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

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

A catalyst for the preparation of acetic acid and acetate by halogen-free gas-phase carbonylation of methanol Preparation method and application

technical field

The invention belongs to the technical field of chemical engineering catalysts, in particular to the preparation of a kind of single-point dispersed oxide of Re, W, Mn, Ti supported by an inert carrier and a kind of single-atom dispersed Rh and Ir and its reaction in methanol Application in the preparation of acetic acid and acetate by halogen-free gas-phase carbonylation.

Background technique

Acetic acid is a very important organic chemical raw material with a wide range of uses. It can be used to produce various follow-up chemical products such as vinyl acetate monomer, anhydride, terephthalic acid, acetate, and cellulose acetate. And the rapid development of acetic acid downstream products, acetic acid production has become an important part of the chemical industry and national economy.

Mature acetic acid production processes include acetylene acetaldehyde method, ethylene acetaldehyde method, ethanol acetaldehyde method, butane oxidation method and methanol carbonylation method. Among them, the methanol carbonylation process plays a dominant role, and the production capacity of acetic acid production equipment using this process has accounted for 81% of the total production capacity of acetic acid. In the past 50 years, the industrialization process of methanol carbonylation to produce acetic acid has roughly experienced three stages of development:

The first stage: In 1960, BSAF Company used cobalt catalyst to realize the industrial production of acetic acid by carbonylation of methanol under relatively high reaction temperature and pressure (250°C, 60MPa). The purity of acetic acid produced by this method is not high, and the main by-products are higher alcohols, higher aldehydes and higher carboxylic acids, and the cost of product separation is relatively high. The second stage: Monsanto has developed a rhodium-iodide (RhI ₃ ) catalytic system with higher activity and selectivity. The temperature and pressure of the reaction are also relatively low (about 175° C., 3.0 MPa). The selectivity of acetic acid based on methanol is more than 99%, and the selectivity based on CO has also reached more than 90%. The corrosion resistance requirements of the device are very high, and an all-zirconium alloy reactor is required. The third stage: the industrialization of Ir catalyst is the production of acetic acid by methanol carbonylation. This process greatly improves the stability of the catalyst, the reaction is carried out under the condition of low water content, and the formation of liquid by-products is reduced, and the conversion rate of CO is improved. Celanese Chemical Company has improved the stability of the Rh catalyst by adding high-concentration inorganic iodides (mainly lithium iodide). After adding lithium iodide and methyl iodide additives, the water content in the reactor can be significantly reduced (about 4 %～5%), while maintaining a high carbonylation rate, the separation cost of the new process is significantly reduced.

Japan's Chiyoda (Chiyoda) and UOP jointly developed the Acetica process, which is based on a heterogeneous Rh catalyst in which active Rh complexes are supported on polyvinylpyridine resin. The strong and weak coordination bond chelating polymer catalyst researched by Yuan Guoqing, Institute of Chemistry, Chinese Academy of Sciences has also formed an independent intellectual property system. The catalyst system has the characteristics of high stability and high activity, and can improve the selectivity of CO utilization.

Although the homogeneous Rh-based and Ir-based catalytic systems have quite high catalytic activity and selectivity, the selectivity of acetic acid is greater than 99%, which has achieved good industrial applications. However, the homogeneous catalyst system has many disadvantages, for example, the precious metal catalyst is easy to lose, the separation of the product and the catalyst is difficult, and the catalyst recycling and recovery are complicated.

Aiming at the shortage of the homogeneous reaction catalytic system mentioned above, some researchers turned their attention to the supported heterogeneous catalytic system, but the supported catalyst system has lower activity than the homogeneous catalytic system, easy removal of active components, and requirements for the carrier. higher questions. The most important thing is that the methanol carbonylation system needs to be carried out with the participation of halogen additives (such as methyl iodide), which will cause serious corrosion of the equipment, requiring the use of Hastelloy or zirconium equipment, which greatly increases the investment cost. The development of a halogen-free carbonylation system for methanol can avoid corrosion of the reaction medium and reduce equipment investment costs, which is of great industrial significance. Halogen-free methanol carbonylation must first solve the problem of methanol activation. In the molecular sieve system, the acidic sites in the MOR molecular sieve promote the coupling of methanol to form dimethyl ether first, and the carbonylation of dimethyl ether to form methyl acetate. However, due to the poor hydrothermal stability of molecular sieves, the direct carbonylation of dimethyl ether to produce methyl acetate is generally studied. Even if dimethyl ether without water is directly used, the problem of carbon deposition on molecular sieves is still serious during the carbonylation process, and the molar ratio of CO/dimethyl ether is required to be very high, up to 50. This severely reduces the CO conversion rate and increases cycle energy consumption. It has been reported in the literature that spatially separated methanol adsorption and activation of active sites can avoid the formation of DME. Therefore, the single-point dispersed acidic sites supported on the inert support can minimize the coupling of two molecules of methanol on the surface, inhibit the formation of dimethyl ether, and simultaneously promote the formation of methyl acetate during the carbonylation reaction of surface methoxy species. . The selection of an inert carrier with a high specific surface area and a large pore size can avoid problems such as carbon deposition, internal diffusion, and carrier hydrothermal instability in the molecular sieve carrier. The rate-determining step of acid-catalyzed carbonylation is mostly CO insertion, while monodisperse Rh and Ir atoms have strong CO insertion ability, but their ability to activate methanol to form methyl or methoxy is poor.

Therefore, simultaneously loading appropriate carbonylation active Rh and Ir single-atom catalysts can enhance the single-point dispersed acid sites and the interaction between Rh and Ir single atoms, which can greatly increase the reaction rate. Herein, we propose a single-site dispersed oxide of Re, W, Mn, Ti and single-atom dispersed Rh and Ir supported on an inert support as a catalyst for the halogen-free carbonylation of methanol to acetic acid and acetate esters. . The catalyst has the advantages of high activity, high selectivity, good stability and the like. At the same time, the equipment investment cost of the process can be reduced, the process is environmentally friendly and has broad industrial application prospects.

Contents of the invention

The object of the present invention is to provide a two-component catalyst of a single-point dispersed oxide of Re, W, Mn, Ti supported by an inert carrier and a single-atom dispersed Rh or Ir and its halogen-free methanol carbonylation to prepare acetic acid and acetate in the application.

Technical scheme of the present invention is:

A supported catalyst for preparing acetic acid and acetate by halogen-free gas-phase carbonylation of methanol. The catalyst is composed of an inert carrier, one of main catalysts Re, W, Mn and Ti oxides and one of co-catalysts Rh or Ir.

The inert carrier is one of alumina, silica, activated carbon, zirconia, and silicon carbide. The main catalyst compounds mainly include 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 ), tetrachloride Manganese (MnCl ₄ ), titanic acid (H ₄ TiO ₄ ), ethyl titanate (C ₈ H ₂₀ O ₄ Ti), titanium tetrachloride (TiCl ₄ ), etc. One of HReO ₄ , H ₂ WO ₄ , KMnO ₄ , and H ₄ TiO ₄ is preferred. Its mass loading in the catalyst is 0.01-15.0%, preferably 1.0-10.0%.

The compounds of the cocatalyst Rh and Ir are conventional transition metal compounds, including oxides, hydroxides, sulfides and chlorides, etc., such as nanometer metal rhodium (Rh), rhodium oxide (Rh ₂ O ₃ , RhO ₂ ) , rhodium acetylacetonate carbonyl (Rh(acac)(CO) ₂ ), dirhodium dichlorotetracarbonyl (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 ), chloroiridic acid (H ₂ IrCl ₆ ) and iridium chloride (IrCl ₃ , IrCl ₄ ), etc., preferably Rh(acac) One of (CO) ₂ , RhCl ₃ , H ₂ IrCl ₆ , IrCl ₃ . The mass loading of metal rhodium Rh or Ir in the catalyst is 0.01-2.0%, preferably 0.05-1%.

The preparation method of the supported catalyst is: dissolve the precursor compounds of the main catalyst Re, W, Mn, Ti, etc. in ultrapure water, add an appropriate amount of arginine or triethanolamine or other complexing agents, and then add the co-catalyst rhodium or The precursor compound of iridium can be used to obtain the impregnation precursor mixed solution. It is then slowly added dropwise to the ethanol or water dispersed inert carrier suspension. Then rotary steaming, drying, calcining, that is, calcining and oxidation at a high temperature of 300-600° C. for 1-2 hours under an oxygen atmosphere to obtain the catalyst of the present invention. The oxygen atmosphere is a mixture of oxygen or oxygen and an inert atmosphere gas, and the oxygen volume concentration in the oxygen atmosphere is more than 20%, preferably more than 50%, most preferably more than 80%; the inert atmosphere gas is one or _both of He, Ar, and N more than one species.

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

Before the reaction, in-situ low-temperature hydrogen reduction is required, the temperature is 100-300°C, preferably 100-200°C, and the reduction time is 0.5-2.0h. The reducing atmosphere is hydrogen or hydrogen and an inert atmosphere gas, and the hydrogen volume concentration in the reducing atmosphere is more than 20%, preferably more than 50%, most preferably more than 80%; the inert atmosphere gas is one or _two of He, Ar, and N above.

The beneficial effects of the present invention are:

Compared with the existing metal catalyst technology for methanol carbonylation, the catalyst of the present invention has a simple preparation method, is applied to the halogen-free gas-phase carbonylation reaction of methanol, does not require a Hastelloy or zirconium material reactor, and has high activity and selectivity , good stability and so on.

In addition, the inert support prepared by the present invention is prepared by a single-point dispersed Re, W, Mn, Ti and other oxides and a single-atom dispersed Rh or Ir catalyst preparation and its use in methanol heterogeneous carbonylation It is a new catalytic system for methanol carbonylation, which is different from the previous methanol carbonylation process involving halogenated hydrocarbon co-catalysts. The main catalyst in the catalyst is a single-point dispersed oxide of Re, etc. as the Lewis acidic site, which can activate methanol very well, and the co-catalyst Rh or Ir in the catalyst can adsorb and activate CO, and realize the rapid insertion of CO, thereby improving the halogen-free methanol The efficiency of carbonylation avoids the long-standing corrosion problem in the process of methanol carbonylation, greatly reduces equipment investment costs, and has industrialization prospects.

Description of drawings

Fig. 1 is embodiment 9Re-Rh/SiO Catalyst X _- ray diffraction (XRD) figure;

Fig. 2 is embodiment 9 Re-Rh/SiO ₂ Catalyst transmission electron microscope (TEM) photo and Re, Rh, Si and Omapping picture.

Discussion of the Figures: In order to demonstrate the single-point and single-atom dispersion of the catalysts described in this application, the Re-Rh/SiO ₂ catalyst prepared as described in Example 9 below was characterized by XRD and TEM. As shown in Figure 1, compared with the XRD spectrum of SiO ₂ , the XRD spectrum of both Re/SiO ₂ and Re-Rh/SiO ₂ did not find the sharp peaks of metal Re and Rh, only one carrier SiO ₂ typical broad peak. Therefore, it can be explained that the metals on the Re-Rh/SiO ₂ catalyst did not agglomerate, and may present a single-point or single-atom dispersed state. As shown in Figure 2, no metal clusters were found in the high-resolution TEM photo of the Re-Rh/SiO ₂ catalyst, and both Re and Rh in the mapping picture have a high degree of dispersion, so it can be speculated that the two are single-point and single atom dispersion.

detailed description

The following examples illustrate but not limit the content to be protected by the present invention.

In order to compare the superiority of the rhenium etc.-rhodium or iridium catalyst supported by the inert carrier in the present invention in the halogen-free carbonylation of methanol, the following specific implementation cases are carried out, and the active metals such as rhenium supported by different inert carriers-rhodium and iridium two-component M ₁ -M ₂ /S catalyst (where M ₁ represents metals such as Re, W, Mn and Ti, M ₂ represents metals such as Rh and Ir, S represents inert supports such as Al ₂ O ₃ , SiO ₂ , AC, ZrO ₂ , SiC, etc. , the mass content of M ₁ metal in the following examples is 5.0%, and the mass content of M ₂ metal is 0.2%). Re-Rh/Al ₂ O ₃ is the rhenium-rhodium catalyst supported by alumina in the present invention; similarly W-Rh/Al ₂ O ₃ is the tungsten-rhodium catalyst supported by alumina in the present invention; Mn-Rh/Al ₂ O ₃ is the manganese-rhodium catalyst supported by alumina in the present invention; Ti-Rh/Al ₂ O ₃ is the titanium-rhodium catalyst supported by alumina in the present invention; Re-Ir/Al ₂ O ₃ is alumina in the present invention Supported rhenium-iridium catalyst; W-Ir/Al ₂ O ₃ is the tungsten-iridium catalyst supported by alumina in the present invention; Mn-Ir/Al ₂ O ₃ is the manganese-iridium catalyst supported by alumina in the present invention; Ti -Ir/Al ₂ O ₃ is the titanium-iridium catalyst supported by alumina in the present invention; the active metal rhenium supported by other supports-rhodium and iridium two-component catalysts are represented in the same form as above. At the same time, taking the Re-Rh/SiO ₂ catalyst as an example, Re-Rh/SiO ₂ (I-XVIII) were prepared under the conditions of different metal precursors, dispersants, oxidation temperatures and different metal loadings. Catalyst preparation method: Dissolve a certain amount of rhenium and other precursor compounds in ultrapure water, add an appropriate amount of triethanolamine or other complexing agents, and then add an appropriate amount of rhodium or iridium precursor compounds to obtain a mixed solution of impregnated precursors . It is then slowly added dropwise to the ethanol or water dispersed inert carrier suspension. Then rotary steaming, drying, calcining, calcining and oxidation at a high temperature of 200-500° C. for 1-2 hours under an oxygen atmosphere to obtain the catalyst of the present invention.

Example 1

Preparation of Re-Rh/Al ₂ O ₃ catalyst: Weigh 0.06746g of HReO ₄ solution and dissolve it in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9285g of Al ₂ O ₃ carrier (specific surface 560m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise thereto at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2 hours, calcination at 450°C in a muffle furnace for 4 hours, and finally oxidation in a tube furnace at 350°C for 1 hour, the Re-Rh/Al ₂ O ₃ catalyst can be obtained.

Example 2

Preparation of W-Rh/Al ₂ O ₃ catalyst: Weigh 0.06795g H ₂ WO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9280g of Al ₂ O ₃ carrier (specific surface 560m ² /g) and evenly disperse it in 20mL of ultrapure water, and add the impregnation precursor solution dropwise thereto at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the W-Rh/Al ₂ O ₃ catalyst can be obtained.

Example 3

Preparation of Mn-Rh/Al ₂ O ₃ catalyst: Weigh 0.1438g KMnO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.8521g of Al ₂ O ₃ carrier (specific surface 560m ² /g) and evenly disperse it in 20mL of ultrapure water, and add the impregnation precursor solution dropwise thereto at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination in a muffle furnace at 450°C for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Mn-Rh/Al ₂ O ₃ catalyst can be obtained.

Example 4

Preparation of Ti-Rh/Al ₂ O ₃ catalyst: 0.1211g H ₄ TiO ₄ was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.8749g of Al ₂ O ₃ carrier (specific surface 560m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary steaming at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Ti-Rh/Al ₂ O ₃ catalyst can be obtained.

Example 5

Preparation of Re-Ir/Al ₂ O ₃ catalyst: Weigh 0.06746g of HReO ₄ solution and dissolve it in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.9294g of Al ₂ O ₃ carrier (specific surface 560m ² /g) and evenly disperse it in 20mL of ultrapure water, and add the impregnation precursor solution dropwise thereto at a rate of 10mL/h, and stir for 12h. Subsequently, rotary steaming at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Ir/Al ₂ O ₃ catalyst can be obtained.

Example 6

Preparation of W-Ir/Al ₂ O ₃ catalyst: 0.06795g H ₂ WO ₄ was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.9289g of Al ₂ O ₃ carrier (specific surface 560m ² /g) and evenly disperse it in 20mL of ultrapure water, and add the impregnation precursor solution dropwise thereto at a rate of 10mL/h, and stir for 12h. Subsequently, rotary steaming at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the W-Ir/Al ₂ O ₃ catalyst can be obtained.

Example 7

Preparation of Mn-Ir/Al ₂ O ₃ catalyst: Weigh 0.1438g KMnO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.8531g of Al ₂ O ₃ carrier (specific surface 560m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Mn-Ir/Al ₂ O ₃ catalyst can be obtained.

Example 8

Preparation of Ti-Ir/Al ₂ O ₃ catalyst: 0.1211g H ₄ TiO ₄ was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.8758g Al ₂ O ₃ carrier (specific surface 560m ² /g) and evenly disperse in 20mL ultrapure water, and add the above impregnation precursor solution dropwise thereto at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination in a muffle furnace at 450°C for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Ti-Ir/Al ₂ O ₃ catalyst can be obtained.

Example 9

Preparation of Re-Rh/SiO ₂ catalyst: Weigh 0.06746g of HReO ₄ solution and dissolve it in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9285g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Rh/SiO ₂ catalyst can be obtained.

Example 10

Preparation of W-Rh/SiO ₂ catalyst: Weigh 0.06795g H ₂ WO ₄ and dissolve in 10mL ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9280g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary steaming at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the W-Rh/SiO ₂ catalyst can be obtained.

Example 11

Preparation of Mn-Rh/SiO ₂ catalyst: Weigh 0.1438g KMnO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.8521g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary steaming at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Mn-Rh/SiO ₂ catalyst can be obtained.

Example 12

Preparation of Ti-Rh/SiO ₂ catalyst: Weigh 0.1211g of H ₄ TiO ₄ and dissolve in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.8749g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary steaming at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Ti-Rh/SiO ₂ catalyst can be obtained.

Example 13

Preparation of Re-Ir/SiO ₂ catalyst: Weigh 0.06746g of HReO ₄ solution and dissolve it in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.9294g SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL ultrapure water, and drop the impregnation precursor solution into it at a rate of 10mL/h, and stir for 12h. Subsequently, rotary steaming at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Ir/SiO ₂ catalyst can be obtained.

Example 14

Preparation of W-Ir/SiO ₂ catalyst: Weigh 0.06795g H ₂ WO ₄ and dissolve in 10mL ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.9289g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the W-Ir/ _SiO2 catalyst can be obtained.

Example 15

Preparation of Mn-Ir/SiO ₂ catalyst: Weigh 0.1438g KMnO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.8531g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Mn-Ir/SiO ₂ catalyst can be obtained.

Example 16

Preparation of Ti-Ir/SiO ₂ catalyst: Weigh 0.1211g H ₄ TiO ₄ and dissolve in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.8758g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary steaming at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Ti-Ir/SiO ₂ catalyst can be obtained.

Example 17

Preparation of Re-Rh/AC catalyst: Weigh 0.06746g of HReO ₄ solution and dissolve it in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9285g of AC carrier (specific surface: 590m ² /g) and evenly disperse it in 20mL of ultrapure water, and add the impregnation precursor solution dropwise thereto at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 4h, and finally calcination in a tube furnace at 450°C for 3h to obtain the Re-Rh/AC catalyst.

Example 18

Preparation of W-Rh/AC catalyst: Weigh 0.06795g of H ₂ WO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9280g of AC carrier (specific surface 590m ² /g) and evenly disperse in 20mL of ultrapure water, and dropwise add the impregnation precursor solution to it at a rate of 10mL/h, and stir for 12h. Subsequently, it was rotary evaporated at 75°C, dried at 120°C for 4h, and finally calcined in a tube furnace at 450°C for 3h to obtain the W-Rh/AC catalyst.

Example 19

Preparation of Mn-Rh/AC catalyst: Weigh 0.1438g KMnO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.8521g of AC carrier (specific surface: 590m ² /g) and evenly disperse it in 20mL of ultrapure water, and add the impregnation precursor solution dropwise thereto at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75° C., drying at 120° C. for 4 h, and finally calcination in a tube furnace at 450° C. for 3 h to obtain the Mn-Rh/AC catalyst.

Example 20

Preparation of Ti-Rh/AC catalyst: Weigh 0.1211g of H ₄ TiO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.8749g of AC carrier (specific surface: 590m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75° C., drying at 120° C. for 4 h, and finally calcination in a tube furnace at 450° C. for 3 h to obtain the Ti-Rh/AC catalyst.

Example 21

Preparation of Re-Ir/AC catalyst: Weigh 0.06746g of HReO ₄ solution and dissolve it in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.9294g of AC carrier (specific surface: 590m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise thereto at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75 °C, drying at 120 °C for 4 h, finally calcination in a tube furnace at 450 °C for 3 h, and finally oxidation in a tube furnace at 350 °C for 1 h, the Re-Ir/AC catalyst can be obtained.

Example 22

Preparation of W-Ir/AC catalyst: Weigh 0.06795g of H ₂ WO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.9289g of AC carrier (specific surface: 590m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 4h, and finally calcination in a tube furnace at 450°C for 3h to obtain the W-Ir/AC catalyst.

Example 23

Preparation of Mn-Ir/AC catalyst: Weigh 0.1438g KMnO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.8531g of AC carrier (specific surface: 590m ² /g) and evenly disperse it in 20mL of ultrapure water, and add the impregnation precursor solution dropwise thereto at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 4h, and finally calcination in a tube furnace at 450°C for 3h to obtain the Mn-Ir/AC catalyst.

Example 24

Preparation of Ti-Ir/AC catalyst: Weigh 0.1211g of H ₄ TiO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.8758g of AC carrier (specific surface: 590m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75° C., drying at 120° C. for 4 h, and finally calcination in a tube furnace at 450° C. for 3 h to obtain the Ti-Ir/AC catalyst.

Example 25

Preparation of Re-Rh/ZrO ₂ catalyst: Weigh 0.06746g of HReO ₄ solution and dissolve it in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9285g ZrO ₂ carrier (specific surface 550m ² /g) and evenly disperse in 20mL ultrapure water, and add the impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75 °C, drying at 120 °C for 2 h, calcination at 450 °C in a muffle furnace for 4 h, and finally oxidation in a tube furnace at 350 °C for 1 h, the Re-Rh/ZrO ₂ catalyst can be obtained.

Example 26

Preparation of W-Rh/ZrO ₂ catalyst: Weigh 0.06795g H ₂ WO ₄ and dissolve in 10mL ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9280g of ZrO ₂ carrier (specific surface 550m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary steaming at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the W-Rh/ZrO ₂ catalyst can be obtained.

Example 27

Preparation of Mn-Rh/ZrO ₂ catalyst: Weigh 0.1438g KMnO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.8521g of ZrO ₂ carrier (specific surface 550m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary steaming at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Mn-Rh/ZrO ₂ catalyst can be obtained.

Example 28

Preparation of Ti-Rh/ZrO ₂ catalyst: Weigh 0.1211g H ₄ TiO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.8749g of ZrO ₂ carrier (specific surface 550m ² /g) and evenly disperse it in 20mL of ultrapure water, and add the impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary steaming at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Ti-Rh/ZrO ₂ catalyst can be obtained.

Example 29

Preparation of Re-Ir/ZrO ₂ catalyst: Weigh 0.06746g of HReO ₄ solution and dissolve it in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.9294g of ZrO ₂ carrier (specific surface 550m ² /g) and evenly disperse it in 20mL of ultrapure water, and add the impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary steaming at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Ir/ZrO ₂ catalyst can be obtained.

Example 30

Preparation of W-Ir/ZrO ₂ catalyst: Weigh 0.06795g H ₂ WO ₄ and dissolve in 10mL ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.9289g of ZrO ₂ carrier (specific surface 550m ² /g) and evenly disperse it in 20mL of ultrapure water, and add the impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the W-Ir/ZrO ₂ catalyst can be obtained.

Example 31

Preparation of Mn-Ir/ZrO ₂ catalyst: Weigh 0.1438g KMnO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.8531g of ZrO ₂ carrier (specific surface 550m ² /g) and evenly disperse in 20mL of ultrapure water, and dropwise add the impregnation precursor solution to it at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Mn _- Ir/ZrO2 catalyst can be obtained.

Example 32

Preparation of Ti-Ir/ZrO ₂ catalyst: Weigh 0.1211g H ₄ TiO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.8758g of ZrO ₂ carrier (specific surface 550m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Ti-Ir/ZrO ₂ catalyst can be obtained.

Example 33

Preparation of Re-Rh/SiC catalyst: Weigh 0.06746g of HReO ₄ solution and dissolve it in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9285g of SiC carrier (specific surface: 520m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise thereto at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Rh/SiC catalyst can be obtained.

Example 34

Preparation of W-Rh/SiC catalyst: Weigh 0.06795g of H ₂ WO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9280g of SiC carrier (specific surface: 520m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise thereto at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the W-Rh/SiC catalyst can be obtained.

Example 35

Preparation of Mn-Rh/SiC catalyst: Weigh 0.1438g KMnO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.8521g of SiC carrier (specific surface: 520m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise thereto at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination in a muffle furnace at 450°C for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Mn-Rh/SiC catalyst can be obtained.

Example 36

Preparation of Ti-Rh/SiC catalyst: Weigh 0.1211g H ₄ TiO ₄ and dissolve in 10mL ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.8749g of SiC carrier (specific surface 520m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise thereto at a rate of 10mL/h, and stir for 12h. Subsequently, rotary steaming at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Ti-Rh/SiC catalyst can be obtained.

Example 37

Preparation of Re-Ir/SiC catalyst: Weigh 0.06746g of HReO ₄ solution and dissolve it in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.9294g of SiC carrier (specific surface: 520m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise thereto at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Ir/SiC catalyst can be obtained.

Example 38

Preparation of W-Ir/SiC catalyst: Weigh 0.06795g of H ₂ WO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.9289g of SiC carrier (specific surface: 520m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise thereto at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination in a muffle furnace at 450°C for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the W-Ir/SiC catalyst can be obtained.

Example 39

Preparation of Mn-Ir/SiC catalyst: Weigh 0.1438g KMnO ₄ and dissolve in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.8531g of SiC carrier (specific surface: 520m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise thereto at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination in a muffle furnace at 450°C for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Mn-Ir/SiC catalyst can be obtained.

Example 40

Preparation of Ti-Ir/SiC catalyst: 0.1211g H ₄ TiO ₄ was weighed and dissolved in 10mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003107g IrCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.8758g of SiC carrier (specific surface: 520m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise thereto at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Ti-Ir/SiC catalyst can be obtained.

Example 41

Preparation of Re-Rh/SiO ₂ (I) catalyst: 0.07203g of NH ₄ ReO ₄ was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9239g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary steaming at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Rh/SiO ₂ (I) catalyst can be obtained.

Example 42

Preparation of Re-Rh/SiO ₂ (II) catalyst: 0.09760 g of ReCl ₅ was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.8983g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Rh/SiO ₂ (II) catalyst can be obtained.

Example 43

Preparation of Re-Rh/SiO ₂ (III) catalyst: 0.06504g of Re ₂ O ₇ was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9309g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Rh/SiO ₂ (III) catalyst can be obtained.

Example 44

Preparation of Re-Rh/SiO ₂ (IV) catalyst: 0.06746 g of HReO ₄ solution was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.002466g Rh ₂ O ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9301g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2 hours, calcination at 450°C in a muffle furnace for 4 hours, and finally oxidation in a tube furnace at 350°C for 1 hour, the Re-Rh/SiO ₂ (IV) catalyst can be obtained.

Example 45

Preparation of Re-Rh/SiO ₂ (V) catalyst: 0.06746 g of HReO ₄ solution was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.005015g Rh(acac)(CO) ₂ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9275g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary steaming at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Rh/SiO ₂ (V) catalyst can be obtained.

Example 46

Preparation of Re-Rh/SiO ₂ (VI) catalyst: 0.06746 g of HReO ₄ solution was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.003778g of Rh ₂ (CO) ₄ Cl ₂ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9288g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Rh/SiO ₂ (VI) catalyst can be obtained.

Example 47

Preparation of Re-Rh/SiO ₂ (VII) catalyst: 0.06746 g of HReO ₄ solution was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3g of arginine and stir for 30min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9285g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Rh/SiO ₂ (VII) catalyst can be obtained.

Example 48

Preparation of Re-Rh/SiO ₂ (VIII) catalyst: 0.06746 g of HReO ₄ solution was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3g of ethylenediamine and stir for 30min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9285g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Rh/SiO ₂ (VIII) catalyst can be obtained.

Example 49

Preparation of Re-Rh/SiO ₂ (IX) catalyst: 0.06746 g of HReO ₄ solution was weighed and dissolved in 10 mL of ultrapure water. Add 0.3 g of ethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9285g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Rh/SiO ₂ (IX) catalyst can be obtained.

Example 50

Preparation of Re-Rh/SiO ₂ (X) catalyst: 0.06746g of HReO ₄ solution was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3 g of ethylene glycol and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9285g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Rh/SiO ₂ (X) catalyst can be obtained.

Example 51

Preparation of Re-Rh/SiO ₂ (XI) catalyst: 0.06746g of HReO ₄ solution was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9285g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 200°C for 1h, the Re-Rh/SiO ₂ (XI) catalyst can be obtained.

Example 52

Preparation of Re-Rh/SiO ₂ (XII) catalyst: 0.06746 g of HReO ₄ solution was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9285g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 250°C for 1h, the Re-Rh/SiO ₂ (XII) catalyst can be obtained.

Example 53

Preparation of Re-Rh/SiO ₂ (XIII) catalyst: 0.06746g of HReO ₄ solution was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9285g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary steaming at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 300°C for 1h, the Re-Rh/SiO ₂ (XIII) catalyst can be obtained.

Example 54

Preparation of Re-Rh/SiO ₂ (XIV) catalyst: 0.06746g of HReO ₄ solution was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9285g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 400°C for 1h, the Re-Rh/SiO ₂ (XIV) catalyst can be obtained.

Example 55

Preparation of Re-Rh/SiO ₂ (XV) catalyst: 0.01349g of HReO ₄ solution was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.001017g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9855g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Rh/SiO ₂ (XV) catalyst can be obtained. (1.0wt%Re-0.05wt%Rh/SiO ₂ )

Example 56

Preparation of Re-Rh/SiO ₂ (XVI) catalyst: 0.01349g of HReO ₄ solution was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.02034g RhCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.9662g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Rh/SiO ₂ (XVI) catalyst can be obtained. (1.0wt%Re-1.0wt%Rh/SiO ₂ )

Example 57

Preparation of Re-Rh/SiO ₂ (XVII) catalyst: 0.1349 g of HReO ₄ solution was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.001017g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.8641g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Rh/SiO ₂ (XVII) catalyst can be obtained. (10.0wt%Re-0.05wt%Rh/SiO ₂ )

Example 58

Preparation of Re-Rh/SiO ₂ (XVIII) catalyst: 0.1349 g of HReO ₄ solution was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3 g of triethanolamine and stir for 30 min. Then add 0.02034g RhCl ₃ and stir for 30 minutes to obtain a mixed solution of impregnation precursor. Weigh 0.8448g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Rh/SiO ₂ (XVIII) catalyst can be obtained. (10.0wt%Re-1.0wt%Rh/SiO ₂ )

Comparative example 1

Preparation of Re-Rh/SiO ₂ (1) catalyst: 0.06746 g of HReO ₄ solution was weighed and dissolved in 10 mL of ultrapure water. Then add 0.3g of sodium dodecylbenzenesulfonate and stir for 30min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9285g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Rh/SiO ₂ (1) catalyst can be obtained.

Comparative example 2

Preparation of Re-Rh/SiO ₂ (2) catalyst: 0.06746g of HReO ₄ solution was weighed and dissolved in 10 mL of ultrapure water, and stirred for 30 min. Then add 0.004067g RhCl ₃ and stir for 30 minutes to obtain a mixed solution for impregnating the precursor. Weigh 0.9285g of SiO ₂ carrier (specific surface 580m ² /g) and evenly disperse in 20mL of ultrapure water, and add the above impregnation precursor solution dropwise at a rate of 10mL/h, and stir for 12h. Subsequently, rotary evaporation at 75°C, drying at 120°C for 2h, calcination at 450°C in a muffle furnace for 4h, and finally oxidation in a tube furnace at 350°C for 1h, the Re-Rh/SiO ₂ (2) catalyst can be obtained.

The application case is the application of the prepared catalyst in the reaction of preparing acetic acid and acetate with methanol and CO as raw materials

Using the catalysts prepared in Examples 1-58 and Comparative Examples 1-2, acetic acid and acetate were prepared according to the following reaction operating conditions. The conversion rate of methanol and the selectivity of acetic acid and acetate are shown in Table 1. (Reaction operating conditions: weigh 0.2g of the above catalyst, in-situ reduction at 200°C for 1h, reaction temperature: 250°C, CO reaction pressure: 1.0MPa, CO/CH ₃ OH=1 (molarratio), LHSV=6h ^-1 )

Table 1

The result shows: comparing Examples 1-8, 9-16, 17-24, 25-32, 33-40 respectively, it can be drawn that the rhenium etc.-rhodium and iridium two-component catalysts supported by different inert carriers have no halogen carbonyl in methanol The activity in chemical applications is better, among which the Re-Rh and Re-Ir two-component catalysts with Re as the main catalyst and Rh and Ir as the co-catalyst are more prominent, and the carrier is preferably SiO ₂ . Comparing Examples 41-58 can be obtained, Re-Rh/SiO _In the preparation process of the catalyst, conditions such as metal precursor, dispersant type, oxidation temperature and metal load have an effect on the dispersion and active state of the active components of the catalyst. certain influence, among which the oxidation temperature is particularly prominent. The metal precursors of the main catalyst are preferably HReO ₄ and NH ₄ ReO ₄ , and the metal precursors of the co-catalyst are preferably RhCl ₃ ; dispersants such as triethanolamine, arginine, and ethanolamine are preferred, and triethanolamine and arginine are more preferred; the oxidation temperature is preferably 350~ 400°C; the loading of the main catalyst is preferably 1.0-10.0%, more preferably 4.0-6.0%, and the loading of the co-catalyst is preferably 0.05-1%, more preferably 0.02-0.04%. Finally, the importance of the type of dispersant is illustrated by taking the anionic surfactant sodium dodecylbenzenesulfonate as dispersant and without dispersant as a comparative example.

Claims (15)

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 ℃.

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