CN114797948A - Supported MCM-41 catalyst, preparation method and application - Google Patents

Supported MCM-41 catalyst, preparation method and application Download PDF

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CN114797948A
CN114797948A CN202210608123.8A CN202210608123A CN114797948A CN 114797948 A CN114797948 A CN 114797948A CN 202210608123 A CN202210608123 A CN 202210608123A CN 114797948 A CN114797948 A CN 114797948A
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catalyst
metal chloride
molecular sieve
gluconic acid
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CN114797948B (en
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万辉
邹鹏程
王磊
管国锋
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Nanjing Tech 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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0333—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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • 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
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • 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
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/044—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
    • 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
    • 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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Abstract

The invention relates to a supported MCM-41 catalyst, a preparation method and application thereof, which are characterized in that a gluconic acid modified MCM-41 molecular sieve is used as a carrier, a transition metal chloride is used as a main active component, and an alkali metal chloride is used as an auxiliary active component. Wherein the transition metal chloride is FeCl 3 、CoCl 2 、NiCl 2 、CuCl 2 Or ZnCl 2 The alkali metal chloride is one of KCl, LiCl or NaCl; the load mass of the transition metal chloride accounts for 10-25% of the total mass of the catalyst, and the load mass of the alkali metal chloride accounts for 2-5% of the total mass of the catalyst. The supported MCM-41 catalyst has high dispersity and high activity, and can simultaneously activate the catalyst AThe alkane is co-converted with carbon dioxide to acetic acid. The catalyst has the characteristics of simple preparation process, low cost, high catalytic activity and the like, and has good industrial application prospect.

Description

Supported MCM-41 catalyst, preparation method and application
Technical Field
The invention belongs to the field of catalysis, and relates to a supported MCM-41 catalyst, a preparation method and application thereof. The method comprises the modification of a carrier and the loading of an active component, and can be used for catalyzing the direct synthesis of acetic acid from methane and carbon dioxide.
Background
Acetic acid is one of important organic acids as a bulk chemical, and is widely applied to industries such as food, medicine, pesticide and the like. The production of acetic acid can adopt artificial synthesis methods and bacterial fermentation methods, wherein the artificial synthesis methods comprise a methanol carbonylation method, an acetaldehyde oxidation method, an ethylene oxidation method and the like, and the bacterial fermentation methods comprise an aerobic fermentation method and an anaerobic fermentation method. The production of acetic acid is mainly carried out by methanol carbonylation method, wherein methanol is used as raw material, methyl iodide is used as intermediate, acetic acid is synthesized by three steps, but the commonly used catalyst is noble metal catalyst, and the economic cost is high.
CH 4 And CO 2 The direct conversion into acetic acid is an atom economic reaction, completely meets the requirement of green chemistry, and shortens the process flow of producing the acetic acid. However, both are very stable substances and the reaction is difficult to proceed thermodynamically. It was found that ZrO 2 /SO 4 2- Can activate methane and promote C-C coupling, the higher the acid strength, the easier the activation of methane, but the lower the specific surface area and the poorer the activity [ New Journal of Chemistry,2021,45(20):8978-]. Cu-based catalysts are effective in activating methane, but tend to agglomerate at high temperatures, leading to catalyst deactivation [ Applied Catalysis B: Environmental,2017,215: 50-59]. Emad N.Al-Shafei ZrO 2 /TiO 2 The catalyst successfully synthesized acetic acid, but the reaction temperature was too high and the yield of acetic acid was low [ Chemical Engineering Journal,2021,419:129416 ]]. Therefore, it is very important to design a high-efficiency catalyst for catalyzing the synthesis of acetic acid from methane and carbon dioxide.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a supported MCM-41 catalyst, and the invention also aims to provide a preparation method of the catalyst and application of the catalyst in catalyzing direct synthesis of acetic acid from methane and carbon dioxide.
In order to achieve the purpose, the invention adopts the technical scheme that:
a supported MCM-41 catalyst features that the gluconic acid modified MCM-41 molecular sieve is used as carrier, the chloride of transition metal is used as main active component, and alkali gold is used as catalystThe metal chloride is taken as an auxiliary active component; wherein the transition metal chloride is FeCl 3 、CoCl 2 、NiCl 2 、CuCl 2 Or ZnCl 2 The alkali metal chloride is one of KCl, LiCl or NaCl; the load mass of the transition metal chloride accounts for 10-25% of the total mass of the catalyst, and the load mass of the alkali metal chloride accounts for 2-5% of the total mass of the catalyst.
The invention also provides a preparation method of the supported MCM-41 catalyst, which comprises the following steps:
the method comprises the following steps: preparing a modified MCM-41 molecular sieve:
pouring the MCM-41 molecular sieve into a gluconic acid solution, stirring for 5-12h at 50-80 ℃, and then centrifuging and drying to obtain a gluconic acid modified MCM-41 molecular sieve; the mass ratio of the gluconic acid solution to the MCM-41 molecular sieve is (30-50) to 1; the molar concentration of the gluconic acid solution is 0.5-3.0 mol/L;
step two: preparation of a supported MCM-41 catalyst:
firstly, placing a modified MCM-41 molecular sieve in a container, then weighing a transition metal chloride and an alkali metal chloride, dissolving in ethanol, stirring until the transition metal chloride and the alkali metal chloride are dissolved to form an ethanol solution, then adding the ethanol solution into a gluconic acid modified MCM-41 molecular sieve, stirring and ultrasonically mixing until the ethanol solution is uniformly mixed, standing for 5-12h, then drying, and placing the mixture in a tubular furnace to be roasted in a protective atmosphere to obtain the supported MCM-41 catalyst.
Based on the technical scheme, preferably, the drying temperature in the step one is 80-120 ℃, and the drying time is 8-12 h.
Based on the technical scheme, preferably, the drying temperature in the step two is 80-100 ℃, and the drying time is 8-12 h; the roasting temperature is 450-500 ℃, the roasting time is 1-3h, and the heating rate is 2-5 ℃/min; the protective atmosphere is one of argon, nitrogen or helium.
The invention also provides an application of the supported MCM-41 catalyst in direct synthesis of acetic acid from methane and carbon dioxide, which comprises the following specific steps: and (3) loading the catalyst into a reaction tube, heating to the reaction temperature under the condition of nitrogen, and introducing raw material gas to perform catalytic reaction.
Preferred above-mentioned feed gas CH 4 With CO 2 The volume ratio is 1 (1-10); the volume space velocity is 360-1200h -1 (ii) a Under the condition of nitrogen, the temperature is 2-5 ℃/min -1 The temperature is raised to the reaction temperature which is 400-450 ℃.
Has the advantages that:
(1) the invention utilizes the gluconic acid to modify the MCM-41 molecular sieve, increases the hydroxyl on the surface of the MCM-41 molecular sieve, and can stabilize the active component and prevent the active component from agglomerating.
(2) The invention has high activity when used for directly synthesizing acetic acid by methane and carbon dioxide.
(3) The preparation method is simple, low in cost and convenient to amplify.
Detailed Description
The present invention is described in more detail by the following examples, which should be construed as merely illustrative and explanatory of the present invention and not limitative of the scope thereof.
Example 1
The method comprises the following steps: preparing a modified MCM-41 molecular sieve:
pouring 5g of MCM-41 molecular sieve into 150g of 0.5mol/L gluconic acid solution, stirring for 5h at 50 ℃, then centrifuging, and drying for 8h at 80 ℃ to obtain the gluconic acid modified MCM-41 molecular sieve.
Step two: preparing a modified MCM-41 molecular sieve loaded active component:
firstly, 1g of modified MCM-41 molecular sieve is placed in a container, and 0.1136g of FeCl is weighed 3 Dissolving 0.0227g of KCl in ethanol, stirring until the KCl is dissolved to form an ethanol solution, adding the ethanol solution into a gluconic acid modified MCM-41 molecular sieve, stirring and ultrasonically mixing until the mixture is uniform, standing for 5 hours, then drying for 8 hours at 80 ℃, placing the mixture in a tubular furnace, raising the temperature to 450 ℃ at the rate of 2 ℃/min, and roasting for 1 hour in the argon atmosphere to obtain 10% FeCl 3 -2% KCl/MCM-41 catalyst.
Example 2
The method comprises the following steps: preparing a modified MCM-41 molecular sieve:
pouring 5g of MCM-41 molecular sieve into 150g of 0.5mol/L gluconic acid solution, stirring for 8h at the temperature of 60 ℃, centrifuging, and drying for 9h at the temperature of 100 ℃ to obtain the gluconic acid modified MCM-41 molecular sieve.
Step two: preparing a modified MCM-41 molecular sieve loaded active component:
first, 1g of modified MCM-41 molecular sieve was placed in a container, and then 0.1136g of CoCl was weighed 2 Dissolving 0.0227g of KCl in ethanol, stirring until the mixture is dissolved to form an ethanol solution, adding the ethanol solution into a gluconic acid modified MCM-41 molecular sieve, stirring and ultrasonically mixing until the mixture is uniform, standing for 8 hours, drying for 8 hours at 90 ℃, placing the mixture in a tube furnace, raising the temperature to 460 ℃ at the rate of 3 ℃/min, and roasting for 1 hour in a nitrogen atmosphere to obtain 10% CoCl 2 -2% KCl/MCM-41 catalyst.
Example 3
The method comprises the following steps: preparing a modified MCM-41 molecular sieve:
pouring 5g of MCM-41 molecular sieve into 150g of 0.5mol/L gluconic acid solution, stirring for 10h at 70 ℃, centrifuging, and drying for 10h at 120 ℃ to obtain the gluconic acid modified MCM-41 molecular sieve.
Step two: preparing a modified MCM-41 molecular sieve loaded active component:
firstly, 1g of modified MCM-41 molecular sieve is placed in a container, and 0.1136g of NiCl is weighed 2 Dissolving 0.0227g of KCl in ethanol, stirring until the KCl is dissolved to form an ethanol solution, adding the ethanol solution into a gluconic acid modified MCM-41 molecular sieve, stirring and ultrasonically mixing until the mixture is uniform, standing for 10 hours, then drying for 10 hours at 90 ℃, putting the mixture in a tube furnace, raising the temperature to 470 ℃ at the rate of 4 ℃/min, and roasting for 1 hour in a nitrogen atmosphere to obtain 10% NiCl 2 -2% KCl/MCM-41 catalyst.
Example 4
The method comprises the following steps: preparing a modified MCM-41 molecular sieve:
pouring 5g of MCM-41 molecular sieve into 200g of 1.0mol/L gluconic acid solution, stirring for 12h at 80 ℃, centrifuging, and drying for 12h at 90 ℃ to obtain the gluconic acid modified MCM-41 molecular sieve.
Step two: preparing a modified MCM-41 molecular sieve loaded active component:
firstly, 1g of modified MCM-41 molecular sieve is placed in a container, and 0.1136g of CuCl is weighed 2 Dissolving 0.0227g of KCl in ethanol, stirring until the mixture is dissolved to form an ethanol solution, adding the ethanol solution into a gluconic acid modified MCM-41 molecular sieve, stirring and ultrasonically mixing until the mixture is uniform, standing for 12 hours, drying for 11 hours at 100 ℃, placing the mixture in a tubular furnace, raising the temperature to 480 ℃ at the rate of 5 ℃/min, and roasting for 1 hour in a helium atmosphere to obtain 10% CuCl 2 -2% KCl/MCM-41 catalyst.
Example 5
The method comprises the following steps: preparing a modified MCM-41 molecular sieve:
pouring 5g of MCM-41 molecular sieve into 200g of 2.0mol/L gluconic acid solution, stirring for 12h at 80 ℃, centrifuging, and drying for 12h at 80 ℃ to obtain the gluconic acid modified MCM-41 molecular sieve.
Step two: preparing a modified MCM-41 molecular sieve loaded active component:
firstly, 1g of modified MCM-41 molecular sieve is placed in a container, and 0.1136g of ZnCl is weighed 2 Dissolving 0.0227g of KCl in ethanol, stirring until the mixture is dissolved to form an ethanol solution, adding the ethanol solution into a gluconic acid modified MCM-41 molecular sieve, stirring and ultrasonically mixing until the mixture is uniform, standing for 12 hours, drying for 12 hours at 100 ℃, placing the mixture in a tube furnace, raising the temperature to 490 ℃ at the rate of 5 ℃/min, and roasting for 1 hour in a nitrogen atmosphere to obtain 10% ZnCl 2 -2% KCl/MCM-41 catalyst.
Example 6
The method comprises the following steps: preparing a modified MCM-41 molecular sieve:
pouring 5g of MCM-41 molecular sieve into 250g of 3.0mol/L gluconic acid solution, stirring for 12h at 80 ℃, then centrifuging, and drying for 12h at 80 ℃ to obtain the gluconic acid modified MCM-41 molecular sieve.
Step two: preparing a modified MCM-41 molecular sieve loaded active component:
firstly, 1g of modified MCM-41 molecular sieve is placed in a containerThen 0.1829g of ZnCl were weighed 2 Dissolving 0.0365g of LiCl in ethanol, stirring until the LiCl is dissolved to form an ethanol solution, adding the ethanol solution into a gluconic acid modified MCM-41 molecular sieve, stirring and ultrasonically mixing until the mixture is uniform, standing for 12h, then drying for 12h at 100 ℃, putting the mixture in a tubular furnace, raising the temperature to 500 ℃ at the rate of 5 ℃/min, and roasting for 1h in a nitrogen atmosphere to obtain 15% ZnCl 2 -3% LiCl/MCM-41 catalyst.
Example 7
The method comprises the following steps: preparing a modified MCM-41 molecular sieve:
pouring 5g of MCM-41 molecular sieve into 250g of 3.0mol/L gluconic acid solution, stirring for 12h at 80 ℃, then centrifuging, and drying for 12h at 80 ℃ to obtain the gluconic acid modified MCM-41 molecular sieve.
Step two: preparing a modified MCM-41 molecular sieve loaded active component:
firstly, 1g of modified MCM-41 molecular sieve is placed in a container, and 0.2630g of ZnCl is weighed 2 And 0.0526g of NaCl is dissolved in ethanol, the mixture is stirred until the mixture is dissolved to form an ethanol solution, then the ethanol solution is added into a gluconic acid modified MCM-41 molecular sieve, the mixture is stirred and ultrasonically treated until the mixture is uniformly mixed, the mixture is kept stand for 12 hours, then the mixture is dried for 12 hours at the temperature of 100 ℃, the dried mixture is placed in a tube furnace, the temperature is increased to 500 ℃ at the heating rate of 5 ℃/min, and the mixture is roasted for 2 hours in the nitrogen atmosphere to obtain 20 percent ZnCl 2 4% NaCl/MCM-41 catalyst.
Example 8
The method comprises the following steps: preparing a modified MCM-41 molecular sieve:
pouring 5g of MCM-41 molecular sieve into 250g of 3.0mol/L gluconic acid solution, stirring for 12h at 80 ℃, then centrifuging, and drying for 12h at 80 ℃ to obtain the gluconic acid modified MCM-41 molecular sieve.
Step two: preparing a modified MCM-41 molecular sieve loaded active component:
firstly, 1g of modified MCM-41 molecular sieve is placed in a container, and 0.3567g of ZnCl is weighed 2 Dissolving 0.0701g of KCl in ethanol, stirring to dissolve to form ethanol solution, adding the ethanol solution into the gluconic acid modified MCM-41 molecular sieve, and stirring and ultrasonically mixing until the mixture is uniformly mixedStanding for 12h, drying at 100 deg.C for 12h, placing in a tube furnace, heating to 500 deg.C at a rate of 5 deg.C/min, and calcining in nitrogen atmosphere for 3h to obtain 25% ZnCl 2 -5% KCl/MCM-41 catalyst.
The supported MCM-41 catalyst is used for catalyzing methane and carbon dioxide to directly synthesize acetic acid:
application example 1
0.1g of 10% FeCl as in example 1 was weighed out 3 -2% KCl/MCM-41 catalyst was loaded into a quartz reaction tube and then placed under nitrogen at 2 ℃/min -1 The temperature is raised to 400 ℃ at the rate of (2), and the volume space velocity of methane and carbon dioxide is 360h -1 Of the feed gas CH 4 ：CO 2 The volume ratio is 1: 1.
Application example 2
0.1g of 10% CoCl as in example 2 was weighed out 2 -2% KCl/MCM-41 catalyst was loaded into a quartz reaction tube and then placed under nitrogen at 2 ℃/min -1 The rate of (A) is increased to the reaction temperature of 410 ℃, and the volume space velocity of methane and carbon dioxide is 720h -1 Of the feed gas CH 4 ：CO 2 The volume ratio is 1: 1.
Application example 3
0.1g of 10% NiCl from example 3 was weighed out 2 -2% KCl/MCM-41 catalyst was loaded into a quartz reaction tube and then at 3 ℃/min under nitrogen -1 The temperature is raised to the reaction temperature of 420 ℃, and the volume space velocity of methane and carbon dioxide is 1000h -1 Of the feed gas CH 4 ：CO 2 The volume ratio is 1: 1.
Application example 4
0.1g of 10% CuCl as in example 4 was weighed out 2 -2% KCl/MCM-41 catalyst was loaded into a quartz reaction tube and then at 3 ℃/min under nitrogen -1 The temperature is raised to 430 ℃ at the rate of (1), and the volume space velocity of methane and carbon dioxide is 1200h -1 Of the feed gas CH 4 ：CO 2 The volume ratio is 1: 1.
Application example 5
0.1g of 10% ZnCl from example 5 was weighed 2 -2% KCl/MCM-41 catalyst was loaded into a quartz reaction tube and then at 4 ℃/min under nitrogen -1 The temperature is raised to 440 ℃ and the volume space velocity of methane and carbon dioxide is 720h -1 Of the feed gas CH 4 ：CO 2 The volume ratio is 1: 2.
Application example 6
0.1g of 15% ZnCl from example 6 was weighed 2 -3% LiCl/MCM-41 catalyst was loaded into a quartz reaction tube and then at 4 ℃/min under nitrogen conditions -1 The temperature is raised to 450 ℃ at the speed rate, and the volume space velocity of methane and carbon dioxide is 1200h -1 Of the feed gas CH 4 ：CO 2 The volume ratio is 1: 5.
Application example 7
0.1g of 20% ZnCl from example 7 was weighed 2 Loading-4% NaCl/MCM-41 catalyst into quartz reaction tube, and then loading at 5 deg.C/min under nitrogen condition -1 The temperature is raised to 450 ℃ at the speed rate, and the volume space velocity of methane and carbon dioxide is 1200h -1 Of the feed gas CH 4 ：CO 2 The volume ratio is 1: 10.
Application example 8
0.1g of 25% ZnCl from example 8 was weighed 2 -5% KCl/MCM-41 catalyst was loaded into a quartz reaction tube and then placed under nitrogen at 5 ℃/min -1 The temperature is raised to 450 ℃ at the speed rate, and the volume space velocity of methane and carbon dioxide is 1200h -1 Of the feed gas CH 4 ：CO 2 The volume ratio is 1: 1.
The test shows that the catalytic performance of the supported MCM-41 catalyst for directly synthesizing acetic acid from methane and carbon dioxide is shown in Table 1.
TABLE 1 catalysis performance of different catalysts for synthesis of acetic acid from methane and carbon dioxide
Selectivity/%) Acetic acid formation Rate/(μmol. g) -1 ·h -1 )
Application example 1 91.2 250.23
Application example 2 89.3 255.64
Application example 3 90.7 258.08
Application example 4 88.6 242.12
Application example 5 94.4 377.56
Application example 6 96.3 407.47
Application example 7 95.7 445.12
Application example 8 96.8 492.33

Claims (7)

1. A load type MCM-41 catalyst is characterized in that a gluconic acid modified MCM-41 molecular sieve is used as a carrier, a transition metal chloride is used as a main active component, and an alkali metal chloride is used as an auxiliary active component; wherein the transition metal chloride is FeCl 3 、CoCl 2 、NiCl 2 、CuCl 2 Or ZnCl 2 The alkali metal chloride is one of KCl, LiCl or NaCl; the load mass of the transition metal chloride accounts for 10-25% of the total mass of the catalyst, and the load mass of the alkali metal chloride accounts for 2-5% of the total mass of the catalyst.
2. A process for preparing a supported MCM-41 catalyst according to claim 1, comprising the specific steps of:
the method comprises the following steps: preparing a modified MCM-41 molecular sieve:
pouring the MCM-41 molecular sieve into a gluconic acid solution, stirring for 5-12h at 50-80 ℃, and then centrifuging and drying to obtain a gluconic acid modified MCM-41 molecular sieve; the mass ratio of the gluconic acid solution to the MCM-41 molecular sieve is (30-50) to 1; the molar concentration of the gluconic acid solution is 0.5-3.0 mol/L;
step two: preparation of a supported MCM-41 catalyst:
firstly, placing a modified MCM-41 molecular sieve in a container, weighing transition metal chloride and alkali metal chloride, dissolving the transition metal chloride and the alkali metal chloride in ethanol, stirring until the transition metal chloride and the alkali metal chloride are dissolved to form an ethanol solution, then adding the ethanol solution into a gluconic acid modified MCM-41 molecular sieve, stirring and ultrasonically mixing until the ethanol solution is uniformly mixed, standing for 5-12h, then drying, and placing the mixture in a tubular furnace to be roasted in a protective atmosphere to obtain the supported MCM-41 catalyst.
3. The method according to claim 2, wherein the drying temperature in the first step is 80-120 ℃ and the drying time is 8-12 h.
4. The method according to claim 2, wherein the drying temperature in the second step is 80-100 ℃, and the drying time is 8-12 h; the roasting temperature is 450-500 ℃, and the roasting time is 1-3 h; the heating rate is 2-5 ℃/min; the protective atmosphere is one of argon, nitrogen or helium.
5. Use of a supported MCM-41 catalyst of claim 1 in the direct synthesis of acetic acid from methane and carbon dioxide.
6. The use of claim 5, wherein the catalytic reaction is carried out in a fixed bed reactor by first charging the catalyst into a reaction tube, then raising the temperature to the reaction temperature under nitrogen, and introducing the feed gas to carry out the catalytic reaction.
7. Use according to claim 6, characterised in that the feed gas CH 4 With CO 2 The volume ratio is 1 (1-10), the volume space velocity is 360- -1 Under the condition of nitrogen, at the speed of 2-5 ℃/min -1 The temperature is raised to the reaction temperature which is 400-450 ℃.
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