CN114160143B - CO (carbon monoxide) 2 Catalyst for preparing methanol by hydrogenation and preparation method and application thereof - Google Patents

CO (carbon monoxide) 2 Catalyst for preparing methanol by hydrogenation and preparation method and application thereof Download PDF

Info

Publication number
CN114160143B
CN114160143B CN202111492089.4A CN202111492089A CN114160143B CN 114160143 B CN114160143 B CN 114160143B CN 202111492089 A CN202111492089 A CN 202111492089A CN 114160143 B CN114160143 B CN 114160143B
Authority
CN
China
Prior art keywords
catalyst
solution
reaction
copper
hours
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.)
Active
Application number
CN202111492089.4A
Other languages
Chinese (zh)
Other versions
CN114160143A (en
Inventor
孙予罕
王慧
吴兆萱
王浩渺
黄超杰
夏林
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.)
Shanghai Cluster Rui Low Carbon Energy Technology Co ltd
Shanghai Advanced Research Institute of CAS
Original Assignee
Shanghai Cluster Rui Low Carbon Energy Technology Co ltd
Shanghai Advanced Research Institute of CAS
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 Shanghai Cluster Rui Low Carbon Energy Technology Co ltd, Shanghai Advanced Research Institute of CAS filed Critical Shanghai Cluster Rui Low Carbon Energy Technology Co ltd
Priority to CN202111492089.4A priority Critical patent/CN114160143B/en
Publication of CN114160143A publication Critical patent/CN114160143A/en
Application granted granted Critical
Publication of CN114160143B publication Critical patent/CN114160143B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B01J23/80—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 zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
    • 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)
  • Catalysts (AREA)

Abstract

The invention provides a CO 2 Catalyst for preparing methanol by hydrogenation, and its preparation method and application are provided. The catalyst comprises zinc oxide and copper nanotubes, wherein the zinc oxide coats the copper nanotubes, and the general formula of the copper nanotubes is Cu 2 Si 2 O 5 (OH) 2 . The preparation method comprises the following steps: and (3) immersing the copper nano tube in a zinc ion-containing impregnating solution, and then roasting to obtain the catalyst. The catalyst is used in preparing methanol through carbon dioxide hydrogenation. CO 2 And H 2 The reaction is carried out in the presence of the catalyst to obtain methanol. The catalyst of the invention has excellent catalytic performance, CO 2 The conversion rate and the methanol selectivity are excellent, and the method provides a wide prospect for subsequent industrial application.

Description

CO (carbon monoxide) 2 Catalyst for preparing methanol by hydrogenation and preparation method and application thereof
Technical Field
The present invention relates to CO 2 The technical field of hydrogenation catalytic conversion, in particular to a catalyst for CO 2 Catalyst for preparing methanol by hydrogenation, and its preparation method and application are provided.
Background
MethanolThe methanol is an important chemical intermediate raw material, can be used as fuel of an internal combustion engine and a fuel cell, and can be used as an alternative chemical raw material to synthesize various chemicals, gasoline and other fuels along with the gradual reduction of non-renewable energy sources. With the recent development of molecular sieve catalysts, technologies such as Methanol To Olefins (MTO), methanol to aromatics (MTG), and the like, the demand of the international market for fuels derived from methanol has rapidly increased (Johnson, d.global Methanol Demand Growth; IHS inc., 2016). Traditional industrial methanol production processes using synthesis gas conversion are mainly faced with catalysts (Cu/ZnO/Al 2 O 3 ) The active site is easy to sinter under the reaction condition, and the production of raw material synthesis gas in the process is often accompanied by the consumption of fossil resources such as coal, natural gas and the like and CO caused by the conversion process 2 Emissions and environmental pollution.
CO 2 Is a major component of greenhouse gases in the atmosphere, which results from the combustion of large amounts of fossil fuels and has led to increasingly global climate change over the last decades. CO emitted into the atmosphere annually by human activity 2 Approximately 400 million tons of atmospheric CO in 2019 2 The content is up to 407ppm, which has increased by 20% in the last 40 years. CO reduction 2 The discharge amount is certainly an urgent issue. If CO is to be used 2 The renewable energy is converted into chemical raw materials, so that the CO can be solved 2 Excessive emissions can also cause CO 2 Become a novel carbon source for replacing the traditional fossil fuel. CO 2 The molecules being chemically inert but incorporating H with high free energy 2 The molecules act as reactants to make the reaction thermodynamically easier, while H 2 If the water is obtained by adopting renewable modes such as electrolytic water or photolytic water, the whole process has wide prospects in environmental and economic aspects. Thus, CO is adopted 2 Catalytic hydrogenation to methanol is an attractive CO reduction 2 Discharging and creating a new scheme for the carbon recycle process.
CO at present 2 The hydrogenation to prepare methanol mainly adopts a supported metal or metal oxide catalyst, and many research teams are devoted to disclosing the influence on the catalysisFactors of catalyst activity, selectivity and stability, wherein ZnO is an important carrier in the preparation of Cu-based catalysts, is used for regulating the morphology of the carrier and for stabilizing copper species, and ZrO can be used 2 ，Al 2 O 3 ，La 2 O 3 And SiO 2 As a further auxiliary agent, functions to better disperse copper species. In recent years based on Cu-based catalysts CO 2 The hydrogenation reaction for preparing methanol is often limited to the surface interface characteristic of the catalyst, and has a breakthrough in catalytic performance.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a CO 2 The catalyst for preparing methanol by hydrogenation and the preparation method and the application thereof solve the problems of low selectivity and low reaction activity of the traditional catalyst.
To achieve the above and other related objects, a first aspect of the present invention provides a CO 2 The catalyst for preparing methanol by hydrogenation comprises zinc oxide and copper nanotubes, wherein the zinc oxide coats the copper nanotubes, and the copper nanotubes have a general formula of Cu 2 Si 2 O 5 (OH) 2 。
Preferably, the zinc oxide comprises 2.5 to 20% by mass of the catalyst, such as 2.5 to 5%, 5 to 10%, 10 to 15% or 15 to 20%.
The second aspect of the present invention provides a method for preparing the above catalyst, wherein the copper nanotubes are immersed in an immersion solution containing zinc ions, dried and baked to obtain the catalyst.
Preferably, the method further comprises at least one of the following technical characteristics:
1) The impregnation solution containing zinc ions is zinc nitrate aqueous solution;
2) The drying temperature is 20-30 ℃, such as 20-25 ℃ or 25-30 ℃;
3) The roasting temperature is 450-550 ℃, such as 450-500 ℃ or 500-550 ℃;
4) The copper nanotube is obtained by a preparation method comprising the following steps: the copper source and the silicon source are subjected to a hydrothermal reaction, and then filtered, washed, dried and baked.
More preferably, in the feature 4), at least one of the following technical features is further included:
41 The copper source is copper nitrate;
42 The silicon source is silica gel;
43 The hydrothermal reaction specifically comprises the following steps: carrying out hydrothermal reaction on an aqueous solution containing a copper source and an ammonium source, and an aqueous solution containing a silicon source and an alkali solution;
44 The temperature of the hydrothermal reaction is 180-200 ℃, such as 180 ℃, 185 ℃, 190 ℃, 195 ℃ or 200 ℃;
45 The drying temperature is 50-80 ℃, such as 50-60 ℃ or 60-80 ℃;
41 The baking temperature is 450-550 ℃, such as 450-500 ℃ or 500-550 ℃.
Even more preferably, feature 43) further comprises at least one of the following technical features:
431 The ammonium source is selected from at least one of ammonium chloride and ammonium nitrate; the pH value of the solution is regulated by weak acidity of an ammonium source, the hydrolysis of a copper source is inhibited, a buffer solution is formed, and the precipitate formed after the alkaline solution is added later has more regular morphology and higher specific surface. In addition, the ammonium source provides free ammonium ions, so that Cu ions form Cu ammonium complex ions, and the Cu ammonium complex ions are coordinated with the silicon oxygen tetrahedron;
432 The concentration of copper ions in the aqueous solution containing the copper source and the ammonium source is 0.12 to 0.16mol/L, such as 0.12 to 0.14mol/L or 0.14 to 0.16mol/L;
433 The concentration of ammonium ions in the aqueous solution containing the copper source and the ammonium source is 0.39 to 0.47mol/L, such as 0.39 to 0.43mol/L or 0.43 to 0.47mol/L;
434 The molar ratio of copper ions to ammonium ions in the aqueous solution containing a copper source and an ammonium source is 1:2.5 to 1:3.5, such as 1:2.5 to 1:3 or 1: 3-1: 3.5;
435 The alkali solution is ammonia water;
436 The concentration of the alkali solution is 17.5 to 19mol/L, such as 17.5 to 18.5mol/L or 18.5 to 19mol/L;
437 The molar ratio of copper ions to alkali in the aqueous solution containing the copper source and the ammonium source is 1:10 to 1:13, as 1:10 to 1:11.5 or 1:11.5 to 1:13.
in a third aspect the invention provides the use of the catalyst described above in the hydrogenation of carbon dioxide to produce methanol.
Preferably, the catalyst is subjected to hydrogenation reduction prior to use in the hydrogenation of carbon dioxide to produce methanol.
More preferably, at least one of the following technical features is further included:
1) The hydrogenation reduction temperature is 200-300 ℃, such as 200-250 ℃ or 250-300 ℃, and can be 200 ℃, 250 ℃ and 300 ℃.
2) The hydrogenation reduction time is 6 to 16h, such as 6 to 12h or 12 to 16h, and can be 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h or 16h.
3) The hydrogenation reduction pressure is 0.01-0.5 Mpa, such as 0.01-0.1 Mpa or 0.1-0.5 Mpa, and can be 0.05Mpa, 0.1Mpa, 0.15Mpa, 0.2Mpa, 0.25Mpa, 0.3Mpa, 0.35Mpa, 0.4Mpa, 0.45Mpa or 0.5Mpa.
4) The hydrogen space velocity of hydrogenation reduction is 2500-3500 ml/g/h, such as 2500-3000 ml/g/h or 3000-3500 ml/g/h.
In a fourth aspect the invention provides a CO 2 Method for preparing methanol by hydrogenation and CO 2 And H 2 The reaction is carried out in the presence of the catalyst to obtain methanol.
Preferably, the method further comprises at least one of the following technical characteristics:
1)CO 2 and H is 2 The volume ratio of (1): 2-1: 7, as 1: 2-1: 3 or 1: 3-1: 7, preparing a base material; more preferably, CO 2 And H is 2 Is 1:3 by volume;
2) The reaction temperature is 240-300 ℃, such as 240-250 ℃, 250-260 ℃, 260-270 ℃, 270-280 ℃ or 280-300 ℃; more preferably, the reaction temperature is 240 ℃;
3) The reaction pressure is 2-7 Mpa, such as 2-5 Mpa or 5-7 Mpa; more preferably, the reaction pressure is 5Mpa;
4) The reaction space velocity is 5000-24000 ml/g/h, such as 5000-8000 ml/g/h, 8000-12000 ml/g/h, 12000-16000 ml/g/h, 16000-20000 ml/g/h or 20000-24000 ml/g/h.
Compared with the prior art, the invention has at least one of the following beneficial effects:
1) The catalyst is a nano tube material based on copper silicate, so that the metal Cu is uniformly distributed on the surface of the nano tube in space, cu particles are effectively inhibited from growing up, the defect that the activity of the traditional Cu-based catalyst is compatible and easy to aggregate is overcome, and the long-range stability of the catalyst under the reaction condition is realized.
2) The catalyst of the invention has excellent catalytic performance, CO 2 The conversion and the methanol selectivity are excellent.
3) Compared with the traditional Cu-based catalyst, the catalyst provided by the invention has higher specific surface area and active site, and the Zn-Cu interface is changed by regulating and controlling the ZnO loading, so that the methanol selectivity is changed. The existence of the Cu-O-SiOx interface can effectively stabilize Cu 0 /Cu + The stable activity of the catalyst is beneficial to large-scale industrial application.
4) The invention provides a novel preparation method of the ZnO coated Cu nanotube catalyst, and the reaction performance evaluation is carried out in a fixed bed reactor, so that the method has the characteristics of high methanol selectivity and long-time stable operation at higher temperature and pressure, and provides a wide prospect for subsequent industrial application.
5) The catalyst of the invention has simple preparation process, is easy to repeat, and can be prepared in large scale.
Drawings
FIG. 1 is an XRD spectrum of copper nanotubes before and after firing in example 1 of the present invention.
Detailed Description
The invention is further illustrated below with reference to examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods and reagents not specifying the formulation in the following examples were carried out or configured under conventional conditions or conditions suggested by the manufacturer.
Example 1
Preparation of copper nanotubes (Cu) by hydrothermal method 2 Si 2 O 5 (OH) 2 ). Copper nitrate and ammonium chloride (1.57 g and 1.39g, respectively) were dissolved in 60mL of deionized water to form a salt solution A, which was then stirred at 30℃for 2 hours, while 5mL of an alkaline solution (saturated aqueous ammonia solution 18.5 mol/L) was added dropwise to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Transferring the solution B into a 100mL stainless steel water heating kettle, heating at 200 ℃ for 48 hours, filtering the precipitate, fully washing with deionized water, vacuum drying at 60 ℃, cooling the solid to room temperature (XRD spectrum is shown as Cu-NPST in figure 1), and roasting in air at 500 ℃ for 2 hours to obtain the copper nanotube catalyst, wherein the XRD spectrum is shown as Cu-NPST-clacination in figure 1. 0.072g of zinc nitrate is dissolved in 5mL of deionized water to form solution C, then the copper nanotube catalyst is fully mixed with the solution C, and the mixture is dried at room temperature and then baked in the air at 500 ℃ for 2 hours, thus obtaining the zinc oxide coated copper nanotube catalyst (ZnO content is 2.5%).
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high-pressure micro-reactor, introducing hydrogen gas to reduce under normal pressure, wherein the reduction airspeed is 3000ml/g/H, the reduction temperature is 250 ℃, the reduction time is 12H, after the reduction process is finished, cooling the reaction furnace to room temperature, and introducing H 2 /CO 2 The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 5000 ml.g -1 ·h -1 The reaction temperature was 240℃and the activity evaluation results are shown in Table 1.
Example 2
Preparation of copper nanotubes (Cu) by hydrothermal method 2 Si 2 O 5 (OH) 2 ). Copper nitrate and ammonium chloride (1.57 g and 1.39g, respectively) were dissolved in 60mL of deionized water to form a salt solution A, which was then stirred at 30℃for 2 hours, while 5mL of an alkaline solution (saturated aqueous ammonia solution 18.5 mol/L) was added dropwise to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Transferring the solution B into a 100mL stainless steel hot pot, heating at 200 ℃ for 48 hours, filtering the precipitate, fully washing with deionized water, vacuum drying at 60 ℃, cooling the solid to room temperature,and then roasting for 2 hours at 500 ℃ in air to obtain the copper nanotube catalyst. 0.145g of zinc nitrate is dissolved in 5mL of deionized water to form solution C, then the copper nanotube catalyst is fully mixed with the solution C, dried at room temperature and roasted for 2 hours at 500 ℃ in air, and the zinc oxide coated copper nanotube catalyst (ZnO content of 5%) is obtained.
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high-pressure micro-reactor, introducing hydrogen gas to reduce under normal pressure, wherein the reduction airspeed is 3000ml/g/H, the reduction temperature is 250 ℃, the reduction time is 12H, after the reduction process is finished, cooling the reaction furnace to room temperature, and introducing H 2 /CO 2 The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 5000 ml.g -1 ·h -1 The reaction temperature was 240℃and the activity evaluation results are shown in Table 1.
Example 3
Preparation of copper nanotubes (Cu) by hydrothermal method 2 Si 2 O 5 (OH) 2 ). Copper nitrate and ammonium chloride (1.57 g and 1.39g, respectively) were dissolved in 60mL of deionized water to form a salt solution A, which was then stirred at 30℃for 2 hours, while 5mL of an alkaline solution (saturated aqueous ammonia solution 18.5 mol/L) was added dropwise to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Transferring the solution B into a 100mL stainless steel water heating kettle, heating at 200 ℃ for 48 hours, filtering the precipitate, fully washing with deionized water, vacuum drying at 60 ℃, cooling the solid to room temperature, and roasting at 500 ℃ in air for 2 hours to obtain the copper nanotube catalyst. 0.29g of zinc nitrate is dissolved in 5mL of deionized water to form solution C, then the copper nanotube catalyst is fully mixed with the solution C, dried at room temperature and roasted for 2 hours at 500 ℃ in air, and the zinc oxide coated copper nanotube catalyst (ZnO content 10%) is obtained.
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high-pressure micro-reactor, introducing hydrogen gas to reduce under normal pressure, wherein the reduction airspeed is 3000ml/g/H, the reduction temperature is 250 ℃, the reduction time is 12H, after the reduction process is finished, cooling the reaction furnace to room temperature, and introducing H 2 /CO 2 The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 5000 ml.g -1 ·h -1 The reaction temperature was 240℃and the activity evaluation results are shown in Table 1.
Example 4
Preparation of copper nanotubes (Cu) by hydrothermal method 2 Si 2 O 5 (OH) 2 ). Copper nitrate and ammonium chloride (1.57 g and 1.39g, respectively) were dissolved in 60mL of deionized water to form a salt solution A, which was then stirred at 30℃for 2 hours, while 5mL of an alkali-soluble (saturated aqueous ammonia 18.5 mol/L) solution was added dropwise to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Transferring the solution B into a 100mL stainless steel water heating kettle, heating at 200 ℃ for 48 hours, filtering the precipitate, fully washing with deionized water, vacuum drying at 60 ℃, cooling the solid to room temperature, and roasting at 500 ℃ in air for 2 hours to obtain the copper nanotube catalyst. 0.435g of zinc nitrate is dissolved in 5mL of deionized water to form solution C, then the copper nanotube catalyst is fully mixed with the solution C, dried at room temperature and roasted for 2 hours at 500 ℃ in air, and the zinc oxide coated copper nanotube catalyst (ZnO content 15%) is obtained.
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high-pressure micro-reactor, introducing hydrogen gas to reduce under normal pressure, wherein the reduction airspeed is 3000ml/g/H, the reduction temperature is 250 ℃, the reduction time is 12H, after the reduction process is finished, cooling the reaction furnace to room temperature, and introducing H 2 /CO 2 The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 5000 ml.g -1 ·h -1 The reaction temperature was 240℃and the activity evaluation results are shown in Table 1.
Example 5
Preparation of copper nanotubes (Cu) by hydrothermal method 2 Si 2 O 5 (OH) 2 ). Copper nitrate and ammonium chloride (1.57 g and 1.39g, respectively) were dissolved in 60mL of deionized water to form a salt solution A, which was then stirred at 30℃for 2 hours, while 5mL of an alkaline solution (saturated aqueous ammonia solution 18.5 mol/L) was added dropwise to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Solution BTransferring to a 100mL stainless steel water heating kettle, heating at 200 ℃ for 48 hours, filtering precipitate, fully washing with deionized water, vacuum drying at 60 ℃, cooling the solid to room temperature, and roasting in air at 500 ℃ for 2 hours to obtain the copper nanotube catalyst. 0.58g of zinc nitrate is dissolved in 5mL of deionized water to form solution C, then the copper nanotube catalyst is fully mixed with the solution C, dried at room temperature and roasted for 2 hours at 500 ℃ in air, and the zinc oxide coated copper nanotube catalyst (ZnO content 20%) is obtained.
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high-pressure micro-reactor, introducing hydrogen gas to reduce under normal pressure, wherein the reduction airspeed is 3000ml/g/H, the reduction temperature is 250 ℃, the reduction time is 12H, after the reduction process is finished, cooling the reaction furnace to room temperature, and introducing H 2 /CO 2 The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 5000 ml.g -1 ·h -1 The reaction temperature was 240℃and the activity evaluation results are shown in Table 1.
Example 6
Preparation of copper nanotubes (Cu) by hydrothermal method 2 Si 2 O 5 (OH) 2 ). Copper nitrate and ammonium chloride (1.57 g and 1.39g, respectively) were dissolved in 60mL of deionized water to form a salt solution A, which was then stirred at 30℃for 2 hours, while 5mL of an alkaline solution (saturated aqueous ammonia solution 18.5 mol/L) was added dropwise to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Transferring the solution B into a 100mL stainless steel water heating kettle, heating at 200 ℃ for 48 hours, filtering the precipitate, fully washing with deionized water, vacuum drying at 60 ℃, cooling the solid to room temperature, and roasting at 500 ℃ in air for 2 hours to obtain the copper nanotube catalyst. 0.29g of zinc nitrate is dissolved in 5mL of deionized water to form solution C, then the copper nanotube catalyst is fully mixed with the solution C, dried at room temperature and roasted for 2 hours at 500 ℃ in air, and the zinc oxide coated copper nanotube catalyst (ZnO content 10%) is obtained.
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high pressure micro-reactor, and introducingReducing with hydrogen at normal pressure and with space velocity of 3000ml/g/H, reducing temperature of 250 deg.c and reducing time of 12H, cooling the reaction furnace to room temperature and introducing H 2 /CO 2 The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 8000 ml.g -1 ·h -1 The reaction temperature was 250℃and the results of activity evaluation are shown in Table 1.
Example 7
Preparation of copper nanotubes (Cu) by hydrothermal method 2 Si 2 O 5 (OH) 2 ). Copper nitrate and ammonium chloride (1.57 g and 1.39g, respectively) were dissolved in 60mL of deionized water to form a salt solution A, which was then stirred at 30℃for 2 hours, while 5mL of an alkaline solution (saturated aqueous ammonia solution 18.5 mol/L) was added dropwise to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Transferring the solution B into a 100mL stainless steel water heating kettle, heating at 200 ℃ for 48 hours, filtering the precipitate, fully washing with deionized water, vacuum drying at 60 ℃, cooling the solid to room temperature, and roasting at 500 ℃ in air for 2 hours to obtain the copper nanotube catalyst. 0.29g of zinc nitrate is dissolved in 5mL of deionized water to form solution C, then the copper nanotube catalyst is fully mixed with the solution C, dried at room temperature and roasted for 2 hours at 500 ℃ in air, and the zinc oxide coated copper nanotube catalyst (ZnO content 10%) is obtained.
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high-pressure micro-reactor, introducing hydrogen gas to reduce under normal pressure, wherein the reduction airspeed is 3000ml/g/H, the reduction temperature is 250 ℃, the reduction time is 12H, after the reduction process is finished, cooling the reaction furnace to room temperature, and introducing H 2 /CO 2 The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 12000 ml.g -1 ·h -1 The reaction temperature was 260℃and the activity evaluation results are shown in Table 1.
Example 8
Preparation of copper nanotubes (Cu) by hydrothermal method 2 Si 2 O 5 (OH) 2 ). Copper nitrate and ammonium chloride (1.57 g and 1.39g respectively) are dissolved in 60mL deionized water to form a salt solutionA, then stirred at 30℃for 2 hours while 5mL of an alkaline solution (saturated aqueous ammonia 18.5 mol/L) was added dropwise to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Transferring the solution B into a 100mL stainless steel water heating kettle, heating at 200 ℃ for 48 hours, filtering the precipitate, fully washing with deionized water, vacuum drying at 60 ℃, cooling the solid to room temperature, and roasting at 500 ℃ in air for 2 hours to obtain the copper nanotube catalyst. 0.29g of zinc nitrate is dissolved in 5mL of deionized water to form solution C, then the copper nanotube catalyst is fully mixed with the solution C, dried at room temperature and roasted for 2 hours at 500 ℃ in air, and the zinc oxide coated copper nanotube catalyst (ZnO content 10%) is obtained.
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high-pressure micro-reactor, introducing hydrogen gas to reduce under normal pressure, wherein the reduction airspeed is 3000ml/g/H, the reduction temperature is 250 ℃, the reduction time is 12H, after the reduction process is finished, cooling the reaction furnace to room temperature, and introducing H 2 /CO 2 The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 16000 ml.g -1 ·h -1 The reaction temperature was 270℃and the activity evaluation results are shown in Table 1.
Example 9
Preparation of copper nanotubes (Cu) by hydrothermal method 2 Si 2 O 5 (OH) 2 ). Copper nitrate and ammonium chloride (1.57 g and 1.39g, respectively) were dissolved in 60mL of deionized water to form a salt solution A, which was then stirred at 30℃for 2 hours, while 5mL of an alkaline solution (saturated aqueous ammonia solution 18.5 mol/L) was added dropwise to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Transferring the solution B into a 100mL stainless steel water heating kettle, heating at 200 ℃ for 48 hours, filtering the precipitate, fully washing with deionized water, vacuum drying at 60 ℃, cooling the solid to room temperature, and roasting at 500 ℃ in air for 2 hours to obtain the copper nanotube catalyst. Dissolving 0.29g zinc nitrate in 5mL deionized water to form solution C, fully mixing the copper nanotube catalyst with the solution C, drying at room temperature, and roasting at 500 ℃ in air for 2 hours to obtain a zinc oxide packageCoated copper nanotube catalyst (ZnO content 10%).
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high-pressure micro-reactor, introducing hydrogen gas to reduce under normal pressure, wherein the reduction airspeed is 3000ml/g/H, the reduction temperature is 250 ℃, the reduction time is 12H, after the reduction process is finished, cooling the reaction furnace to room temperature, and introducing H 2 /CO 2 The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 20000 ml.g -1 ·h -1 The reaction temperature was 280℃and the activity evaluation results are shown in Table 1.
Example 10
Preparation of copper nanotubes (Cu) by hydrothermal method 2 Si 2 O 5 (OH) 2 ). Copper nitrate and ammonium chloride (1.57 g and 1.39g, respectively) were dissolved in 60mL of deionized water to form a salt solution A, which was then stirred at 30℃for 2 hours, while 5mL of an alkaline solution (saturated aqueous ammonia solution 18.5 mol/L) was added dropwise to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Transferring the solution B into a 100mL stainless steel water heating kettle, heating at 200 ℃ for 48 hours, filtering the precipitate, fully washing with deionized water, vacuum drying at 60 ℃, cooling the solid to room temperature, and roasting at 500 ℃ in air for 2 hours to obtain the copper nanotube catalyst. 0.29g of zinc nitrate is dissolved in 5mL of deionized water to form solution C, then the copper nanotube catalyst is fully mixed with the solution C, dried at room temperature and roasted for 2 hours at 500 ℃ in air, and the zinc oxide coated copper nanotube catalyst (ZnO content 10%) is obtained.
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high-pressure micro-reactor, introducing hydrogen gas to reduce under normal pressure, wherein the reduction airspeed is 3000ml/g/H, the reduction temperature is 250 ℃, the reduction time is 12H, after the reduction process is finished, cooling the reaction furnace to room temperature, and introducing H 2 /CO 2 The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 24000 ml.g -1 ·h -1 The reaction temperature was 300℃and the activity evaluation results are shown in Table 1.
Table 1 catalytic performance data in examples
The above examples are provided to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, many modifications and variations of the methods and compositions of the invention set forth herein will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in the art are intended to be within the scope of the present invention.

Claims (1)

1. CO (carbon monoxide) 2 A process for preparing methanol by hydrogenation, characterized in that CO 2 And H 2 Reacting in the presence of a zinc oxide coated copper nanotube catalyst to obtain methanol; preparation of copper nanotube Cu by hydrothermal method 2 Si 2 O 5 (OH) 2 : 1.57g of copper nitrate and 1.39g of ammonium chloride are dissolved in 60mL of deionized water to form a salt solution A, then the salt solution A is stirred for 2 hours at 30 ℃, and 5mL of alkaline solution which is 18.5mol/L saturated ammonia water is added dropwise to form a blue solution B; then 1g of silica gel is dissolved in the blue solution B and fully stirred; transferring the obtained solution into a 100mL stainless steel water heating kettle, heating at 200 ℃ for 48 hours, filtering the precipitate, fully washing with deionized water, vacuum drying at 60 ℃, cooling the solid to room temperature, and roasting at 500 ℃ in air for 2 hours to obtain the copper nanotube catalyst; dissolving 0.29g of zinc nitrate in 5mL of deionized water to form a solution C, fully mixing the copper nanotube catalyst with the solution C, drying at room temperature, and roasting in air at 500 ℃ for 2 hours to obtain a zinc oxide coated copper nanotube catalyst, wherein the zinc oxide accounts for 10% of the catalyst by mass; placing the obtained zinc oxide coated copper nanotube catalyst in a fixed stateIntroducing hydrogen into a bed high-pressure micro-reactor to reduce under normal pressure, wherein the reduction airspeed is 3000 ml.g -1 ·h -1 The reduction temperature is 250 ℃, the reduction time is 12 hours, after the reduction process is finished, the reaction furnace is cooled to room temperature, and H is introduced 2 /CO 2 The reaction is carried out by the reaction gas with the volume ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 8000 ml.g -1 ·h -1 The reaction temperature was 250 ℃.
CN202111492089.4A 2021-12-08 2021-12-08 CO (carbon monoxide) 2 Catalyst for preparing methanol by hydrogenation and preparation method and application thereof Active CN114160143B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111492089.4A CN114160143B (en) 2021-12-08 2021-12-08 CO (carbon monoxide) 2 Catalyst for preparing methanol by hydrogenation and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111492089.4A CN114160143B (en) 2021-12-08 2021-12-08 CO (carbon monoxide) 2 Catalyst for preparing methanol by hydrogenation and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114160143A CN114160143A (en) 2022-03-11
CN114160143B true CN114160143B (en) 2024-01-30

Family

ID=80484292

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111492089.4A Active CN114160143B (en) 2021-12-08 2021-12-08 CO (carbon monoxide) 2 Catalyst for preparing methanol by hydrogenation and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114160143B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115155602B (en) * 2022-08-02 2023-06-30 西部金属材料股份有限公司 Metal oxide-copper composite catalyst and preparation method and application thereof
CN117797797A (en) * 2024-03-01 2024-04-02 太原理工大学 Method for regulating and controlling active site of copper-based catalyst and catalyst

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103241763A (en) * 2013-04-15 2013-08-14 天津大学 Preparation method of gold/metal oxide core-shell structural nano material
WO2016020656A2 (en) * 2014-08-04 2016-02-11 Isis Innovation Limited Methanol production process
CN105884576A (en) * 2016-04-15 2016-08-24 中国科学院上海高等研究院 Copper-based catalyst with Cu and Zn Bi-MOF (bi-metal organic framework) as precursor as well as preparation method and application of copper-based catalyst
CN109364931A (en) * 2018-11-05 2019-02-22 江南大学 A kind of hydrogenation of carbon dioxide catalyst for methanol of core-shell structure and preparation method thereof
CN109876813A (en) * 2019-03-20 2019-06-14 华侨大学 A kind of preparation method and applications of copper zinc composite catalyst
CN112517017A (en) * 2020-11-30 2021-03-19 陕西延长石油（集团）有限责任公司 Methyl acetate hydrogenation doped copper silicate nanotube catalyst, and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103241763A (en) * 2013-04-15 2013-08-14 天津大学 Preparation method of gold/metal oxide core-shell structural nano material
WO2016020656A2 (en) * 2014-08-04 2016-02-11 Isis Innovation Limited Methanol production process
CN105884576A (en) * 2016-04-15 2016-08-24 中国科学院上海高等研究院 Copper-based catalyst with Cu and Zn Bi-MOF (bi-metal organic framework) as precursor as well as preparation method and application of copper-based catalyst
CN109364931A (en) * 2018-11-05 2019-02-22 江南大学 A kind of hydrogenation of carbon dioxide catalyst for methanol of core-shell structure and preparation method thereof
CN109876813A (en) * 2019-03-20 2019-06-14 华侨大学 A kind of preparation method and applications of copper zinc composite catalyst
CN112517017A (en) * 2020-11-30 2021-03-19 陕西延长石油（集团）有限责任公司 Methyl acetate hydrogenation doped copper silicate nanotube catalyst, and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Yuan Sheng et al.."Structured Assemblages of Single-Walled 3d Transition Metal Silicate Nanotubes as Precursors for Composition-Tailorable Catalysts".《Chemistry of Materials》.2015,第27卷第658-667页. *

Also Published As

Publication number Publication date
CN114160143A (en) 2022-03-11

Similar Documents

Publication Publication Date Title
CN114160143B (en) CO (carbon monoxide) 2 Catalyst for preparing methanol by hydrogenation and preparation method and application thereof
CN113058595A (en) Ru-based ammonia decomposition hydrogen production catalyst and preparation method thereof
CN109201096B (en) CO2Catalyst for preparing low-carbon mixed alcohol by hydrogenation and application thereof
CN112174764A (en) Application of iron-based catalyst in catalyzing carbon dioxide hydrogenation to synthesize low-carbon olefin
CN107335446B (en) Cobalt-based catalyst for preparing mixed alcohol from synthesis gas by one-step method and preparation and application thereof
CN114272950A (en) CH (physical channel)4、CO2Catalyst for reforming preparation of synthesis gas and preparation method and application thereof
CN111992213B (en) Preparation method of core-shell catalyst for preparing cyclohexanol by catalytic hydrogenation and deoxidation of guaiacol
CN111905752B (en) Method for synthesizing dimethyl carbonate by using superfine cobalt-cerium bimetallic nano catalyst as catalyst
CN111167518A (en) Catalyst CuZn/UiO-66 for synthesizing methanol by carbon dioxide hydrogenation and preparation method thereof
CN110368933A (en) It is a kind of using Ce-Ti composite oxides as ruthenium-based ammonia synthetic catalyst of carrier and preparation method thereof
CN109499577A (en) The preparation of Cu-Ni base catalyst for inverse water gas reaction and application method
CN111841541A (en) Preparation method and application of CuFeC catalyst
CN109999878A (en) For photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst and preparation method thereof
CN113145113A (en) Carbon dioxide hydrogenation catalyst, preparation method and application thereof
CN113600202A (en) Catalyst for decomposing nitrous oxide, preparation method thereof and nitrous oxide decomposition method
CN114534732B (en) Synthesis method of catalyst for preparing hydrogen by steam reforming of propane
CN115318298A (en) Copper-based ternary catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method and application thereof
CN114950439A (en) Efficient water photolysis hydrogen production MOF TiO 2 -NiO material and preparation method and application thereof
CN109433202B (en) Ruthenium-based catalyst loaded on barium tantalate surface and application thereof in ammonia synthesis
CN113522293A (en) Preparation method and application of catalyst for hydrogen production by dry reforming of methane and carbon dioxide
CN114713237B (en) Preparation and application of copper-cerium oxide-titanium dioxide catalyst with controllable structure
CN110479259B (en) Supported Ru-based catalyst with molybdenum oxide-zinc oxide-zirconium oxide composite oxide as carrier
CN110152675A (en) The method of low carbon alcohol by synthetic gas catalyst, preparation method and low carbon alcohol by synthetic gas
CN110317233A (en) Metallic nickel and Metallic Manganese Complex and the preparation method and application thereof
CN114832839B (en) Iron-based solid super acid catalyst synthesized by persulfate in auxiliary mode, preparation and application

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