CN112791743B - Catalyst for producing methyl acetate by dimethyl ether carbonylation, preparation method and application thereof - Google Patents
Catalyst for producing methyl acetate by dimethyl ether carbonylation, preparation method and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
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- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
Abstract
The application discloses a catalyst for producing methyl acetate by dimethyl ether carbonylation, a preparation method and an application thereof. The catalyst contains a modified H-MOR molecular sieve; the modified H-MOR molecular sieve is prepared by exchanging the H-MOR molecular sieve with pyridinium. Dimethyl ether and feed gas containing carbon monoxide are led to pass through a reactor filled with an acidic molecular sieve catalyst for selectively regulating and controlling active sites, the reaction temperature is 150-280 ℃, the reaction pressure is 0.5-25.0 MPa, and the dimethyl ether airspeed is 0.2-4 h‑1Reacting under the condition to produce methyl acetate.
Description
Technical Field
The invention relates to a catalyst for producing methyl acetate by dimethyl ether carbonylation, a preparation method and application thereof, belonging to the field of catalysis.
Background
The ethanol is used as a clean energy source and can be used as a gasoline additive to partially replace gasoline, the octane number of the gasoline is improved, the full combustion of the gasoline is effectively promoted, and the emission of carbon monoxide and hydrocarbons in automobile exhaust is reduced.
From coal resources, the production of ethanol by synthesis gas is an important direction for the development of the coal chemical industry in China, and has wide market prospect. The method has the advantages of clean utilization of coal resources, relieving the contradiction of shortage of petroleum resources, improving the energy safety of China, and having important strategic significance and profound influence. At present, the process routes for preparing ethanol from coal are mainly divided into two types: firstly, ethanol is directly prepared from synthesis gas, but a noble metal rhodium catalyst is needed, so that the cost of the catalyst is high; the other is that the synthetic gas is hydrogenated to prepare the ethanol through the acetic acid, the synthetic gas is firstly subjected to the methanol liquid phase carbonylation to prepare the acetic acid, and then is hydrogenated to synthesize the ethanol. The process of the route is mature, but the equipment needs special alloy with corrosion resistance and has higher cost.
U.S. Pat. No. 4, 20070238897, 1 discloses molecular sieves having an eight-membered ring channel structure, such as MOR, FER and OFF asEther carbonylation catalyst, with eight-membered ring channel size greater than 0.25X 0.36nm, under the conditions of 165 deg.C and 1MPa, 0.163-MeOAc (g-Cat. h) is obtained-1The space-time yield of (a). WO2008132450A1 reports that the performance of the MOR catalyst modified by copper and silver is obviously superior to that of an unmodified MOR catalyst under the conditions of hydrogen atmosphere and 350 ℃ of 250-. CN102950018A discloses the data of dimethyl ether carbonylation reaction on rare earth ZSM-35/MOR eutectic molecular sieve. The results show that the activity and stability of the eutectic molecular sieve are obviously superior to those of the ZSM-35 alone, and the stability of the eutectic molecular sieve is obviously superior to that of the MOR catalyst alone.
CN101613274A utilizes pyridine organic amine to modify mordenite molecular sieve catalyst, and finds that the modification of the molecular sieve can greatly improve the stability of the catalyst. The conversion rate of dimethyl ether is 10-60%, the selectivity of methyl acetate is more than 99%, and the activity of the catalyst is kept stable after 48 hours of reaction. The above documents disclose a large number of research results on carbonylation of dimethyl ether, the catalysts of which are mainly focused on MOR, FER, etc. having an eight-membered ring structure. The catalyst is extremely easy to deactivate after being stably operated for less than 100 hours in the publicly reported results, and the related results cannot meet the requirements of industrial production.
Disclosure of Invention
The invention aims to provide a catalyst, which takes an H-MOR molecular sieve prepared by performing pyridinium exchange treatment on a sample containing the H-MOR molecular sieve as an active component, and provides a new catalyst system for producing methyl acetate from dimethyl ether.
Optionally, the H-MOR molecular sieve has a silicon-aluminum atomic ratio of 6-50.
Alternatively, the H-MOR molecular sieve has an upper limit on the silicon to aluminum atomic ratio selected from 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 20, 25, 30, 35, 40, 45, or 50; the lower limit is selected from 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 20, 25, 30, 35, 40, or 45.
Alternatively, the pyridinium salt has a structural formula shown in formula I:
wherein R is1，R2Independently selected from H-, F-, Br-, CH3O-、CH3-、CH3CH2-、 CH3(CH2)nCH2-、(CH3)2CH-、(CH3)2CHCH2-any of; wherein, 0<n≤ 4；
R3Selected from H-, CH3-、CH3CH2-、CH3CH2CH2-、CH3CH2CH2CH2-any of;
x is selected from-F, -Cl, -Br, -I, -COOCH3、-SO4 2-、-NO3Any one of the above groups.
Optionally, the pyridine salt is preferably one or a mixture of any several of pyridine hydrochloride, pyridine hydrogen bromide salt, pyridine hydrogen fluoride salt, picoline hydrochloride, picoline hydrogen bromide salt, picoline hydrogen fluoride salt, pyridine sulfate, pyridine acetate and pyridine nitrate.
In another aspect of the present application, there is provided a method for preparing the catalyst as described above.
The preparation method of the catalyst comprises the following steps:
and (3) placing a sample containing the H-MOR molecular sieve in a solution containing pyridinium, performing exchange treatment for 1-10H at the temperature of 20-100 ℃, and washing, filtering and drying a product to obtain the catalyst.
Optionally, the concentration of the pyridinium in the solution containing the pyridinium is 0.05-2 mol/L.
Optionally, the upper limit of the concentration of the pyridinium salt in the pyridinium salt containing solution is selected from the group consisting of 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L, or 2.0 mol/L; the lower limit is selected from 0.05mol/L, 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L or 1.9 mol/L.
Optionally, the ratio of the mass of the H-MOR to the volume of the solution of the pyridinium salt is 5-100 g/mL.
Optionally, the exchange temperature is 30-80 ℃ and the time is 2-6 hours.
Optionally, repeating the exchanging step 2-8 times.
As an embodiment, the method for preparing the catalyst comprises the steps of:
performing exchange treatment on a sample containing the H-MOR molecular sieve for 1-10 hours at the temperature of 20-100 ℃ by using a pyridinium solution, and washing, filtering and drying a product; repeating the steps for 2-8 times to obtain the dimethyl ether methyl acetate catalyst.
In another aspect of the present application, there is provided a process for producing methyl acetate by carbonylation of dimethyl ether, wherein dimethyl ether and a feed gas containing carbon monoxide are introduced into a reactor, contacted with any one of the catalysts described above and the catalyst prepared by any one of the methods described above, and reacted to obtain methyl acetate.
Optionally, the reaction temperature is 150-280 ℃, the reaction pressure is 0.5-25.0 MPa, and the mass space velocity of dimethyl ether is 0.2-3 h-1；
In the raw material gas, the molar ratio of carbon monoxide to dimethyl ether is 0.1: 1-30: 1.
Optionally, the upper limit of the reaction temperature is selected from 170 ℃, 180 ℃, 200 ℃, 210 ℃, 220 ℃, 240 ℃, 260 ℃ or 280 ℃; the lower limit is selected from 150 deg.C, 170 deg.C, 180 deg.C, 200 deg.C, 210 deg.C, 220 deg.C, 240 deg.C or 260 deg.C.
Alternatively, the upper limit of the reaction pressure is selected from 1MPa, 1.5MPa, 2MPa, 0.5MPa, 2.5MPa, 3MPa, 5MPa, 6MPa, 8MPa, 10MPa, 12MPa, 15MPa, 18MPa, 20MPa, 22MPa or 25 MPa; the lower limit is selected from 0.5MPa, 1MPa, 1.5MPa, 2MPa, 0.5MPa, 2.5MPa, 3MPa, 5MPa, 6MPa, 8MPa, 10MPa, 12MPa, 15MPa, 18MPa, 20MPa or 22 MPa.
Alternatively, the upper limit of the mass space velocity of dimethyl ether is selected from 0.3h-1、0.5h-1、0.8h-1、1.0h-1、 1.2h-1、1.5h-1、1.8h-1、2.0h-1、2.2h-1、2.5h-1、2.8h-1Or 3.0h-1(ii) a The lower limit is selected from 0.2h-1、0.3h-1、0.5h-1、0.8h-1、1.0h-1、1.2h-1、1.5h-1、1.8h-1、2.0h-1、 2.2h-1、2.5h-1Or 2.8h-1。
Alternatively, the molar ratio of carbon monoxide to dimethyl ether is any ratio between 0.1:1, 0.2:1, 0.5:1, 0.8:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 5:1, 6:1, 8:1, 10:1, 12:1, 15:1, 18:1, 20:1, 22:1, 25:1, 28:1, 30:1, and ranges between any two ratios.
The operating conditions such as the ratio of dimethyl ether to carbon monoxide in the raw material gas, the reaction temperature, the reaction pressure, the space velocity and the like can be selected by a person skilled in the art according to actual needs.
As an implementation mode, the reaction temperature is 160-280 ℃, the reaction pressure is 0.5-20.0 MPa, and the mass space velocity of dimethyl ether is 0.2-3.0 h-1；
In the raw material gas, the molar ratio of carbon monoxide to dimethyl ether is 0.1: 1-20: 1.
Further preferably, the temperature is 170-260 ℃, the pressure is 1.0-15.0 MPa, and the mass space velocity of dimethyl ether is 0.2-3.0 h-1And the molar ratio of carbon monoxide to dimethyl ether is 0.2: 1-15: 1.
Optionally, the carbon monoxide-containing raw material gas further comprises any one or more of hydrogen, nitrogen, argon, carbon dioxide and methane.
Optionally, the volume content of the carbon monoxide is 15-100% based on the total volume of the raw gas containing the carbon monoxide.
In one embodiment, the raw gas containing carbon monoxide may contain any one or more of hydrogen, nitrogen, argon, carbon dioxide and methane in addition to carbon monoxide; preferably, the volume content of the carbon monoxide is 15-100%, and the volume content of any one or more of other gases such as hydrogen, nitrogen, argon, carbon dioxide and methane is 0-85%, based on the total volume of the raw gas containing the carbon monoxide.
The skilled person can select a suitable reactor according to the actual production needs. Preferably, the reactor is a fixed bed reactor.
Benefits of the present application include, but are not limited to:
(1) the invention provides a catalyst for producing methyl acetate from dimethyl ether, which has the advantages of high activity, high space-time yield of methyl acetate, good stability and the like.
(2) The invention provides a preparation method of a catalyst, which can realize the directional elimination and protection of an acid site of the catalyst and provides a new method for the preparation of a molecular sieve catalyst.
(3) The catalyst is applied to the reaction of producing methyl acetate by dimethyl ether carbonylation, not only can ensure high product yield and long service life, but also has wide adjustable range of reaction process conditions, so that the catalyst has universality and extremely wide industrial application range.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, the starting materials in the examples of the present application were all purchased commercially, wherein the H-MOR samples were provided by the energy technology corporation of the extended intermediate sciences (Dalian).
The analysis method in the examples of the present application is as follows:
the dimethyl ether conversion and methyl acetate selectivity analysis were performed using on-line chromatography.
The conversion, selectivity, in the examples of the present application were calculated as follows:
in the examples of the present application, the dimethyl ether conversion and methyl acetate selectivity were calculated on a carbon mole basis:
dimethyl ether conversion x (DME) ═ 1-2 × DME/(2 × DME +2MAc + Ac + MeOH + Σ (n × C)nHm)))*100. DME is reactor outlet concentration, MAc is reactor outlet methyl acetate concentration, Ac is reactor outlet acetic acid concentration, MeOH is reactor outlet methanol concentration, CnHmIs the concentration of hydrocarbons at the reactor outlet, and n and m are the number of carbon and hydrogen atoms of the hydrocarbon species, respectively.
Methyl acetate selectivity: s (MAc) ═ 2 × MAc/(2MAc + Ac + MeOH + Σ (n × C)nHm)*))*100
Acetic acid selectivity: s (MAc) ═ Ac/(2MAc + Ac + MeOH + Σ (n × C)nHm)*))*100
MAc is reactor outlet methyl acetate concentration, Ac is reactor outlet acetic acid concentration, MeOH is reactor outlet methanol concentration, CnHmIs the concentration of the hydrocarbon species at the reactor outlet, and n and m are the carbon and hydrogen atoms of the hydrocarbon species, respectively.
In the examples, the atomic ratio of Si to Al of H-MOR is represented by "Si/Al".
Example 1
Putting 100.0g H-MOR (Si/Al ═ 15) molecular sieve into 1000mL pyridine hydrochloride solution with concentration of 1.0mol/L, processing at 80 ℃ for 4h, filtering, washing, drying, repeating the above steps 3 times to obtain catalyst # 1.
Example 2
Respectively replacing pyridine hydrochloride with a mixed solution of pyridine bromide, picoline hydrochloride, ethylpyridine hydrochloride, pyridine sulfate, pyridine acetate and (0.2mol/L of pyridine bromide +0.2mol/L of picoline hydrochloride +0.1mol/L of pyridine sulfate +0.1mol/L of pyridine acetate +0.2mol/L of pyridine hydrochloride); all preparation procedures are consistent with those of example 1, and catalysts No. 2, No. 3, No. 4, No. 5, No. 6 and No. 7 are prepared in sequence.
Example 3
The pyridine hydrochloride concentrations were changed to 0.5, 1.5, and 2.0mol/L, and all preparation procedures were kept the same as in example 1, and catalysts # 8, # 9, and # 10 were prepared in this order.
Example 4
When the treatment temperature was changed to 20 ℃, 50 ℃ and 100 ℃, the other conditions were kept the same as in example 1, and catalysts # 11, # 12 and # 13 were prepared in this order.
Example 5
When the treatment time was changed to 1 hour, 8 hours, and 10 hours, catalysts # 14, # 15, and # 16 were prepared in this order under the same conditions as in example 1.
Example 6
When the above step 3 times is repeated after drying and changed into 2 times, 5 times and 8 times, other conditions are kept consistent with those of example 1, and catalysts 17#, 18#, and 19# are prepared in sequence.
Example 7
When the molar ratio of Si to Al atoms of H-MOR is respectively 6.5, 10, 20, 30, 40 and 50, the other conditions are kept consistent with those of example 1, and catalysts 20#, 21#, 22#, 23#, 24# and 25# are prepared in sequence.
Example 8
The above catalyst was examined for performance under the following conditions.
1.0g of catalyst is loaded into a fixed bed reactor with the inner diameter of 8mm, the temperature is raised to 250 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, the temperature is kept for 4 hours, then the reaction temperature is lowered to 200 ℃ under the nitrogen atmosphere, and the dimethyl ether with the composition is prepared by the following steps: CO: n is a radical of2The raw material gas with the ratio of 5:35:60 passes through a reactor, the reaction pressure is 2.0MPa, the reaction temperature is 200 ℃, and the gas volume space velocity GHSV is 2250 mL/g.h. The catalytic reaction was run for 100 hours and the results are shown in Table 1.
TABLE 1 evaluation results of dimethyl ether carbonylation catalysts with different catalysts
Table 1 shows that the molecular sieve silica-alumina ratio has a significant effect on activity.
The catalytic results of samples 9# to 19# were similar to sample 1 #.
Example 9
Dimethyl ether carbonylation reaction result under different reaction temperatures
1.0g of catalyst is loaded into a fixed bed reactor with the inner diameter of 8mm, the temperature is raised to 250 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, the temperature is kept for 4 hours, and then the temperature is lowered to the reaction temperature under the nitrogen atmosphere, and the catalyst is prepared by the following steps: CO: n is a radical of2The raw material gas with the ratio of 5:35:60 is introduced into a reactor, the reaction pressure is 2.0MPa, and the gas volume space velocity GHSV is 4500 mL/g.h. The reaction temperatures were 170 deg.C, 210 deg.C, 240 deg.C and 260 deg.C, respectively. The results of the catalytic reaction run for 100 hours are shown in Table 2.
TABLE 2 reaction results at different reaction temperatures
| Reactor inlet temperature (. degree.C.) | 170 | 210 | 240 | 260 |
| Conversion ratio of dimethyl ether (%) | 16.7 | 55.6 | 60.4 | 75.8 |
| Methyl acetate selectivity (%) | 99.5 | 99.0 | 98.1 | 98.0 |
| Acetic acid selectivity (%) | 0.3 | 0.5 | 0.9 | 1.1 |
As can be seen in table 2, increasing the temperature promoted the carbonylation to proceed.
Example 10
Dimethyl ether carbonylation reaction result under different reaction pressures
The catalyst used was a sample # 1, the reaction pressures were 1.0, 6.0, 10.0 and 15.0MPa, the reaction temperature was 200 ℃, and the gas volume space velocity GHSV was 4500mL/g · h, except that the other conditions were the same as in example 5. After the reaction was run for 100h, the reaction results are shown in Table 3.
TABLE 3 results of reactions at different reaction pressures
As can be seen in Table 3, it is shown that increasing the pressure promotes the carbonylation.
Example 11
Dimethyl ether carbonylation reaction result under different dimethyl ether space velocities
The catalyst used is 1# sample, and the dimethyl ether feeding airspeeds are respectively 0.5, 1, 2 and 2.5h-1The reaction temperature was 200 ℃ and the other conditions were the same as in example 5. After the reaction was run for 100 hours, the reaction results are shown in Table 4.
TABLE 4 reaction results at different space velocities of dimethyl ether
| Dimethyl ether feed space velocity (h)-1) | 0.5 | 1 | 2.0 | 2.5 |
| Conversion ratio of dimethyl ether (%) | 45.5 | 25.4 | 12.1 | 7.8 |
| Methyl acetate selectivity (%) | 99.3 | 99.1 | 99.0 | 98.7 |
| Acetic acid selectivity (%) | 0.1 | 0.5 | 0.6 | 0.8 |
As can be seen in Table 4, it is shown that increasing the volumetric space velocity, the contact time of the reactants decreases, which is detrimental to the carbonylation process.
Example 12
Dimethyl ether carbonylation reaction result under different molar ratios of carbon monoxide to dimethyl ether
The catalyst used was a sample # 1, the molar ratios of carbon monoxide and dimethyl ether were 0.2, 0.5, 2, 6 and 12, respectively, the reaction temperature was 200 ℃ and the gas volume space velocity GHSV was 4500mL/g · h, otherwise the conditions were the same as in example 5. After the reaction was run for 100 hours, the reaction results are shown in Table 5.
TABLE 5 results of reactions with different volume ratios of dimethyl ether and carbon monoxide
| Carbon monoxide/dimethyl ether molar ratio | 12 | 8 | 4 | 2 | 0.5 | 0.2 |
| Conversion ratio of dimethyl ether (%) | 85.5 | 60.6 | 28.8 | 15.8 | 5.3 | 2.0 |
| Methyl acetate selectivity (%) | 99.4 | 98.9 | 99.1 | 99.0 | 98.3 | 98.3 |
As can be seen in Table 5, increasing the CO/DME molar ratio helps to promote carbonylation.
Example 13
Dimethyl ether carbonylation reaction result of carbon monoxide-containing feed gas containing different inert gases
The catalyst used is a 1# sample, and the space velocity of dimethyl ether feeding is 0.23h-1The carbon monoxide feed gas contained an inert gas, the molar ratio of carbon monoxide to dimethyl ether at the inlet of the reactor was maintained at 7:1, and the reaction temperature was 200 ℃ under the same conditions as in example 5. After the reaction was run for 100 hours, the reaction results are shown in Table 6.
TABLE 6 reaction results when the carbon monoxide-containing feed gas contains an inert gas
Table 6 shows that the inert gas has less influence on the reaction.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (13)
1. A method for producing methyl acetate by dimethyl ether carbonylation is characterized in that dimethyl ether and feed gas containing carbon monoxide are introduced into a reactor and contact with a catalyst to react to obtain methyl acetate;
the catalyst contains a modified H-MOR molecular sieve;
the modified H-MOR molecular sieve is prepared by exchanging the H-MOR molecular sieve with pyridinium;
the silicon-aluminum atomic ratio of the H-MOR molecular sieve is 12-18.
2. The method of claim 1, wherein the pyridinium salt has the formula I:
wherein R is1，R2Independently selected from H-, F-, Br-, CH3O-、CH3-、CH3CH2-、CH3(CH2)nCH2-、(CH3)2CH-、(CH3)2CHCH2-any of; wherein, 0<n≤4；
R3Selected from H-, CH3-、CH3CH2-、CH3CH2CH2-、CH3CH2CH2CH2-any of;
x is selected from-F, -Cl, -Br, -I, -COOCH3、-NO3Any one of the above groups.
3. The method according to claim 1, wherein the pyridine salt is selected from one or more of pyridine hydrochloride, pyridine hydrogen bromide salt, pyridine hydrogen fluoride salt, picoline hydrochloride, picoline hydrogen bromide salt, picoline hydrogen fluoride salt, pyridine sulfate, pyridine acetate and pyridine nitrate.
4. A process according to any one of claims 1 to 3, characterized in that the catalyst is prepared by a process comprising the steps of:
and (3) placing a sample containing the H-MOR molecular sieve in a solution containing pyridinium, performing exchange treatment for 1-10H at the temperature of 20-100 ℃, and washing, filtering and drying a product to obtain the catalyst.
5. The method according to claim 4, wherein the concentration of the pyridinium salt in the solution containing the pyridinium salt is 0.05-2 mol/L.
6. The process of claim 4, wherein the ratio of the mass of said H-MOR molecular sieve to the volume of said pyridinium solution is from 5 to 100 g/mL.
7. The method according to claim 4, wherein the temperature of the exchange is 30-80 ℃ and the time is 2-6 hours.
8. The method of claim 4, wherein the step of exchanging is repeated 2-8 times.
9. The method of claim 1, wherein the reaction temperature is 150-280 ℃, the reaction pressure is 0.5-25.0 MPa, and the mass space velocity of dimethyl ether is 0.2-3 h-1；
In the raw material gas, the molar ratio of carbon monoxide to dimethyl ether is 0.1: 1-30: 1.
10. The method according to claim 9, wherein the reaction temperature is 160 to 280 ℃ and the reaction pressure is 0.5 to 20.0 MPa;
in the raw material gas, the molar ratio of carbon monoxide to dimethyl ether is 0.1: 1-20: 1.
11. The method of claim 10, wherein the reaction temperature is 170 to 260 ℃ and the reaction pressure is 1.0 to 15.0 MPa;
in the raw material gas, the molar ratio of carbon monoxide to dimethyl ether is 0.2: 1-15: 1.
12. The method of claim 1, wherein the carbon monoxide-containing feed gas further comprises any one or more of hydrogen, nitrogen, argon, carbon dioxide, and methane.
13. The method according to claim 12, wherein the volume content of carbon monoxide is 15 to 100% based on the total volume of the carbon monoxide-containing raw material gas.
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| EP2189215A1 (en) * | 2008-11-19 | 2010-05-26 | BP Chemicals Limited | Carbonylation process catalysed by mordenite supported on inorganic oxides |
| CN103896767A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method used for preparing methyl acetate |
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