CN108067222B - Activated carbon carrier-supported sulfur-promoted iridium-based catalyst and preparation and application thereof - Google Patents

Activated carbon carrier-supported sulfur-promoted iridium-based catalyst and preparation and application thereof Download PDF

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CN108067222B
CN108067222B CN201611003633.3A CN201611003633A CN108067222B CN 108067222 B CN108067222 B CN 108067222B CN 201611003633 A CN201611003633 A CN 201611003633A CN 108067222 B CN108067222 B CN 108067222B
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CN108067222A (en
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丁云杰
任周
宋宪根
吕元
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Dalian Institute of Chemical Physics of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/468—Iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B01J27/045—Platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B01J31/30—Halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation

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Abstract

A sulfur-promoted iridium-based catalyst for preparing methyl acetate and acetic acid by heterogeneous carbonylation of methanol and a preparation method thereof. The catalyst consists of three parts, namely a main active component, a sulfur auxiliary agent and a carrier, wherein the main active component is Ir and metal oxide, and the contents of the Ir and the metal oxide are 0.01-5.0% and 0.1-30% of the weight of the catalyst; the content of the sulfur-containing auxiliary agent is 0.1-30% of the weight of the catalyst. The carrier is coconut shell carbon, and the specific surface area of the coconut shell carbon is 500-1100m2(ii)/g, the average pore diameter is 1 to 200 nm. According to the invention, a sulfur-promoted Ir-based catalyst is formed by loading a main active component and a sulfur-containing precursor on a carrier through an impregnation method. In a fixed bed reactor, under the action of certain temperature and pressure, the catalyst and methyl iodide3OH/CO can be converted into methyl acetate and acetic acid with high activity and high selectivity.

Description

Activated carbon carrier-supported sulfur-promoted iridium-based catalyst and preparation and application thereof
Technical Field
The invention belongs to the technical field of heterogeneous catalytic carbonylation, and particularly relates to an iridium-based catalyst promoted by sulfur loaded on activated carbon, a preparation method of the iridium-based catalyst and application of the iridium-based catalyst in methyl acetate preparation and acetic acid reaction through heterogeneous carbonylation of methanol.
Background
Methyl acetate is increasingly replacing acetone, butanone, ethyl acetate, cyclopentane, etc. internationally. Because it does not limit the discharge of organic pollutants, it can reach the new environmental standard of paint, printing ink, resin and adhesive factories. The synthesis of ethanol by methyl acetate hydrogenation is also one of the main ways for preparing ethanol by coal at present. The preparation method mainly comprises (1) directly carrying out esterification reaction on acetic acid and methanol by taking sulfuric acid as a catalyst to generate a methyl acetate crude product, then dehydrating by using calcium chloride, neutralizing by using sodium carbonate, and fractionating to obtain a methyl acetate finished product. (2) Dimethyl ether is synthesized by carbonylation on an H-MOR molecular sieve catalyst, but the carbon deposition of the molecular sieve is seriously inactivated, and the space-time yield is lower. (3) When the methanol is carbonylated to prepare the acetic acid, the methyl acetate exists as a byproduct, but the selectivity is low and the separation cost is high. The vast majority of the current commercially viable methyl acetate synthesis routes go through the intermediate step of acetic acid.
Currently, the methanol carbonylation process dominates in the industrial production of acetic acid, and the production capacity of the current acetic acid production device adopting the process accounts for 94 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 BSAF company first achieved the commercial production of acetic acid by the methanol carbonylation process using a cobalt catalyst at relatively high reaction temperatures and pressures (250 ℃, 60MPa) in 1960. And a second stage: the company Monsanto developed rhodium-iodides (RhI) with higher activity and selectivity3) A catalytic system. The reaction temperature and pressure were also relatively low (about 175 ℃ C., 3.0MPa), and the selectivity of acetic acid based on methanol was 99% or more, and the selectivity based on CO was also 90% or more. 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 catalysts is the methanol carbonylation process for the production of acetic acid. 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.
The company Chiyoda, japan, and UOP jointly developed the acitica process based on a heterogeneous Rh catalyst in which an active Rh complex is chemically immobilized on a polyvinylpyridine resin. The strong and weak coordinate bond chelating polymer catalyst which is formed by researching and combining the Yuan-national Cynanchum Paniculatum of the chemical research institute 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.
However, since the homogeneous catalyst itself has the disadvantages of easy loss of active components, difficult separation, etc., some researchers have focused on the supported heterogeneous catalyst system. The heterogeneous catalysis system can achieve the characteristics that the catalyst and the product are convenient to separate, the concentration of the catalyst is not limited by solubility, and the like, and can improve the productivity and the like by increasing the concentration of the catalyst. The supported heterogeneous catalyst system can be roughly divided into a polymer carrier, an activated carbon carrier, an inorganic oxide carrier and other systems according to different carriers, but the supported catalyst system has the problems of lower activity than the homogeneous catalyst system, easy removal of active ingredients, higher requirement on the carrier and the like. And methyl acetate prepared by methanol heterogeneous carbonylation with high selectivity directly skips the acetic acid synthesis route, thereby avoiding using expensive zirconium materials, further converting a small amount of acetic acid into ester by a reaction-distillation technology, and saving mass production cost.
The activated carbon supported iridium system is applied to carbonylation, which has two problems. Firstly, although TOF of acetyl in carbonylation reaction of the system can reach 1000h-1However, the TOF is compared with that of a similar hydroformylation reaction TOF (5000--1) Still far from each other, so that there is still a need for improvement and research on the activity of the catalyst, and further improvement and improvement of the activity of the catalyst are desired. In general, the activity of the catalyst can be improved by adding some metal or nonmetal auxiliary agent or changing the acid treatment mode. Sulfonation is a research focus at present, sulfonic acid can be used as an auxiliary agent to improve the reactivity of some reactions, so that the addition of sulfuric acid or organic sulfonic acid can be considered to improve the TOF of the carbonylation reaction.
Disclosure of Invention
The invention aims to provide an activated carbon-supported sulfur-promoted iridium-based catalyst and application thereof in the reaction of preparing methyl acetate and acetic acid from methanol through carbonylation, so that the activity of the catalyst is improved to a great extent, and the selectivity of by-product methane is reduced.
The technical scheme of the invention is as follows:
the sulfur-promoted iridium-based catalyst for preparing methyl acetate and acetic acid by carbonylation of methanol and a preparation method thereof are mainly characterized in that the catalyst consists of three parts, namely a main active component, a sulfur auxiliary agent and a carrier, wherein the main active component is Ir and metal oxide, and a sulfur auxiliary agent precursor is common sulfur-containing inorganic acid and organic acid; the carrier is coconut shell carbon, and the specific surface area of the coconut shell carbon is 500-1100m2(ii)/g, the average pore diameter is 1-200 nm;
wherein the content of the main active component Ir is 0.1-5.0% of the weight of the catalyst; wherein the metal oxide is La2O3、Mo3O4、Fe2O3、Co3O4、NiO、CeO2、RuO2The content is 0.1-30.0% of the weight of the catalyst.
Wherein the content of 1-18 mol/L sulfuric acid, 0.1-5 mol/L benzenesulfonic acid, 1-12 mol/L thioacetic acid and 1-5 mol/L thiophenol is 0.1-30.0% of the weight of the catalyst. The sulfur-promoted iridium-based catalyst for preparing methyl acetate and acetic acid by carbonylation of methanol according to claim 1 and 7, wherein the sulfur-promoted iridium-based catalyst is characterized in that Ir metal and a metal oxide precursor are dissolved in water or ethanol in the presence of sulfur-containing inorganic acid or organic acid, the obtained solution is co-impregnated on activated carbon, the solvent is evaporated by water bath at 60-80 ℃, the solvent is dried in an oven at 100-120 ℃ for 5-15 h, and N is2Roasting for 2-6 h at 200-800 ℃ under protection.
The CO and the pumped reactants such as methanol and the like enter a fixed bed reactor filled with the granular catalyst of the invention to carry out methanol carbonylation reaction, and the main product is methyl acetate.
The temperature of the carbonylation reaction is 180-280 ℃, the pressure is 0.5-3.5MPa, and the liquid volume space velocity is 0.1-15h-1。
The cocatalyst reactant also comprises methyl iodide which accounts for 1-35.0% of the weight of the methanol.
The volume ratio of hydrogen to CO in the reaction gas is 0.1-2.
The main reactor is made of hastelloy.
A sulfur promoted iridium-based catalyst for the carbonylation of methanol is used in the conversion of methanol/CO to methyl acetate and in the reaction of acetic acid.
The invention has the beneficial effects that:
compared with the existing methanol carbonylation technology of the activated carbon supported iridium catalyst, the activated carbon supported sulfur promoted iridium-based catalyst has higher activity in the heterogeneous carbonylation reaction of methanol.
Detailed Description
The following examples illustrate but do not limit what is intended to be protected by the present invention.
In the embodiment, the mass fraction of concentrated HCl is 37.5%, the mass fraction of concentrated sulfuric acid is 98%, the concentration of dilute sulfuric acid is 2mol/L, the concentration of dilute benzenesulfonic acid is 1mol/L, the concentration of thioacetic acid is 2mol/L, the concentration of thiophenol is 3mol/L, the concentration of benzenesulfonic acid is 3mol/L, and the concentration of benzenesulfonic acid is 3 mol/L.
Example 1
Weighing 0.0863g IrCl3Dissolved in 17.17g of water at 65 ℃. A further 3mL of concentrated HCl and 0.0423gLa were added2O3Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 280 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported iridium-based catalyst.
Example 2
Weighing 0.0863g IrCl3Dissolved in 17.17g of water at 65 ℃. 0.75ml of 2mol/L dilute sulfuric acid and 0.0423gLa were added2O3Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 280 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 3
Weighing 0.0863g IrCl3Dissolved in 17.17g of water at 65 ℃. 1.5ml of 2mol/L dilute sulfuric acid and 0.0423gLa were added2O3Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 280 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 4
Weighing 0.0863g IrCl3Dissolved in 17.17g of water at 65 ℃. 3.75ml of 2mol/L dilute sulfuric acid and 0.0423gLa were added2O3Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 280 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 5
Weighing 0.0863g IrCl3Dissolved in 17.17g of water at 65 ℃. 7.5ml of 2mol/L dilute sulfuric acid and 0.0423gLa were added2O3Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 280 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 6
Weighing 0.0863g IrCl3Dissolved in 17.17g of water at 65 ℃. 15ml of 2mol/L dilute sulfuric acid and 0.0423gLa are added2O3Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 280 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 7
Weighing 0.0863g IrCl3Dissolved in 17.17g of water at 65 ℃. 30ml of 2mol/L dilute sulfuric acid and 0.0423gLa are added2O3Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 170 ℃ for 10h, and roasting at 280 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 8
Weighing 0.0863g IrCl3Dissolved in 17.17g of water at 65 ℃. 7.8ml of 1mol/L benzenesulfonic acid and 0.0423gLa were further added2O3Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 170 ℃ for 10h, and roasting at 280 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 9
Weighing 0.0863g IrCl3Dissolved in 17.17g of water at 65 ℃. 15ml of 2mol/L dilute sulfuric acid and 0.0423gLa are added2O3Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 350 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 10
Weighing 0.0863g IrCl3Dissolved in 17.17g of water at 65 ℃. 15ml of 2mol/L dilute sulfuric acid and 0.0423gLa are added2O3Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 450 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 11
0 is weighed out.0863gIrCl3Dissolved in 17.17g of water at 65 ℃. 15ml of 2mol/L dilute sulfuric acid and 0.0423gLa are added2O3Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 650 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 12
Weighing 0.0863g IrCl3Dissolved in 17.17g of water at 65 ℃. 15ml of 2mol/L dilute sulfuric acid and 0.0423gLa are added2O3Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 800 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 13
Weighing 0.0863g IrCl3Dissolved in 17.17g of water at 65 ℃. Then 15ml of 2mol/L dilute sulfuric acid and 0.0256 gGluO are added2Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 800 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 14
Weighing 0.0863g IrCl3Dissolved in 17.17g of water at 65 ℃. 15ml of 2mol/L dilute sulfuric acid and 0.0288g of CeO are added2Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 15
Weighing 0.0863g IrCl3Dissolved in 17.17g of water at 65 ℃. 15ml of 2mol/L thioacetic acid and 0.0321gMo were added3O4Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 800 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 16
Weighing 0.0863g IrCl3Dissolved in 17.17g of water at 65 ℃. Then 15ml of 3mol/L thiophenol and 0.0312g of Co are added3O4Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 350 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 17
Weighing 0.0863gH2IrCl6Dissolved in 17.17g of water at 65 ℃. 15ml of 3mol/L benzenesulfinic acid and 0.0208g Fe were added2O3Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 350 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 18
Weighing 0.0863g IrCl3Dissolved in 17.17g of water at 65 ℃. 15ml of 2mol/L benzenesulfonic acid and 0.0138g of NiO were added thereto, stirred until dissolved, and then 5g of coconut charcoal was impregnated. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 450 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 19
Weighing 0.4001g IrCl3Dissolved in 17.17g of water at 65 ℃. 15ml of 2mol/L dilute sulfuric acid and 0.0423gLa are added2O3Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 800 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 20
Weighing 0.0863g IrCl3Dissolved in 17.17g of water at 65 ℃. 60ml of 2mol/L dilute sulfuric acid and 0.0423gLa are added2O3Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 800 ℃ for 4h under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Example 21
Weighing 0.0863g IrCl3Dissolved in 17.17g of water at 65 ℃. 60ml of 2mol/L dilute sulfuric acid and 0.4230gLa are added2O3Stirred until dissolved, and then impregnated with 5g of coconut shell charcoal. Evaporating solvent in 65 deg.C water bath, and oven at 120 deg.CDrying for 10h, and roasting for 4h at 800 ℃ under the protection of nitrogen to obtain the active carbon-supported sulfur-promoted iridium-based catalyst.
Application example: the prepared catalyst is applied to the reaction for preparing methyl acetate by taking methanol/CO as a raw material.
Activation of the catalyst: before the catalyst is used, CO/H is in the reactor2＝10(GHSV＝3840h-1) In-situ reduction activation is carried out in a flow under the conditions: raising the temperature from room temperature to 235 ℃ at the temperature of 4 ℃/min under the pressure of 2.5MPa, and keeping the temperature for 1 hour to obtain the activated sulfur-promoted iridium-based catalyst. The reaction conditions are as follows: 235 ℃, 2.5MPa, CH3OH/CO/H220/30/3 (mole ratio), CH3OH/CH3I (mass ratio) is 8:1, methanol LHSV is 4.8h-1The catalyst volume was 0.5 mL. After the reaction tail gas is cooled by a cold trap, the gas product is analyzed on line, and the chromatographic instruments are Agilent 7890A GC, PQ packed columns and TCD detectors. Off-line analysis of liquid phase product, FFAP capillary chromatographic column, FID detector. And (4) performing internal standard analysis, wherein isobutanol is used as an internal standard substance.
Methyl acetate and acetic acid were prepared according to the above procedure using the sulfur-promoted iridium-based catalysts prepared in examples 1-18, with the methanol conversion, methane selectivity, methyl acetate selectivity, and acetic acid selectivity shown in table 1.
TABLE 1 results of the methanol carbonylation reaction of the examples
Figure BDA0001152711700000061
The results show that the activity of the sulfur-containing catalyst is far better than that of a hydrochloric acid-containing catalyst by comparing 1,6,7,18,19,20 and 21, and the mass fraction of Ir is optimally 0.5-2.0 wt% of the total mass of the catalyst; the mass fraction of the metal oxide is 0.2-8.0wt% of the total mass of the catalyst; the mass fraction of the sulfur-containing compound is optimally 1-30.0 wt% of the total mass of the catalyst.

Claims (13)

1. An activated carbon-supported sulfur-promoted iridium-based catalyst characterized by: the iridium-based catalyst comprises a main active component, a sulfur auxiliary agent and a carrier, wherein the main active component is iridium and transition metal oxide except iridium, the carrier is activated carbon, and the sulfur auxiliary agent is a sulfur-containing compound; the sulfur-containing compound is a roasting product of sulfur acid at the temperature of 200-450 ℃; the sulfur acid is one or more of benzene sulfonic acid, benzene sulfinic acid, benzene sulfenic acid, sulfuric acid, thioacetic acid and thiophenol;
the iridium accounts for 0.01 to 5.0 weight percent of the total mass of the catalyst; the transition metal oxide except iridium accounts for 0.1-30.0 wt% of the total mass of the catalyst; the sulfur-containing compound accounts for 1-30.0 wt% of the total mass of the catalyst;
the preparation process of the iridium-based catalyst comprises the following steps: dissolving an iridium metal precursor and transition metal oxides except iridium in water and/or ethanol in the presence of sulfuric acid, soaking the obtained solution on activated carbon, evaporating the solvent in a water bath at 60-80 ℃, drying in an oven at 100-120 ℃ for 5-15 h, and drying with N2Roasting at the temperature of 200 ℃ and 450 ℃ for 2-6 h under protection.
2. The sulfur-promoted iridium-based catalyst of claim 1 wherein:
the sulfur-containing acid is one or more of sulfuric acid, benzenesulfonic acid, thioacetic acid and thiophenol, iridium accounts for 0.1-4.0 wt% of the total mass of the catalyst, and transition metal oxides except iridium account for 0.1-10wt% of the total mass of the catalyst.
3. The sulfur-promoted iridium-based catalyst of claim 1 wherein:
the iridium accounts for 0.5-2.0 wt% of the total mass of the catalyst, and the transition metal oxide except the iridium accounts for 0.2-8.0wt% of the total mass of the catalyst.
4. The sulfur-promoted iridium-based catalyst of claim 1 wherein: the carrier is coconut shell carbon, the specific surface area of the coconut shell carbon is 500-2The average pore diameter of the coconut shell carbon is 1-200 nm.
5. The sulfur-promoted iridium-based catalyst of claim 4 wherein: the carrier is coconutThe specific surface area of the shell carbon and the coconut shell carbon is 550-900m2The average pore diameter of the coconut shell carbon is 5-100 nm.
6. The sulfur-promoted iridium-based catalyst of claim 1 wherein: the transition metal oxide except iridium is La2O3、Mo3O4、Fe2O3、Co3O4、NiO、CeO2、RuO2One or more than two of them.
7. A process for the preparation of a sulfur-promoted iridium-based catalyst as claimed in any one of claims 1 to 6 wherein: dissolving an iridium metal precursor and transition metal oxides except iridium in water and/or ethanol in the presence of sulfuric acid, soaking the obtained solution on activated carbon, evaporating the solvent in a water bath at 60-80 ℃, drying in an oven at 100-120 ℃ for 5-15 h, and drying with N2Roasting at the temperature of 200 ℃ and 450 ℃ for 2-6 h under protection.
8. The method of claim 7, wherein: the sulfur acid is one or more than two of 0.1-5 mol/L benzenesulfonic acid, 1-18 mol/L sulfuric acid, 1-12 mol/L thioacetic acid and 1-5 mol/L thiophenol;
the iridium metal precursor is IrCl3·3H2O and/or H2IrCl6·6H2O; the transition metal oxide other than iridium is La2O3、Mo3O4、Fe2O3、Co3O4、NiO、CeO2、RuO2One or more than two of them.
9. The method of claim 8, wherein: the sulfur acid is one or more than two of 1-18 mol/L sulfuric acid, 0.1-5 mol/L benzenesulfonic acid, 1-12 mol/L thioacetic acid and 1-5 mol/L thiophenol.
10. Use of a sulphur promoted iridium based catalyst as claimed in any one of claims 1 to 6 in the carbonylation of heterogeneous methanol to produce methyl acetate.
11. Use according to claim 10, characterized in that: the adopted main reactor is made of hastelloy; the reaction temperature is 180 ℃ and 280 ℃, and the reaction pressure is 0.5-3.5 MPa; the iridium-based catalyst is activated or not activated before use, and the activation conditions are as follows: GHSV =4000h-1，CO/H2=10, pressure 0.5-3.5MPa, heating rate 1-10oC/min is heated from room temperature to 170-290℃/minoAnd C, keeping for 1-3 hours to obtain the activated iridium-based catalyst.
12. Use according to claim 11, characterized in that: the space velocity of the volume of the reaction liquid is 0.1-15h-1The molar ratio of CO to methanol is 1-2, and H is generated in the reaction process2And CO in a volume ratio of 0.1 to 2.
13. Use according to claim 10 or 11, characterized in that: the reaction raw material contains a cocatalyst of methyl iodide, and the addition amount of the cocatalyst is 1-35.0wt% of methanol.
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