CN116713030A - Molecular sieve catalyst for preparing low-carbon alcohol by carbon dioxide selective hydrogenation, preparation method and application - Google Patents

Molecular sieve catalyst for preparing low-carbon alcohol by carbon dioxide selective hydrogenation, preparation method and application Download PDF

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CN116713030A
CN116713030A CN202310402933.2A CN202310402933A CN116713030A CN 116713030 A CN116713030 A CN 116713030A CN 202310402933 A CN202310402933 A CN 202310402933A CN 116713030 A CN116713030 A CN 116713030A
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catalyst
molecular sieve
selective hydrogenation
carbon dioxide
aluminum
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李兰冬
柴玉超
刘向群
武光军
关乃佳
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Nankai University
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Nankai University
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    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/763—CHA-type, e.g. Chabazite, LZ-218
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/783—CHA-type, e.g. Chabazite, LZ-218
    • 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
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a molecular sieve catalyst for preparing low-carbon alcohol by selective hydrogenation of carbon dioxide, a preparation method and application thereof, in particular to construction of an M-silicon-aluminum molecular sieve system and application thereof in selective hydrogenation of acetylene, and the problems of high content of transition metal, complex structure, high production cost, high energy consumption of process flow and the like in the conventional process of using the catalytic system in the preparation of low-carbon alcohol by selective hydrogenation of carbon dioxide by synthesizing an M (copper, chromium and the like) -molecular sieve catalytic system by a hydrothermal method and applying the M (copper, chromium and the like) molecular sieve catalytic system to the reaction of preparing the low-carbon alcohol by selective hydrogenation of the carbon dioxide are solved. The Cu-molecular sieve is prepared by one-step hydrothermal synthesis and is applied to selective hydrogenation of carbon dioxide, the catalyst is low in cost and easy to obtain, the preparation process is simple, the catalytic activity is high, the stability is good, and the catalyst can be applied to the process of preparing low-carbon alcohol by selective hydrogenation of carbon dioxide under a milder condition, shows excellent catalytic activity and selectivity, and can be applied to industrial production of preparing low-carbon alcohol (such as methanol) by selective hydrogenation of carbon dioxide.

Description

Molecular sieve catalyst for preparing low-carbon alcohol by carbon dioxide selective hydrogenation, preparation method and application
Technical Field
The invention relates to a molecular sieve catalyst for preparing low-carbon alcohol by selective hydrogenation of carbon dioxide, a preparation method and application thereof, in particular to construction of an M-silicon-aluminum molecular sieve system and application thereof in selective hydrogenation of acetylene, and the M (copper, chromium and the like) -molecular sieve catalyst system is synthesized by a hydrothermal method and applied to a reaction for preparing low-carbon alcohol by selective hydrogenation of carbon dioxide.
Background
CO 2 As a large amount of renewable carbon source compounds in nature, the compound is an ideal energy source supplementing source. CO 2 Is an important proposition faced by human beings. By H 2 CO from clean energy sources 2 The hydrogenation for preparing low-carbon alcohol chemicals such as methanol, ethanol and the like is a feasible strategy for realizing sustainable utilization of carbon resources.
CO 2 Hydrogenation to methanol or ethanol is a research hotspot in the current catalysis field, but the design and construction of the catalyst system still face a plurality of difficulties and challenges. On the one hand, CO 2 The chemical inertness of the molecule makes it difficult to be activated effectively; on the other hand, in CO 2 In the process of preparing methanol/ethanol by hydrogenation, CO is easy to accompany 2 The occurrence of side reactions such as methanation and Reverse Water Gas Shift (RWGS) limits the selectivity to the target product. To solve CO 2 A series of catalysts and corresponding preparation strategies are developed successively, and one of the most widely used methods is to dope metal auxiliaries to regulate the surface charge of active sites and the electronic properties such as d-band center, such as most of Cu-based catalysts. In addition, build heightActive metal oxide interfaces and exerting their synergistic catalytic effect are also an effective strategy for methanol synthesis, as is the CuZnAl catalytic material (the main composition of which comprises Cu0, zn0 and a 1203) that has been commercialized today. Although the related art achieves higher yields of lower alcohols, it is inevitable to face some technical drawbacks: for example, the content of transition metal in CuZnAl is higher (Cu content is more than 60 percent), the cost of the catalyst is higher, and the economic benefit of the whole catalytic process is influenced; in order to improve the yield of the low-carbon alcohol in the production process, a higher reaction temperature (more than 300 ℃) is often adopted, and the production cost is greatly improved.
Disclosure of Invention
The invention aims to provide a molecular sieve catalyst for preparing low-carbon alcohol by carbon dioxide selective hydrogenation, a preparation method and application thereof, which can solve the problems of high cost, high energy consumption and the like of a CuZnAl composite catalyst in the traditional production process. The catalyst provided by the invention is a low-cost catalyst, has extremely high single Cu or single Cr dispersity and excellent stability, and can be used for preparing CO 2 In the hydrogenation reaction, excellent catalytic activity and low-carbon alcohol selectivity can be obtained by catalysis under the action of an M-molecular sieve system.
The molecular sieve catalyst for preparing the low-carbon alcohol by the selective hydrogenation of the carbon dioxide provided by the invention is formed by taking Cu or Cr as a main active ingredient, compounding alkali metal and taking a silicon-aluminum molecular sieve as a carrier, wherein the load of Cu or Cr is 0.5-15% of the mass of the catalyst; the alkali metal accounts for 0.8-8% of the mass of the catalyst.
The synthesis method of the molecular sieve catalyst provided by the invention comprises the following main steps: the method comprises the steps of taking soluble copper salt (or chromium salt), organic amine complexing agent, alkali source, aluminum source and silicon source as raw materials, performing one-step synthesis through a hydrothermal method, washing a product with water to be neutral, drying, roasting, putting a roasted sample into an alkali metal nitrate solution for ion exchange, and then performing suction filtration, washing, drying and roasting.
The soluble copper salt is copper nitrate or copper acetate (or soluble chromium salt chromium nitrate); the organic amine complexing agent is small molecular organic amine such as ethylenediamine, diethylenetriamine, tetraethylenepentamine and the like, siloxane amine compounds and the like; siloxane amines, such as 3-aminopropyl triethoxysilane, are preferred.
Optionally, the alkali source is sodium hydroxide; the silicon source is any one of silica sol, tetraethoxysilane, silica aerosol amorphous silica powder or silicate; the aluminum source is any one of aluminum sol, aluminum isopropoxide, meta-aluminate, aluminate and pseudo-boehmite.
Optionally, the alkali metal M is lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium or the like; the silicon-aluminum molecular sieve comprises FAU, MOR, CHA, MFI and other structures.
The preparation method of the molecular sieve catalyst for preparing low-carbon alcohol by selective hydrogenation of carbon dioxide provided by the invention specifically comprises the following steps:
1) Dissolving soluble copper salt in water to obtain copper salt water solution, stirring with organic amine complexing agent for 10-40min, and stirring according to H 2 0:Si0 2 =10-1000, cu (or Cr): si0 2 =0.002-0.2、NaOH：Si0 2 =0.5-10、Al：Si0 2 The aluminum source, the alkali source and the silicon source are added in sequence according to the proportion of 0.05-0.5, and the mixture is fully stirred for 30-300min, so as to obtain initial gel.
2) Adding the initial gel into a high-pressure reaction kettle, carrying out static crystallization for 6-168h, cooling to room temperature, carrying out suction filtration and washing on the product to be neutral, putting into a 50-200 ℃ oven for drying for 12-24h, and then roasting in a muffle furnace at 300-600 ℃ for 2-8h.
3) And (3) placing the roasted sample in the step (2) into 0.1-1mol/L of alkali metal (M) nitrate solution, carrying out ion exchange for 1-60h under the water bath condition of 10-90 ℃, and drying and roasting to obtain the M-molecular sieve catalyst.
The invention provides an application method of a molecular sieve catalyst for preparing low-carbon alcohol by selective hydrogenation of carbon dioxide, which comprises the following steps:
1) Adding 0.1-0.5g of catalyst into a reactor with a constant pressure fixed bed, pretreating the catalyst with hydrogen at 200-400 ℃ for 1h, cooling to room temperature, and then introducing hydrogen and CO 2 Gas, hydrogen and CO 2 The molar ratio of (2) to (5), the total airspeed of (10) to (100) ml/min and the pressure of (0.5) to (4.0) MPa.
2) And heating the reactor to 100-350 ℃ to obtain the product.
3) The product was analyzed by gas chromatography directly connected to a fixed bed.
The M-molecular sieve catalyst provided by the invention has the advantages of higher yield, low cost, direct application, simple preparation process, easy operation and stable structural performance; catalyst in CO 2 The selective hydrogenation reaction shows excellent catalytic activity and higher yield of methanol or ethanol, the service life of the catalyst is longer, the catalyst can be recycled for multiple times, and the catalytic activity is not obviously reduced; the catalytic process is environment-friendly and pollution-free, and can be used for preparing CO 2 The method is widely popularized and applied in the reaction of preparing the low-carbon alcohol by selective hydrogenation. In a word, the invention has higher activity and methanol selectivity, thus having industrial application prospect.
Drawings
FIG. 1 is a diagram showing neutron diffraction and structural analysis of a catalyst prepared according to the present invention.
FIG. 2 is a graph comparing the performance of Cu@FAU catalyst prepared by the invention with that of a conventional typical catalyst.
Description of the embodiments
The present invention will be described in further detail and fully with reference to the following examples.
The specific experimental methods and apparatus referred to in the examples below were either conventional or carried out under conditions recommended by the manufacturer's instructions, and the reagents referred to were commercially available, unless otherwise specified.
Examples
Dissolving a certain amount of soluble copper salt (copper nitrate) in water to obtain copper salt water solution, stirring with organic amine (3-aminopropyl triethoxysilane) complexant for 30min, and stirring according to H 2 0:Si0 2 =20、Cu：Si0 2 =0.08、NaOH：Si0 2 =0.7、Al：Si0 2 The mixture ratio of=0.1 is added with sodium metaaluminate, sodium hydroxide and silica sol in sequence, and the mixture is fully stirred for 100min, so as to obtain initial gel.
Adding the initial gel into a high-pressure reaction kettle, carrying out static crystallization for 100 hours at 100 ℃, cooling to room temperature, carrying out suction filtration and washing on the product to be neutral, putting the product into a 100 ℃ oven for drying for 12 hours, and then roasting the product in a 550 ℃ muffle furnace for 6 hours.
And respectively placing the roasted samples into 1mol/L sodium nitrate (or potassium nitrate) solution, carrying out ion exchange for 12 hours under the water bath condition of 80 ℃, and respectively obtaining a Cu-Na-silicon aluminum molecular sieve (named as Cu-Na-Z) and a Cu-K-silicon aluminum molecular sieve (named as Cu-K-Z) after drying and roasting. Wherein the silicon-aluminum atomic ratio of the catalyst is 12, the mass content of Cu is 3%, and the mass ratio of Cu to alkali metal is 2:1.
The application of the catalyst in the carbon dioxide selective hydrogenation reaction comprises the following steps:
adding 0.2g of catalyst into a reactor with a constant pressure fixed bed, pretreating the catalyst with hydrogen at 300 ℃ for 1h, cooling to room temperature, and then introducing hydrogen and CO 2 Hydrogen and CO 2 The molar ratio of (C) was 3, the total space velocity was 35 ml/min, and the pressure was 3 MPa.
The reaction product is obtained by raising the temperature of the reactor to 250 ℃.
The product was analyzed by gas chromatography. The gas chromatograph is Tianmei 7900 gas chromatograph, and matched with an FID detector, and the model of the capillary chromatographic column is Agilent HP-PLOT Q. The product is separated by adopting temperature programming, and the temperature programming steps are as follows: initial temperature of 60 o C, preserving heat for 3 min, then adding 15 o Heating to 200 deg.C/min o C, preserving heat for 5 min. The conversion rate of the raw materials and the selectivity of the target products are calculated by a normalization method. The results of the catalytic performance evaluation are shown in Table 1:
TABLE 1 influence of different alkali metals on carbon dioxide Selective hydrogenation reactions
Catalyst CO 2 Conversion (mol%) Methanol selectivity (%) Yield of methanol (mmol/g/h)
Cu-Na-Z 11.5 89.5 12.5
Cu-K-Z 9.2 90.3 10.3
The catalytic performance evaluation result shows that: catalyst samples containing different alkali metals M, which CO under the same reaction conditions 2 The conversion rate of Cu-Na-Z system catalyst shows the most excellent catalytic activity in the selective hydrogenation reaction of carbon dioxide, and the yield of methanol is as high as 12.5 mmol/g/h.
In the examples, experiments were performed with chromium nitrate instead of copper nitrate, with the desired results.
Examples
The catalyst used in this example is Cu-Na-Z, the influence of the duration of continuous reaction on the selective hydrogenation activity of Cu-Na-Z catalyst in carbon dioxide is examined, and the evaluation of catalytic performance is shown in Table 2:
TABLE 2 influence of the duration of the continuous reaction on the hydrogenation activity of Cu-Na-Z in carbon dioxide
Duration of continuous reaction CO 2 Conversion (mol%) Methanol selectivity (%) Methanol yield (mmol/g/h)
1 h 11.5 89.5 12.5
5 h 11.6 89.3 12.4
8 h 11.4 89.5 12.3
20 h 11.2 89.4 12.2
40 h 11.4 89.5 12.4
The catalytic performance evaluation result shows that: within a certain time range, CO is increased with the time of continuous reaction 2 The conversion rate of alkyne and the selectivity of methanol can be kept relatively stable, and the catalytic activity is not obviously reduced when the reaction time is 40 hours, which indicates that the catalyst of the Cu-Na-Z system has excellent catalytic stability.

Claims (10)

1. A molecular sieve catalyst for preparing low-carbon alcohol by carbon dioxide selective hydrogenation is characterized in that the catalyst is formed by taking metal Cu or Cr as a main active ingredient, compounding alkali metal and taking a silicon-aluminum molecular sieve as a carrier, wherein the load of the metal Cu or Cr is 0.5-15% of the mass of the catalyst; the alkali metal accounts for 0.8-8% of the mass of the catalyst;
the synthesis method mainly comprises the following steps: the method comprises the steps of taking soluble copper salt (or chromium salt), organic amine complexing agent, alkali source, aluminum source and silicon source as raw materials, performing one-step synthesis through a hydrothermal method, washing a product with water to be neutral, drying, roasting, putting a roasted sample into an alkali metal nitrate solution for ion exchange, and then performing suction filtration, washing, drying and roasting.
2. The catalyst of claim 1, wherein: the loading of the metal active ingredient is 3% of the mass of the catalyst; the mass ratio of the metal active component to the alkali metal is 2:1.
3. The method for preparing the molecular sieve catalyst for preparing low-carbon alcohol by selective hydrogenation of carbon dioxide as claimed in claim 1, which is characterized by comprising the following steps: the method specifically comprises the following steps:
1) Dissolving soluble copper salt or chromium salt in water to obtain copper salt water solution, stirring with organic amine complexing agent for 10-40min, and stirring according to H 2 0:Si0 2 =10-1000, cu or Cr: si0 2 =0.002-0.2、NaOH：Si0 2 =0.5-10、Al：Si0 2 Adding aluminum source, alkali source and silicon source in sequence in a proportion of 0.05-0.5, and stirring for 30-300min to obtain initial gel;
2) Adding the initial gel into a high-pressure reaction kettle, carrying out static crystallization for 6-168h, cooling to room temperature, carrying out suction filtration and washing on the product to be neutral, putting the product into a 50-200 ℃ oven for drying for 12-24h, and then roasting the product in a muffle furnace at 300-600 ℃ for 2-8h;
3) And (3) placing the roasted sample in the step (2) into 0.1-1mol/L alkali metal nitrate solution, carrying out ion exchange for 1-60h under the water bath condition of 10-90 ℃, and drying and roasting to obtain the M-silicon-aluminum molecular sieve catalyst.
4. A method of preparation according to claim 3, characterized in that: the soluble copper salt is copper nitrate or copper acetate; the soluble chromium salt is chromium nitrate.
5. A method of preparation according to claim 3, characterized in that: the organic amine complexing agent is small molecular organic amine and siloxane amine compounds such as ethylenediamine, diethylenetriamine, tetraethylenepentamine and the like; siloxane amine compounds are preferred.
6. A method of preparation according to claim 3, characterized in that: the alkali source is sodium hydroxide; the silicon source is any one of silica sol, tetraethoxysilane, silica aerosol amorphous silica powder or silicate; the aluminum source is any one of aluminum sol, aluminum isopropoxide, meta-aluminate, aluminate and pseudo-boehmite.
7. A method of preparation according to claim 3, characterized in that: the alkali metal is lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium or barium.
8. A method of preparation according to claim 3, characterized in that: the M-silicon aluminum molecular sieve comprises a FAU, MOR, CHA, MFI structure.
9. The method for using the molecular sieve catalyst for preparing low-carbon alcohol by selective hydrogenation of carbon dioxide as claimed in claim 1, which is characterized in that: comprising the following steps:
1) Adding 0.1-0.5g of catalyst into a reactor with a constant pressure fixed bed, pretreating the catalyst with hydrogen at 200-400 ℃ for 1h, cooling to room temperature, and then introducing hydrogen and CO 2 Gas, hydrogen and CO 2 The molar ratio of (2) to (5), the total airspeed of (10) to (100) ml/min and the pressure of (0.5) to (4.0) MPa;
2) Heating the reactor to 100-350 ℃ to obtain a product;
3) The product was analyzed by gas chromatography directly connected to a fixed bed.
10. The method of manufacturing according to claim 9, wherein: the lower alcohol is methanol.
CN202310402933.2A 2023-02-09 2023-04-17 Molecular sieve catalyst for preparing low-carbon alcohol by carbon dioxide selective hydrogenation, preparation method and application Pending CN116713030A (en)

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