cathode electrode material;
step 2, adding anhydrous copper sulfate, cobalt sulfate heptahydrate, sodium citrate and sodium sulfate into deionized water, uniformly stirring to obtain a solution a, adjusting the pH value of the solution a, and placing the solution a into a constant-temperature water bath kettle to obtain an electrolyte;
step 3, placing the cathode electrode material and the anode electrode material obtained in the step 1 into the electrolyte obtained in the step 2, connecting the cathode electrode material and the anode electrode material by adopting a numerical control constant current electroplating power supply, and electrolyzing to obtain a copper-cobalt-based catalyst sample;
and 4, washing the copper-cobalt-based catalyst sample obtained in the step 3 into a container, drying and roasting, tabletting and grinding after the drying, and screening by using a 40-60-mesh sieve to obtain the copper-cobalt-based catalyst.
2. The method for preparing the copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas according to claim 1, wherein the carbon nanotube treatment process in the step 1 is as follows: heating the carbon nano tube in concentrated nitric acid to 80-100 ℃, refluxing for 4-6 h, filtering and washing to be neutral after the end, drying overnight in a drying oven at 110 ℃ for 10h, grinding, and screening by using a 200-mesh sieve for later use.
3. The preparation method of the copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas according to claim 1, wherein the evaporation coating process in the step 1 is as follows: weighing 0.05-0.06 g of phenolic resin and 0.06-0.07 g of polyvinylidene fluoride, and adding into 20-25 ml of N, N-dimethylPerforming ultrasonic oscillation in acetamide for 15-25 min, adding 0.25-0.3 g of treated carbon nano tube, continuing ultrasonic oscillation for 8-12 min to obtain a mixed solution, using a titanium plate with the size of 12 x 12cm to be placed above a constant-temperature water bath kettle at 80 ℃, and then placing a titanium plate with the size of 100-144 cm in an overhead manner2The carbon paper is placed on a titanium plate, the mixed solution is uniformly dripped on the surface of the carbon paper by a layer by a burette and is evaporated to dryness, the dripping and evaporating processes of the mixed solution are circulated until the dripping of the mixed solution is finished, and the mixed solution is naturally dried, so that the evaporation coating is finished.
4. The method for preparing the copper-cobalt-based catalyst for preparing the lower alcohol from the synthesis gas as claimed in claim 1, wherein the volume of the deionized water in the step 2 is 1L; the concentration of anhydrous copper sulfate in the solution a is 5-10 g/L, the concentration of cobalt sulfate heptahydrate is 30-50 g/L, the concentration of sodium citrate is 40-60 g/L and the concentration of sodium sulfate is 20 g/L; adjusting the pH value to 3.5-5.5, wherein a sulfuric acid solution or a sodium hydroxide solution is adopted as a solution for adjusting the pH value; the temperature of the water bath is 45-55 ℃.
5. The method for preparing the copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas according to claim 1, wherein the current density of electrolysis in the step 3 is 2.1-3.7A/dm2The electrolysis time is 20-40 min.
6. The method for preparing the copper-cobalt-based catalyst for preparing the low-carbon alcohol from the synthesis gas according to claim 1, wherein the anode electrode material in the step 3 is a graphite plate.
7. The preparation method of the copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas according to claim 6, wherein the thickness of the carbon paper and the graphite plate is 2 mm.
8. The method for preparing the copper-cobalt-based catalyst for preparing the low-carbon alcohol from the synthesis gas as claimed in claim 1, wherein the drying temperature in the step 4 is85-120 ℃ for 8-10 h; calcined in N2The reaction is carried out under the atmosphere, the temperature is 350-450 ℃, and the time is 3.5-4.5 h.
9. The preparation method of the copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas according to claim 1, wherein the specific surface area of the carbon nanotubes in the step 1 is 100-120 m2A pipe diameter of 30 to 50nm and a pipe length of g<10 μm, and a bulk density of 0.12-0.25 g/cm3The carbon content is more than or equal to 98 percent.
CN201910887262.7A 2019-09-19 2019-09-19 Preparation method of copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas Active CN110665510B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910887262.7A CN110665510B (en) 2019-09-19 2019-09-19 Preparation method of copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910887262.7A CN110665510B (en) 2019-09-19 2019-09-19 Preparation method of copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas

Publications (2)

Publication Number Publication Date
CN110665510A true CN110665510A (en) 2020-01-10
CN110665510B CN110665510B (en) 2022-04-29

Family

ID=69078334

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910887262.7A Active CN110665510B (en) 2019-09-19 2019-09-19 Preparation method of copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas

Country Status (1)

Country Link
CN (1) CN110665510B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115555023A (en) * 2022-09-28 2023-01-03 西安工程大学 Preparation method of copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1669649A (en) * 2004-12-31 2005-09-21 厦门大学 Promoting cobalt-copper base catalyst for preparation of low carbon mixed alcohol-carbon nano tube from synthetic gas and preparing method thereof
CN102185131A (en) * 2011-04-13 2011-09-14 长安大学 Preparation method of porous current collector/tin-base alloy/carbon nano-tube integrated electrode
CN104233379A (en) * 2014-09-05 2014-12-24 昆明理工大学 Electro-deposition preparation method of carbon nano tube-copper base composite powder
CN104233401A (en) * 2013-06-13 2014-12-24 无锡市森信精密机械厂 Electroplating preparation method for Cu-Co alloy
CN107442125A (en) * 2017-09-05 2017-12-08 济南大学 A kind of preparation method and application of carbon-based copper cobalt/cobalt oxide nanometer sheet catalyst
CN107829107A (en) * 2017-09-25 2018-03-23 中国科学院山西煤炭化学研究所 A kind of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst and its preparation method and application
CN107899576A (en) * 2017-11-20 2018-04-13 西安工程大学 A kind of preparation method of catalyst for low carbon alcohol by synthetic gas
CN110165230A (en) * 2019-06-14 2019-08-23 齐鲁工业大学 A method of bioelectrochemical system anode is prepared using carbon nanotube and carbon fiber

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1669649A (en) * 2004-12-31 2005-09-21 厦门大学 Promoting cobalt-copper base catalyst for preparation of low carbon mixed alcohol-carbon nano tube from synthetic gas and preparing method thereof
CN102185131A (en) * 2011-04-13 2011-09-14 长安大学 Preparation method of porous current collector/tin-base alloy/carbon nano-tube integrated electrode
CN104233401A (en) * 2013-06-13 2014-12-24 无锡市森信精密机械厂 Electroplating preparation method for Cu-Co alloy
CN104233379A (en) * 2014-09-05 2014-12-24 昆明理工大学 Electro-deposition preparation method of carbon nano tube-copper base composite powder
CN107442125A (en) * 2017-09-05 2017-12-08 济南大学 A kind of preparation method and application of carbon-based copper cobalt/cobalt oxide nanometer sheet catalyst
CN107829107A (en) * 2017-09-25 2018-03-23 中国科学院山西煤炭化学研究所 A kind of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst and its preparation method and application
CN107899576A (en) * 2017-11-20 2018-04-13 西安工程大学 A kind of preparation method of catalyst for low carbon alcohol by synthetic gas
CN110165230A (en) * 2019-06-14 2019-08-23 齐鲁工业大学 A method of bioelectrochemical system anode is prepared using carbon nanotube and carbon fiber

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
GONZALO PRIETO ET AL.: "Design and Synthesis of Copper–Cobalt Catalysts for the Selective Conversion of Synthesis Gas to Ethanol and Higher Alcohols", 《ANGEWANDTE CHEMIE》 *
HO TING LUK ET AL.: "Status and prospects in higher alcohols synthesis from syngas", 《CHEMICAL SOCIETY REVIEWS》 *
M. GUPTA ET AL.: "Electrodeposited Cu–ZnO and Mn–Cu–ZnO nanowire/tube catalysts for higher", 《CATALYSIS TODAY》 *
MAYANK GUPTA ET AL.: "Novel Pulse Electrodeposited Co−Cu−ZnO Nanowire/tube Catalysts for C1−C4 Alcohols and C2−C6 (Except C5) Hydrocarbons from CO and H2", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 *
SHAOLI FU ET AL.: "Electrodeposition and Properties of Composites Consisting of Carbon Nanotubes and Copper", 《JOURNAL OF MATERIALS ENGINEERING AND PERFORMANCE》 *
SONIA EUGENIO ET AL.: "Copper-cobalt foams as active and stable catalysts for hydrogen release by hydrolysis of sodium borohydride", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 *
YIBO YAN ET AL.: "Carbon nanotube catalysts: recent advances in synthesis, characterization and applications", 《CHEMICAL SOCIETY REVIEWS》 *
刘巍等: "铜基碳纳米管复合薄膜电沉积制备工艺", 《材料科学与工艺》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115555023A (en) * 2022-09-28 2023-01-03 西安工程大学 Preparation method of copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas

Also Published As

Publication number Publication date
CN110665510B (en) 2022-04-29

Similar Documents

Publication Publication Date Title
CN107715884B (en) A kind of metal load type biomass half char catalyst and preparation method thereof
CN108714429B (en) Rod-shaped CoP/CoP2Preparation method of nano composite electrocatalyst
CN105728020A (en) Preparation method for core-shell type iron carbide catalyst
CN112044458A (en) Multi-level metal phosphide and preparation method and application thereof
CN112791739A (en) Preparation and application of carbon dioxide electrochemical reduction catalyst
CN111346642A (en) High-dispersion metal nanoparticle/biomass carbon composite electrode material and preparation method and application thereof
CN110628038A (en) Covalent triazine organic framework, limited-area metal catalyst, preparation method and application
CN114032576A (en) Preparation method of defect nanofiber carbon carrier coupled iron monatomic catalyst
CN112675893A (en) Method for preparing monatomic catalyst by using adsorbed-resolved waste adsorbent
CN110665510B (en) Preparation method of copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas
CN110639488A (en) Application of biomass-based carbon material in electrochemical reduction of carbon dioxide
CN113512738B (en) Ternary iron-nickel-molybdenum-based composite material water electrolysis catalyst, and preparation method and application thereof
CN113957458A (en) g-C3N4Preparation and electrocatalytic properties of/two-dimensional porphyrin MOF material
CN112670526B (en) Preparation method and application of amorphous manganese dioxide modified shrimp shell carbon base frame
CN106423171A (en) Ni/Cu/M catalyst for catalytic methanol synthesis reaction and preparation method thereof
CN112108138B (en) Biomass hydrothermal carbon carrier catalyst and preparation method and application thereof
CN111974383A (en) Coconut shell activated carbon supported platinum catalyst and preparation method and application thereof
CN107899576B (en) Preparation method of catalyst for preparing low-carbon alcohol from synthesis gas
PENG et al. Preparation and investigation of Fe-MIL-101 as efficient catalysts for oxygen evolution reaction
CN113684499B (en) Preparation method and application of nickel-nitrogen co-doped carbon-based catalyst with high metal loading efficiency
CN112138654B (en) Catalyst for hydromethanation of carbon dioxide and application thereof
CN112237931B (en) Bulk phase nickel phosphide catalyst, preparation method and application in phenol hydrodeoxygenation
CN112281183B (en) Cluster-shaped bismuth selenide, preparation method thereof and application of cluster-shaped bismuth selenide in electrocatalytic reduction of carbon dioxide
CN110180592B (en) Preparation method of catalyst for carbon dioxide hydrogenation reaction
CN111822024B (en) Environment-friendly copper-iron MOF material with two-dimensional nano wall array structure and controllable iron content and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant