CN113941329B

CN113941329B - Preparation method and application of catalyst for preparing acetic acid and acetic ester through halogen-free gas-phase carbonylation of methanol

Info

Publication number: CN113941329B
Application number: CN202010686820.6A
Authority: CN
Inventors: 丁云杰; 袁乔; 宋宪根; 冯四全
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2020-07-16
Filing date: 2020-07-16
Publication date: 2022-12-23
Anticipated expiration: 2040-07-16
Also published as: CN113941329A

Abstract

A preparation method and application of a catalyst for preparing acetic acid and acetic ester by halogen-free gas-phase carbonylation of methanol. The catalyst consists of three parts of a main catalyst, a cocatalyst and a carrier. The invention provides a catalyst for preparing acetic acid and acetic ester by halogen-free gas-phase carbonylation of methanol, which consists of one kind of oxides of Re, W, mn, ti and the like which are dispersed in a single point and one kind of Rh or Ir which is dispersed in a single atom. The catalyst is used in a fixed bed reactor, and under the action of certain temperature and pressure and the catalyst, CH ₃ OH and CO can be converted into acetic acid and acetic ester with high activity and high selectivity.

Description

Preparation method and application of catalyst for preparing acetic acid and acetic ester through halogen-free gas-phase carbonylation of methanol

Technical Field

The invention belongs to the technical field of chemical engineering catalysts, and particularly relates to preparation of a catalyst of a single-point dispersed oxide of Re, W, mn and Ti and a catalyst of monoatomic dispersed Rh and Ir which are loaded on an inert carrier, and application of the catalyst in preparation of acetic acid and acetic ester by halogen-free gas-phase carbonylation of methanol.

Background

Acetic acid is a very important organic chemical raw material, has very wide application, can be used for producing various subsequent chemical products such as vinyl acetate monomers, acid anhydride, terephthalic acid, acetic ester, acetate fibers and the like, and particularly, the production of the acetic acid becomes an important component of the chemical field and the national economy along with the rapid development of the downstream products of the terephthalic acid and the acetic acid.

Mature acetic acid production processes include the acetylene acetaldehyde process, the ethylene acetaldehyde process, the ethanol acetaldehyde process, the butane oxidation process, and the methanol carbonylation process. Among them, the methanol carbonylation process is dominant, and the production capacity of the current acetic acid production device adopting the process accounts for 81 percent of the total production capacity of acetic acid. The industrial process for the carbonylation of methanol to produce acetic acid has gone through roughly three stages of development over the past 50 years:

the first stage is as follows: the industrial production of acetic acid by methanol carbonylation was first achieved in 1960 by BSAF using cobalt catalysts at higher reaction temperatures and pressures (250 ℃,60 MPa). The acetic acid produced by the method has low purity, the main byproducts are higher alcohol, higher aldehyde and higher carboxylic acid, and the product separation cost is higher. And a second stage: the company Monsanto developed rhodium-iodides (RhI) with higher activity and selectivity ₃ ) A catalytic system. The reaction temperature and pressure are also relatively low (about 175 ℃,3.0 MPa), the selectivity of acetic acid based on methanol is more than 99%, and the selectivity based on CO is more than 90%. The corrosion resistance of the device is very high, and a full zirconium alloy reaction kettle is needed. And a third stage: the industrialization of Ir catalyst is the production of acetic acid by methanol carbonylation. The process greatly improves the stability of the catalyst, the reaction is carried out under the condition of lower water content, the generation of liquid by-products is reduced, and the conversion rate of CO is improved. Celanese chemical company adds high-concentration inorganic iodide (mainly lithium iodide), improves the stability of Rh catalyst, and after adding lithium iodide and methyl iodide auxiliary agent, the water content in the reactor can be obviously reduced (about 4-5%), and simultaneously higher carbonylation rate can be maintained, and the separation cost of the new process is obviously reduced.

The company Chiyoda, japan, and UOP jointly developed an actica process based on a heterogeneous Rh catalyst in which an active Rh complex is supported on a polyvinylpyridine resin. The strong and weak coordinate bond chelating high molecular catalyst researched and combined by Yuan Guoqing of the institute of chemistry of Chinese academy of sciences also forms an independent intellectual property system, and the catalyst system has the characteristics of high stability, high activity and the like and can improve the selectivity of CO utilization.

Although homogeneous Rh-based and Ir-based catalytic systems have quite high catalytic activity and selectivity, the selectivity of acetic acid is more than 99 percent, and good industrial application is achieved. However, homogeneous catalyst systems have many disadvantages, such as high loss of precious metal catalyst, difficult separation of product from catalyst, and complex catalyst recycling and recovery.

In view of the above insufficiency of homogeneous phase catalytic systems, some researchers have focused on supported heterogeneous catalytic systems, but the supported catalyst systems have the problems of lower activity than the homogeneous catalytic systems, easy removal of active components, higher requirements for carriers, and the like. Most importantly, the methanol carbonylation system needs to be carried out in the presence of a halogen additive (such as methyl iodide), which causes serious corrosion of equipment, hastelloy or zirconium material equipment needs to be adopted, and the investment cost is greatly increased. The development of the methanol halogen-free carbonylation system can avoid the corrosion of reaction media and reduce the investment cost of equipment, and has important industrial significance. Halogen-free methanol carbonylation first addresses the problem of methanol activation. In the molecular sieve system, the acidic sites in the MOR molecular sieve promote methanol to be coupled first to form dimethyl ether, and the dimethyl ether is carbonylated to form methyl acetate. However, due to the poor hydrothermal stability of molecular sieves, the direct carbonylation of dimethyl ether to produce methyl acetate has generally been studied. Even if dimethyl ether containing no water is directly used, the problem of carbon deposition of a molecular sieve in the carbonylation process is still serious, and the molar ratio of CO/dimethyl ether is required to be very high and can reach 50. Severely reducing CO conversion and increasing cycle energy consumption. The literature reports that spatially separated methanol adsorption and activation of active sites can avoid the formation of dimethyl ether. Therefore, the single-point dispersed acid sites loaded on the inert carrier can reduce the coupling of two molecules of methanol on the surface to the maximum extent, inhibit the generation of dimethyl ether and promote the generation of methyl acetate in the carbonylation reaction process of the surface methoxy species. The inert carrier with high specific surface area and large pore diameter is selected, so that the problems of carbon deposition, internal diffusion, unstable carrier hydrothermal property and the like in the molecular sieve carrier can be avoided. The rate-controlled step of acid-catalyzed carbonylation is mostly CO insertion, while the monodisperse Rh and Ir atoms possess strong CO insertion ability, but their ability to activate methanol to form methyl or methoxy groups is poor.

Therefore, a proper amount of Rh and Ir monatomic catalyst with better carbonylation activity is loaded at the same time, the interaction between the single-point dispersed acidic site and Rh and Ir monatomic is strengthened, and the reaction rate can be greatly improved. Here we propose a catalyst of mono-disperse oxides of Re, W, mn, ti and mono-disperse Rh and Ir supported on an inert carrier for the halogen-free carbonylation of methanol to produce acetic acid and acetate. The catalyst has the advantages of high activity, high selectivity, good stability and the like. Meanwhile, the equipment investment cost of the process can be reduced, and the method is environment-friendly and has wide industrial application prospect.

Disclosure of Invention

The invention aims to provide a double-component catalyst of single-point dispersed oxides of Re, W, mn and Ti and monoatomic dispersed Rh or Ir loaded on an inert carrier and application thereof in preparing acetic acid and acetic ester by halogen-free methanol carbonylation.

The technical scheme of the invention is as follows:

a supported catalyst for preparing acetic acid and acetic ester by halogen-free gas-phase carbonylation of methanol. The catalyst consists of inert carrier, one kind of oxide of main catalyst Re, W, mn and Ti and one kind of co-catalyst Rh or Ir.

The inert carrier is one of alumina, silicon oxide, active carbon, zirconia and silicon carbide. The compound of the main catalyst mainly comprises perrhenic acid (HReO) ₄ ) Ammonium perrhenate (NH) ₄ ReO ₄ ) Rhenium pentachloride (Recl) ₅ ) Rhenium oxide (Re) ₂ O ₇ ) Tungstic acid (H) ₂ WO ₄ ) Ammonium tungstate [ (NH) ₄ ) ₁₀ W ₁₂ O ₄₁ ]Tungsten hexachloride (WCl) ₆ ) Tungsten pentachloride (WCl) ₅ ) Potassium permanganate (KMnO) ₄ ) Manganese tetrachloride (MnCl) ₄ ) Titanic acid (H) ₄ TiO ₄ ) Ethyl titanate (C) ₈ H ₂₀ O ₄ Ti), titanium tetrachloride (TiCl) ₄ ) And the like. Preferred HReO ₄ 、H ₂ WO ₄ 、KMnO ₄ 、H ₄ TiO ₄ One kind of (1). The mass loading of the catalyst is 0.01-15.0%, preferably 1.0-10.0%.

The compounds of the cocatalyst Rh and Ir are conventionalTransition metal compounds, including oxides, hydroxides, sulfides, chlorides, etc., such as rhodium nanometal (Rh), rhodium oxide (Rh) ₂ O ₃ 、RhO ₂ ) Rhodium acetylacetonate carbonyl (Rh (acac) (CO) ₂ ) Dichlorotetracarbonyldirhodium (Rh) ₂ (CO) ₄ Cl ₂ ) And rhodium trichloride (RhCl) ₃ ) Iridium oxide (Ir) ₂ O ₃ 、IrO ₂ ) Iridium hydroxide (Ir (OH) ₃ 、Ir(OH) ₄ ) Chloro iridic acid (H) ₂ IrCl ₆ ) And iridium chloride (IrCl) ₃ 、IrCl ₄ ) Etc., preferably Rh (acac) (CO) ₂ 、RhCl ₃ 、H ₂ IrCl ₆ 、IrCl ₃ One kind of (1). The mass loading of the rhodium Rh or Ir in the catalyst is 0.01 to 2.0%, preferably 0.05 to 1%.

The preparation method of the supported catalyst comprises the following steps: dissolving precursor compounds of main catalysts Re, W, mn, ti and the like in ultrapure water, adding a proper amount of arginine or triethanolamine or other complexing agents, and adding precursor compounds of co-catalysts rhodium or iridium to obtain an impregnation precursor mixed solution. It is then slowly added dropwise to a suspension of ethanol or water-dispersed inert carrier. Then rotary steaming, drying and roasting, namely roasting and oxidizing for 1-2 h at the high temperature of 300-600 ℃ in the oxygen atmosphere to obtain the catalyst. The oxygen atmosphere is oxygen or oxygen mixed with inert atmosphere gas, and the volume concentration of the oxygen in the oxygen atmosphere is more than 20%, preferably more than 50%, and most preferably more than 80%; the inert atmosphere gas is He, ar, N ₂ One or more than two of them.

The catalyst of one of rhenium, tungsten, manganese and titanium and one of rhodium or iridium metal loaded by the inert carrier is mainly used for preparing acetic acid and acetate by halogen-free gas-phase carbonylation of methanol, the reaction temperature is 150-300 ℃, the reaction pressure is 0.1-3.5 MPa, and the liquid volume space velocity of the methanol is 0.1-15h ^-1 CO and CH ₃ The molar ratio of OH is 0.25-10. The main products of the reaction are acetic acid and acetic ester, and a small amount of dimethyl ether by-product is generated.

Before the reaction, in-situ low-temperature hydrogen reduction is needed, the temperature is 100-300 ℃, preferably 100-200 ℃, and the reduction time isIs 0.5 to 2.0 hours. The reducing atmosphere is hydrogen or hydrogen and inert atmosphere gas, and the volume concentration of the hydrogen in the reducing atmosphere is more than 20%, preferably more than 50%, and most preferably more than 80%; the inert atmosphere gas is He, ar, N ₂ One or more than two of them.

The invention has the beneficial effects that:

compared with the existing methanol carbonylation metal catalysis technology, the catalyst provided by the invention has the advantages of simple preparation method, no need of Hastelloy or zirconium material reactor, high activity and selectivity, good stability and the like, and is applied to the methanol halogen-free gas-phase carbonylation reaction.

In addition, the preparation of the catalyst which is loaded by the inert carrier and consists of one of oxides of Re, W, mn, ti and the like which are dispersed in a single point and one of Rh or Ir which are dispersed in a single atom and the application of the catalyst in the heterogeneous carbonylation of methanol are different from the methanol carbonylation process in which the prior halohydrocarbon cocatalyst participates, and the catalyst is a brand new methanol carbonylation catalyst system. The main catalyst in the catalyst is oxides of single-point dispersed Re and the like as Lewis acid sites and can well activate methanol, and the cocatalyst Rh or Ir in the catalyst can adsorb and activate CO and realize quick insertion of CO, so that the efficiency of halogen-free carbonylation of methanol is improved, the corrosion problem in the process of carbonylation of methanol for a long time is avoided, the equipment investment cost is greatly reduced, and the catalyst has an industrial prospect.

Drawings

FIG. 1 shows example 9Re-Rh/SiO ₂ Catalyst X-ray diffraction (XRD) pattern;

FIG. 2 shows example 9Re-Rh/SiO ₂ Catalyst Transmission Electron Microscopy (TEM) pictures with Re, rh, si and O mapping.

The figures discuss: to demonstrate the bicomponent metal single site and monoatomic dispersion of the catalysts described herein, re-Rh/SiO prepared as described in example 9 below was used ₂ The catalyst was characterized by XRD and TEM. As shown in FIG. 1, with SiO ₂ XRD spectrum comparison, re/SiO ₂ And Re-Rh/SiO ₂ No peaks of metal Re and Rh are found in both XRD spectrograms, and only one SiO carrier is present ₂ Typically broad peak. Thus, re-R can be illustratedh/SiO ₂ The metal on the catalyst does not agglomerate and may be present in a single-site or monoatomic dispersion. As shown in FIG. 2, re-Rh/SiO ₂ The high-resolution TEM photograph of the catalyst does not show metal clusters, and the mapping picture thereof shows a high degree of dispersion of both Re and Rh, and thus it can be presumed that both are single-site and monoatomic.

Detailed Description

The following examples illustrate but do not limit the invention claimed.

To compare the superiority of the catalyst of the invention in halogen-free carbonylation of methanol with rhenium or other rhodium or iridium, the following specific examples were carried out using different inert carrier-supported active metals rhenium or other rhodium, iridium bicomponent M ₁ -M ₂ catalyst/S (where M is ₁ Represents a metal such as Re, W, mn and Ti, M ₂ Rh and Ir metal, S Al ₂ O ₃ 、SiO ₂ 、AC、ZrO ₂ Inert carriers such as SiC, M in the following examples ₁ The mass content of the metal is 5.0 percent and M ₂ The mass content of the metal is 0.2%). Re-Rh/Al ₂ O ₃ Is a rhenium-rhodium catalyst supported on alumina in accordance with the present invention; in the same way, W-Rh/Al ₂ O ₃ Is an alumina-supported tungsten-rhodium catalyst of the present invention; mn-Rh/Al ₂ O ₃ Is an alumina-supported manganese-rhodium catalyst of the present invention; ti-Rh/Al ₂ O ₃ Is a titanium-rhodium catalyst supported on alumina in the present invention; re-Ir/Al ₂ O ₃ Is a rhenium-iridium catalyst supported on alumina in the present invention; W-Ir/Al ₂ O ₃ Is an alumina-supported tungsten-iridium catalyst in the present invention; mn-Ir/Al ₂ O ₃ Is an alumina-supported manganese-iridium catalyst of the present invention; ti-Ir/Al ₂ O ₃ Is a titanium-iridium catalyst supported on alumina in the present invention; other carrier supported active metal rhenium-rhodium iridium bi-component catalyst is expressed in the same manner. At the same time, with Re-Rh/SiO ₂ Taking the catalyst as an example, respectively preparing Re-Rh/SiO under the conditions of different metal precursors, dispersants, oxidation temperatures, different metal loading amounts and the like ₂ (I-XVIII). The preparation method of the catalyst comprises the following steps: a certain massDissolving the precursor compound of rhenium and the like in ultrapure water, adding a proper amount of triethanolamine or other complexing agents, and adding a proper amount of the precursor compound of rhodium or iridium to obtain an impregnation precursor mixed solution. It is then slowly added dropwise to a suspension of ethanol or water-dispersed inert carrier. Then rotary steaming, drying, roasting, and roasting and oxidizing for 1-2 h at high temperature of 200-500 ℃ in oxygen atmosphere to obtain the catalyst of the invention.

Example 1

Re-Rh/Al ₂ O ₃ Preparation of the catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.004067g RhCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9285g Al ₂ O ₃ Carrier (specific surface 560 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/Al ₂ O ₃ A catalyst.

Example 2

W-Rh/Al ₂ O ₃ Preparation of the catalyst: weighing 0.06795g H ₂ WO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9280g Al ₂ O ₃ Carrier (specific surface 560 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 2h, roasting in a muffle furnace at 450 ℃ for 4h, and finally oxidizing in a tubular furnace at 350 ℃ for 1h to obtain W-Rh/Al ₂ O ₃ A catalyst.

Example 3

Mn-Rh/Al ₂ O ₃ Preparation of the catalyst: weighing 0.1438g KMnO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then add into0.004067g RhCl ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.8521g Al ₂ O ₃ Carrier (specific surface 560 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 2h, roasting in a muffle furnace at 450 ℃ for 4h, and finally oxidizing in a tubular furnace at 350 ℃ for 1h in an oxygen atmosphere to obtain Mn-Rh/Al ₂ O ₃ A catalyst.

Example 4

Ti-Rh/Al ₂ O ₃ Preparation of the catalyst: weighing 0.1211g H ₄ TiO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.8749g Al ₂ O ₃ Carrier (specific surface 560 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, carrying out rotary evaporation at the temperature of 75 ℃, drying at the temperature of 120 ℃ for 2 hours, roasting in a muffle furnace at the temperature of 450 ℃ for 4 hours, and finally oxidizing in a tubular furnace at the temperature of 350 ℃ for 1 hour to obtain Ti-Rh/Al ₂ O ₃ A catalyst.

Example 5

Re-Ir/Al ₂ O ₃ Preparation of the catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9294g Al ₂ O ₃ Carrier (specific surface 560 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 2h, roasting in a muffle furnace at 450 ℃ for 4h, and finally oxidizing in a tubular furnace at 350 ℃ in an oxygen atmosphere for 1h to obtain Re-Ir/Al ₂ O ₃ A catalyst.

Example 6

W-Ir/Al ₂ O ₃ Preparation of the catalyst: weighing 0.06795g H ₂ WO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9289g Al ₂ O ₃ Carrier (specific surface 560 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 2h, roasting in a muffle furnace at 450 ℃ for 4h, and finally oxidizing in a tubular furnace at 350 ℃ in an oxygen atmosphere for 1h to obtain W-Ir/Al ₂ O ₃ A catalyst.

Example 7

Mn-Ir/Al ₂ O ₃ Preparation of the catalyst: weighing 0.1438g KMnO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.8531g Al ₂ O ₃ Carrier (specific surface 560 m) ² G) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 2h, roasting in a muffle furnace at 450 ℃ for 4h, and finally oxidizing in a tubular furnace at 350 ℃ in an oxygen atmosphere for 1h to obtain Mn-Ir/Al ₂ O ₃ A catalyst.

Example 8

Ti-Ir/Al ₂ O ₃ Preparation of the catalyst: weighing 0.1211g H ₄ TiO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.8758g Al ₂ O ₃ Carrier (specific surface 560 m) ² G) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 2h, roasting in a muffle furnace at 450 ℃ for 4h, and finally oxidizing in a tubular furnace at 350 ℃ in an oxygen atmosphere for 1h to obtain Ti-Ir/Al ₂ O ₃ A catalyst.

Example 9

Re-Rh/SiO ₂ Preparation of the catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.004067g RhCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9285g SiO ₂ Support (specific surface 580 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ A catalyst.

Example 10

W-Rh/SiO ₂ Preparation of the catalyst: weighing 0.06795g H ₂ WO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.004067g RhCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9280g SiO ₂ Support (specific surface 580 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 2h, roasting in a muffle furnace at 450 ℃ for 4h, and finally oxidizing in a tubular furnace at 350 ℃ for 1h to obtain W-Rh/SiO ₂ A catalyst.

Example 11

Mn-Rh/SiO ₂ Preparation of the catalyst: weighing 0.1438g KMnO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.8521g SiO are weighed ₂ Support (specific surface 580 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 2h, roasting in a muffle furnace at 450 ℃ for 4h, and finally oxidizing in a tubular furnace at 350 ℃ for 1h in an oxygen atmosphere to obtain Mn-Rh/SiO ₂ A catalyst.

Example 12

Ti-Rh/SiO ₂ CatalysisPreparation of the agent: weighing 0.1211g H ₄ TiO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.8749g SiO ₂ Support (specific surface 580 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 2h, roasting in a muffle furnace at 450 ℃ for 4h, and finally oxidizing in a tubular furnace at 350 ℃ for 1h to obtain Ti-Rh/SiO ₂ A catalyst.

Example 13

Re-Ir/SiO ₂ Preparation of the catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9294g SiO ₂ Support (specific surface 580 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 2h, roasting in a muffle furnace at 450 ℃ for 4h, and finally oxidizing in a tubular furnace at 350 ℃ in an oxygen atmosphere for 1h to obtain Re-Ir/SiO ₂ A catalyst.

Example 14

W-Ir/SiO ₂ Preparation of the catalyst: weighing 0.06795g H ₂ WO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9289g SiO ₂ Support (specific surface 580 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 2h, roasting in a muffle furnace at 450 ℃ for 4h, and finally oxidizing in a tubular furnace at 350 ℃ in an oxygen atmosphere for 1h to obtain W-Ir/SiO ₂ A catalyst.

Example 15

Mn-Ir/SiO ₂ Preparation of the catalyst:weighing 0.1438g KMnO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.8531g SiO ₂ Support (specific surface 580 m) ² G) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 2h, roasting in a muffle furnace at 450 ℃ for 4h, and finally oxidizing in a tubular furnace at 350 ℃ in an oxygen atmosphere for 1h to obtain Mn-Ir/SiO ₂ A catalyst.

Example 16

Ti-Ir/SiO ₂ Preparation of the catalyst: weighing 0.1211g H ₄ TiO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.8758g SiO ₂ Support (specific surface 580 m) ² G) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 2h, roasting in a muffle furnace at 450 ℃ for 4h, and finally oxidizing in a tubular furnace at 350 ℃ in an oxygen atmosphere for 1h to obtain Ti-Ir/SiO ₂ A catalyst.

Example 17

Preparation of Re-Rh/AC catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.9285g AC carrier (specific surface 590 m) is weighed ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, spin-steaming at 75 ℃, drying at 120 ℃ for 4h, and finally roasting in a tubular furnace at 450 ℃ for 3h under argon atmosphere to obtain the Re-Rh/AC catalyst.

Example 18

Preparation of W-Rh/AC catalyst: weighing 0.06795g H ₂ WO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine is added and stirred for 30min. 0.004067g RhCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9280g AC carrier (specific surface 590 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. And then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 4h, and finally roasting in a tubular furnace at 450 ℃ for 3h under the argon atmosphere to obtain the W-Rh/AC catalyst.

Example 19

Preparation of Mn-Rh/AC catalyst: weighing 0.1438g KMnO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.8521g AC carrier (specific surface 590 m) is weighed ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. And then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 4h, and finally roasting in a tubular furnace at 450 ℃ for 3h under the argon atmosphere to obtain the Mn-Rh/AC catalyst.

Example 20

Preparation of Ti-Rh/AC catalyst: weighing 0.1211g H ₄ TiO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.004067g RhCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.8749g AC carrier (specific surface 590 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. And then, carrying out rotary evaporation at the temperature of 75 ℃, drying at the temperature of 120 ℃ for 4 hours, and finally roasting in a tubular furnace at the temperature of 450 ℃ for 3 hours to obtain the Ti-Rh/AC catalyst.

Example 21

Preparation of Re-Ir/AC catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9294g AC carrier (specific surface 590 m) ² /g) was uniformly dispersed in 20mL of ultrapure water, and the above was added dropwise thereto at a rate of 10mL/hDipping the precursor solution and stirring for 12h. And then, carrying out rotary evaporation at the temperature of 75 ℃, drying at the temperature of 120 ℃ for 4h, finally roasting at the temperature of 450 ℃ in an argon atmosphere in a tubular furnace for 3h, and finally oxidizing at the temperature of 350 ℃ in an oxygen atmosphere in the tubular furnace for 1h to obtain the Re-Ir/AC catalyst.

Example 22

Preparation of W-Ir/AC catalyst: weighing 0.06795g H ₂ WO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.9289g AC carrier (specific surface 590 m) is weighed ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. And then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 4h, and finally roasting in a tubular furnace at 450 ℃ for 3h under the argon atmosphere to obtain the W-Ir/AC catalyst.

Example 23

Preparation of Mn-Ir/AC catalyst: weighing 0.1438g KMnO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.8531g AC carrier (specific surface 590 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. And then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 4h, and finally roasting in a tubular furnace at 450 ℃ for 3h under the argon atmosphere to obtain the Mn-Ir/AC catalyst.

Example 24

Preparation of Ti-Ir/AC catalyst: weighing 0.1211g H ₄ TiO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.8758g AC carrier (specific surface 590 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. And then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 4h, and finally roasting in a tubular furnace at 450 ℃ for 3h under the argon atmosphere to obtain the Ti-Ir/AC catalyst.

Example 25

Re-Rh/ZrO ₂ Preparation of the catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.004067g RhCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.9285g ZrO was weighed ₂ Carrier (specific surface 550 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/ZrO ₂ A catalyst.

Example 26

W-Rh/ZrO ₂ Preparation of the catalyst: weighing 0.06795g H ₂ WO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.9280g ZrO was weighed ₂ Carrier (specific surface 550 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain the W-Rh/ZrO ₂ A catalyst.

Example 27

Mn-Rh/ZrO ₂ Preparation of the catalyst: weighing 0.1438g KMnO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.004067g RhCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.8521g ZrO was weighed ₂ Carrier (specific surface 550 m) ² G) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Mn-Rh/ZrO ₂ A catalyst.

Example 28

Ti-Rh/ZrO ₂ Preparation of the catalyst: weighing 0.1211g H ₄ TiO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.8749g ZrO were weighed ₂ Carrier (specific surface 550 m) ² G) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Ti-Rh/ZrO ₂ A catalyst.

Example 29

Re-Ir/ZrO ₂ Preparation of the catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.9294g ZrO was weighed ₂ Carrier (specific surface 550 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Ir/ZrO ₂ A catalyst.

Example 30

W-Ir/ZrO ₂ Preparation of the catalyst: weighing 0.06795g H ₂ WO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.9289g ZrO was weighed ₂ Carrier (specific surface 550 m) ² G) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 2h, roasting in a muffle furnace at 450 ℃ for 4h, and finally oxidizing in a tubular furnace at 350 ℃ in an oxygen atmosphere for 1h to obtain W-Ir/ZrO ₂ A catalyst.

Example 31

Mn-Ir/ZrO ₂ Preparation of the catalyst: weighing 0.1438g KMnO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.8531g ZrO was weighed ₂ Carrier (specific surface 550 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 2h, roasting in a muffle furnace at 450 ℃ for 4h, and finally oxidizing in a tubular furnace at 350 ℃ for 1h to obtain Mn-Ir/ZrO ₂ A catalyst.

Example 32

Ti-Ir/ZrO ₂ Preparation of the catalyst: weighing 0.1211g H ₄ TiO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.8758g ZrO was weighed ₂ Carrier (specific surface 550 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Ti-Ir/ZrO ₂ A catalyst.

Example 33

Preparation of Re-Rh/SiC catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.9285g SiC carrier (specific surface 520 m) is weighed ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. And then, carrying out rotary evaporation at the temperature of 75 ℃, drying at the temperature of 120 ℃ for 2 hours, roasting at the temperature of 450 ℃ in a muffle furnace for 4 hours, and finally oxidizing at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace for 1 hour to obtain the Re-Rh/SiC catalyst.

Example 34

Preparation of W-Rh/SiC catalyst: 0 is weighed out.06795g H ₂ WO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.004067g RhCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.9280g SiC carrier (specific surface 520 m) is weighed ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. And then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 2h, roasting in a muffle furnace at 450 ℃ for 4h, and finally oxidizing in a tubular furnace at 350 ℃ for 1h to obtain the W-Rh/SiC catalyst.

Example 35

Preparation of Mn-Rh/SiC catalyst: weighing 0.1438g KMnO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.8521g SiC carrier (specific surface 520 m) is weighed ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. And then, carrying out rotary evaporation at the temperature of 75 ℃, drying at the temperature of 120 ℃ for 2 hours, roasting at the temperature of 450 ℃ in a muffle furnace for 4 hours, and finally oxidizing at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace for 1 hour to obtain the Mn-Rh/SiC catalyst.

Example 36

Preparation of Ti-Rh/SiC catalyst: weighing 0.1211g H ₄ TiO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.8749g SiC carrier (specific surface 520 m) is weighed ² G) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. And then, carrying out rotary evaporation at the temperature of 75 ℃, drying at the temperature of 120 ℃ for 2 hours, roasting at the temperature of 450 ℃ in a muffle furnace for 4 hours, and finally oxidizing at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace for 1 hour to obtain the Ti-Rh/SiC catalyst.

Example 37

Preparation of Re-Ir/SiC catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.9294g SiC carrier (specific surface 520 m) is weighed ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. And then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 2h, roasting in a muffle furnace at 450 ℃ for 4h, and finally oxidizing in a tubular furnace at 350 ℃ for 1h in an oxygen atmosphere to obtain the Re-Ir/SiC catalyst.

Example 38

Preparation of W-Ir/SiC catalyst: weighing 0.06795g H ₂ WO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.9289g SiC carrier (specific surface 520 m) is weighed ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. And then, carrying out rotary evaporation at the temperature of 75 ℃, drying at the temperature of 120 ℃ for 2 hours, roasting in a muffle furnace at the temperature of 450 ℃ for 4 hours, and finally oxidizing in a tubular furnace at the temperature of 350 ℃ for 1 hour to obtain the W-Ir/SiC catalyst.

Example 39

Preparation of Mn-Ir/SiC catalyst: weighing 0.1438g KMnO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.8531g SiC carrier (specific surface 520 m) is weighed ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. And then, carrying out rotary evaporation at the temperature of 75 ℃, drying at the temperature of 120 ℃ for 2 hours, roasting in a muffle furnace at the temperature of 450 ℃ for 4 hours, and finally oxidizing in a tubular furnace at the temperature of 350 ℃ for 1 hour to obtain the Mn-Ir/SiC catalyst.

Example 40

Preparing a Ti-Ir/SiC catalyst: weighing 0.1211g H ₄ TiO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.003107g IrCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.8758g SiC carrier (specific surface 520 m) is weighed ² Per g) uniformityThe obtained solution was dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. And then, carrying out rotary evaporation at 75 ℃, drying at 120 ℃ for 2h, roasting in a muffle furnace at 450 ℃ for 4h, and finally oxidizing in a tubular furnace at 350 ℃ for 1h in an oxygen atmosphere to obtain the Ti-Ir/SiC catalyst.

Example 41

Re-Rh/SiO ₂ (I) Preparation of the catalyst: weighing 0.07203g NH ₄ ReO ₄ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.004067g RhCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9239g SiO ₂ Support (specific surface 580 m) ² G) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (I) A catalyst.

Example 42

Re-Rh/SiO ₂ (II) preparation of the catalyst: weighing 0.09760g ReCl ₅ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.8983g SiO ₂ Support (specific surface 580 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (II) a catalyst.

Example 43

Re-Rh/SiO ₂ (III) preparation of the catalyst: 0.06504g Re is weighed ₂ O ₇ Dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9309g SiO ₂ Support (specific surface 580 m) ² /g) are uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12 hours. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (III) a catalyst.

Example 44

Re-Rh/SiO ₂ (IV) preparation of the catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.002466g Rh were added ₂ O ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9301g SiO ₂ Support (specific surface 580 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (IV) a catalyst.

Example 45

Re-Rh/SiO ₂ (V) preparation of catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.005015g Rh (acac) (CO) was added ₂ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9275g SiO ₂ Support (specific surface 580 m) ² G) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (V) a catalyst.

Example 46

Re-Rh/SiO ₂ (VI) preparation of the catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.003778g Rh were added ₂ (CO) ₄ Cl ₂ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9288g SiO ₂ Carrier(specific surface 580m ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (VI) a catalyst.

Example 47

Re-Rh/SiO ₂ (VII) preparation of catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g arginine was added and stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9285g SiO ₂ Support (specific surface 580 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (VII) a catalyst.

Example 48

Re-Rh/SiO ₂ (VIII) preparation of the catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then, 0.3g of ethylenediamine was added thereto, and the mixture was stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9285g SiO ₂ Support (specific surface 580 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (VIII) a catalyst.

Example 49

Re-Rh/SiO ₂ (IX) preparation of the catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then, 0.3g of ethanolamine was added thereto, and the mixture was stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9285g SiO ₂ Vector (ratio)Surface 580m ² G) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (IX) a catalyst.

Example 50

Re-Rh/SiO ₂ (X) preparation of the catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then, 0.3g of ethylene glycol was added thereto, and the mixture was stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9285g SiO ₂ Support (specific surface 580 m) ² G) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (X) a catalyst.

Example 51

Re-Rh/SiO ₂ (XI) preparation of the catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.004067g RhCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9285g SiO ₂ Support (specific surface 580 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 200 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (XI) a catalyst.

Example 52

Re-Rh/SiO ₂ (XII) preparation of the catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. 0.004067g RhCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9285g SiO ₂ Carrier (Bibiao watch)Surface 580m ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 250 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (XII) a catalyst.

Example 53

Re-Rh/SiO ₂ Preparation of (XIII) catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.9285g SiO are weighed ₂ Support (specific surface 580 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 300 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (XIII) catalyst.

Example 54

Re-Rh/SiO ₂ (XIV) preparation of the catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9285g SiO ₂ Support (specific surface 580 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 400 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (XIV) a catalyst.

Example 55

Re-Rh/SiO ₂ (XV) preparation of the catalyst: weighing 0.01349g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.001017g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9855g SiO ₂ Carrier(specific surface 580m ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (XV) catalyst. (1.0wt% Re-0.05wt% Rh/SiO ₂ )

Example 56

Re-Rh/SiO ₂ (XVI) preparation of the catalyst: weighing 0.01349g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.02034g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.9662g SiO are weighed ₂ Support (specific surface 580 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (XVI) catalyst. (1.0wt% Re-1.0wt% Rh/SiO ₂ )

Example 57

Re-Rh/SiO ₂ (XVII) preparation of the catalyst: weighing 0.1349g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then 0.001017g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.8641g SiO ₂ Support (specific surface 580 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (XVII) catalyst. (10.0wt% Re-0.05wt% Rh/SiO ₂ )

Example 58

Re-Rh/SiO ₂ (XVIII) preparation of the catalyst: weighing 0.1349g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g triethanolamine was added and stirred for 30min. Then add0.02034g RhCl ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.8448g SiO ₂ Support (specific surface 580 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (XVIII) catalyst. (10.0wt% Re-1.0wt% Rh/SiO ₂ )

Comparative example 1

Re-Rh/SiO ₂ (1) Preparation of the catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water. Then 0.3g of sodium dodecyl benzene sulfonate is added and stirred for 30min. 0.004067g RhCl was then added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. 0.9285g SiO are weighed ₂ Support (specific surface 580 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (1) A catalyst.

Comparative example 2

Re-Rh/SiO ₂ (2) Preparation of the catalyst: weighing 0.06746g HReO ₄ The solution was dissolved in 10mL of ultrapure water and stirred for 30min. Then 0.004067g RhCl was added ₃ And stirring for 30min to obtain the mixed solution for dipping the precursor. Weighing 0.9285g SiO ₂ Support (specific surface 580 m) ² And/g) was uniformly dispersed in 20mL of ultrapure water, and the above impregnation precursor solution was added dropwise thereto at a rate of 10mL/h, followed by stirring for 12h. Then, rotary steaming is carried out at the temperature of 75 ℃, drying is carried out for 2h at the temperature of 120 ℃, roasting is carried out for 4h at the temperature of 450 ℃ in a muffle furnace, and finally oxidation is carried out for 1h at the temperature of 350 ℃ in an oxygen atmosphere in a tubular furnace to obtain Re-Rh/SiO ₂ (2) A catalyst.

The application case is the application of the prepared catalyst in the reaction of preparing acetic acid and acetic ester by taking methanol and CO as raw materials

Using the catalysts prepared in examples 1-58 and comparative examples 1-2The acetic acid and acetic ester were prepared by using the following reaction conditions, and the conversion of methanol and the selectivity of acetic acid and acetic ester are shown in Table 1. (reaction operating conditions: 0.2g of the above catalyst is weighed and reduced for 1h at 200 ℃ in situ, the reaction temperature is 250 ℃, the CO reaction pressure is 1.0MPa, and CO/CH ₃ OH＝1(molar ratio)，LHSV＝6h ^-1 )

TABLE 1

The results show that: comparison of examples 1-8, 9-16, 17-24, 25-32, and 33-40, respectively, shows that the bi-component catalysts of rhenium, etc. -rhodium and iridium, supported on different inert carriers, have better activity in methanol halogen-free carbonylation applications, wherein the bi-component catalysts of Re-Rh and Re-Ir, in which the main catalyst is Re and the co-catalyst is Rh and Ir, are prominent, and the carrier is preferably SiO ₂ . Re-Rh/SiO, obtainable in comparative examples 41 to 58 ₂ In the preparation process of the catalyst, conditions such as metal precursors, dispersant types, oxidation temperature, metal loading capacity and the like have certain influence on the dispersion degree and the activity state of active components of the catalyst, wherein the oxidation temperature is particularly prominent. The main catalyst metal precursor is preferably HReO ₄ And NH ₄ ReO ₄ The cocatalyst metal precursor is preferably RhCl ₃ (ii) a Preferably triethanolamine, arginine, ethanolamine and other dispersing agents, and more preferably triethanolamine and arginine; the oxidation temperature is preferably 350-400 ℃; the loading of the main catalyst is preferably 1.0 to 10.0%, more preferably 4.0 to 6.0%, and the loading of the co-catalyst is preferably 0.05 to 1%, more preferably 0.02 to 0.04%. Finally, anionic surfactant sodium dodecyl benzene sulfonate is used as a dispersing agent and is not dispersedThe agent is a comparative example illustrating the importance of the dispersant type.

Claims

1. A preparation method of a methanol gas-phase carbonylation catalyst is characterized by comprising the following steps:

1) Preparing a main catalyst precursor solution, adding a dispersing agent into the main catalyst precursor solution, and adding a precursor of a cocatalyst into the main catalyst precursor solution to obtain a precursor mixed impregnation solution;

2) Dropwise adding the mixed impregnation liquid into an ethanol and/or water dispersed inert carrier suspension, carrying out rotary evaporation, drying, and roasting and oxidizing at the high temperature of 300-600 ℃ for 1-2h under the oxygen atmosphere to obtain a product catalyst;

the catalyst consists of a main catalyst, a cocatalyst and a carrier; the main catalyst is one or more than two of oxides of Re, W, mn and Ti; the cocatalyst is one or two of Rh and Ir; the carrier is one or more than two of alumina, silicon oxide, active carbon, zirconia and silicon carbide.

2. The method for preparing the catalyst according to claim 1, wherein:

the dispersant is one or more of arginine, triethanolamine, ethylene glycol, ethanolamine and ethylenediamine, and the concentration of the dispersant in the mixed impregnation liquid is 0.1 to 1.0g/mL of water.

3. The method for preparing the catalyst according to claim 1, wherein:

the mass loading capacity of the main catalyst in the catalyst is 0.01-15.0%; the mass loading capacity of the cocatalyst is 0.01-2.0%.

4. The method for preparing the catalyst according to claim 1, wherein:

the main catalyst is dispersed on the carrier in single point, and the cocatalyst is dispersed on the carrier in single atom.

5. The method for preparing the catalyst according to claim 1, wherein:

the specific surface area of the carrier is 50-600m ² Between/g.

6. The method for preparing the catalyst according to claim 1, wherein:

the precursor compound of the main catalyst is mainly perrhenic acid (HReO) ₄ ) Ammonium perrhenate (NH) ₄ ReO ₄ ) Rhenium pentachloride (Recl) ₅ ) Tungstic acid (H) ₂ WO ₄ ) Ammonium tungstate [ (NH) ₄ ) ₁₀ W ₁₂ O ₄₁ ]Tungsten hexachloride (WCl) ₆ ) Tungsten pentachloride (WCl) ₅ ) Potassium permanganate (KMnO) ₄ ) Manganese tetrachloride (MnCl) ₄ ) Titanic acid (H) ₄ TiO ₄ ) Ethyl titanate (C) ₈ H ₂₀ O ₄ Ti), titanium tetrachloride (TiCl) ₄ ) One or more than two of them; the concentration of the main catalyst in the mixed impregnation liquid is 0.02-0.5g/mL of water;

the precursor of the cocatalyst is one or more than two of conventional transition metal compounds, and oxide, hydroxide, sulfide and chloride of Rh and/or Ir; the concentration of the cocatalyst in the mixed impregnation solution is 0.001-0.01g/mL of water.

7. The method for preparing the catalyst according to claim 2, wherein: the concentration of the dispersing agent in the mixed impregnation liquid is 0.2 to 0.5g/mL of water.

8. The method for preparing the catalyst according to claim 3, wherein: the mass loading capacity of the main catalyst in the catalyst is 1.0-10.0%; the mass loading capacity of the cocatalyst is 0.05-1%.

9. The method for preparing the catalyst according to claim 5, wherein:

the specific surface area of the carrier is 350-500m ² Between/g.

10. The method for preparing the catalyst according to claim 6, wherein:the precursor compound of the main catalyst mainly comprises HReO ₄ 、H ₂ WO ₄ 、KMnO ₄ 、 H ₄ TiO ₄ One or more than two of them; the concentration of the main catalyst in the mixed impregnation liquid is 0.05-0.3g/mL of water; the precursor of the cocatalyst is Rh ₂ O ₃ 、RhCl ₃ 、H ₂ IrCl ₆ 、IrCl ₃ One or more than two of them; the concentration of the cocatalyst in the mixed impregnation liquid is 0.002-0.005g/mL of water.

11. A catalyst prepared by the preparation method of any one of claims 1 to 10.

12. Use of the catalyst of claim 11 in the halogen-free carbonylation of methanol to produce acetic acid and acetate.

13. Use according to claim 12, characterized in that: before reaction, the catalyst needs in-situ hydrogen reduction at 100-300 deg.c for 0.5-2.0 hr.

14. Use according to claim 12 or 13, characterized in that: a fixed bed reactor is adopted, the reaction temperature is 150 to 300 ℃, the reaction pressure is 0.1 to 3.5MPa, and the space velocity of the volume of the methanol liquid is 0.1 to 15h ^-1 CO and CH ₃ The molar ratio of OH is 0.25 to 10; the main products of the reaction are acetic acid and methyl acetate, and the byproduct is dimethyl ether.

15. Use according to claim 13, characterized in that: the temperature is 100 to 200 ℃.