CN111514926B - Molecular sieve catalyst, and preparation method and application thereof - Google Patents
Molecular sieve catalyst, and preparation method and application thereof Download PDFInfo
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- CN111514926B CN111514926B CN201910107338.XA CN201910107338A CN111514926B CN 111514926 B CN111514926 B CN 111514926B CN 201910107338 A CN201910107338 A CN 201910107338A CN 111514926 B CN111514926 B CN 111514926B
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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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- 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
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
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- B01J2229/34—Reaction with organic or organometallic compounds
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
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Abstract
The application discloses a molecular sieve catalyst, a preparation method and application thereof, wherein the molecular sieve catalyst contains a modified Na-MOR molecular sieve; the modification comprises the following steps: through organic ammonium salt exchange, dealumination treatment and ammonium ion exchange. The catalyst obtained by the method is used for producing methyl acetate by dimethyl ether in one step, has high activity and stable performance, and can meet the requirement of industrial production.
Description
Technical Field
The application relates to a molecular sieve catalyst, a preparation method and application thereof, belonging to the field of catalysis.
Background
With the rapid development of modern industry, the contradiction between energy supply and demand is more and more prominent. As a large energy consumption country and a large energy shortage country, China urgently needs to find alternative energy. The ethanol is used as a clean energy source, has good intersolubility, can be used as a blending component to be blended into gasoline to partially replace the gasoline, improves the octane number and oxygen content of the gasoline, effectively promotes the full combustion of the gasoline, and reduces the emission of carbon monoxide and hydrocarbons in automobile exhaust. The ethanol is used as a partial substitute of the vehicle fuel, so that the vehicle fuel in China can present diversified structural characteristics. At present, the fuel ethanol developed by using grains, particularly corn, as the raw material in China is the third largest fuel ethanol production and consumption country which is second to Brazil and America, but according to the national conditions of China, the ethanol production by using grains as the raw material has a plurality of adverse factors, and the fuel ethanol developed by China in the future is more non-grain routes.
From coal resources, the production of ethanol by synthesis gas is an important direction for the development of novel 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, the cost of the catalyst is high, and the yield of rhodium is limited; 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. 3, 20070238897, 1 discloses that molecular sieves having an eight-member ring channel structure, such as MOR, FER and OFF, as ether carbonylation catalysts and eight-member ring channel sizes greater than 0.25X 0.36nm, obtained 0.163-MeOAc (g-Cat. h) in the presence of mordenite as a catalyst at 165 ℃ and 1MPa-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
According to one aspect of the present application, a molecular sieve catalyst is provided, which has high activity and stable performance, and can meet the requirements of industrial production.
The application provides a catalyst for producing methyl acetate by dimethyl ether carbonylation, a preparation method and application thereof. The catalyst is prepared by exchanging Na-MOR molecular sieve (sodium mordenite molecular sieve) with tetraalkylammonium chloride and its derivatives, treating with acid and/or water vapor, and exchanging with ammonium chloride and/or ammonium nitrate. Dimethyl ether and feed gas containing carbon monoxide are passed through a reactor containing a catalyst containing a selectively regulated active site acidic molecular sieve, 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. The catalyst provided by the invention has high activity and stable performance, and can meet the requirements of industrial production.
The molecular sieve catalyst is characterized in that the molecular sieve catalyst contains a modified Na-MOR molecular sieve;
the modification comprises the following steps: through organic ammonium salt exchange, dealumination treatment and ammonium ion exchange.
Optionally, the dealumination treatment is selective dealumination (directional dealumination of molecular sieves).
Optionally, the modified Na-MOR molecular sieve is the active component.
Optionally, the ammonium ion exchange is followed by calcination.
Optionally, the modifying comprises: sequentially carrying out organic ammonium salt exchange, dealumination treatment and ammonium ion exchange.
Optionally, the modifying comprises: sequentially carrying out organic ammonium salt exchange, acid and/or water vapor treatment and ammonium ion exchange.
Optionally, the modifying comprises: sequentially carrying out organic ammonium salt exchange, acid treatment, water vapor treatment and ammonium ion exchange.
Optionally, the organic ammonium salt is selected from at least one of alkyl ammonium chloride salt and alkyl ammonium nitrate salt.
Optionally, the molecular sieve catalyst is a modified Na-MOR molecular sieve.
Optionally, the organic ammonium salt exchange is an alkyl ammonium halide salt exchange.
Optionally, the molecular sieve catalyst is a modified Na-MOR molecular sieve;
the modification is alkyl ammonium chloride salt exchange, acid and/or water vapor treatment and ammonium nitrate exchange.
Optionally, the modification is sequentially carried out by alkyl ammonium chloride salt exchange, acid and/or water vapor treatment and ammonium nitrate exchange.
Optionally, the modification is alkyl ammonium chloride salt exchange, acid treatment, water vapor treatment, and ammonium nitrate exchange in sequence.
Optionally, the alkyl ammonium halide salt is selected from at least one of the compounds having the formula shown in formula I:
wherein R is1，R2，R3Independently selected from C1～C10One of the alkyl groups of (a);
R4is selected from C1～C10Alkyl of (C)6～C10One of the aryl groups of (a);
x is selected from at least one of F, Cl, Br or I.
Optionally, X is selected from one of F, Cl, Br or I.
Alternatively, R1，R2，R3Independently selected from C1～C6One of the alkyl groups of (1).
Alternatively, R1，R2，R3Independently selected from C1～C4One of the alkyl groups of (1).
Alternatively, R1，R2，R3The same is true.
Alternatively, R1，R2，R3Are not identical.
Alternatively, R4Is selected from C6～C8One of aryl groups of (1).
Alternatively, R4Is selected from C6～C8And (3) one of the alkyl-substituted benzenes of (1).
Optionally, the alkyl ammonium halide salt is an alkyl ammonium chloride salt.
Alternatively, R in formula I1，R2，R3Independently selected from CH3-、CH3CH2-、CH3(CH2)nCH2-、(CH3)2CH-、(CH3)2CHCH2-、CH3CH2(CH3) Any one of CH-groups;
R4is CH3-、CH3-、CH3CH2-、CH3(CH2)mCH2-、(CH3)2CH-、(CH3)2CHCH2-、CH3CH2(CH3)CH-、C6H5-、CH3C6H4-、(CH3)2C6H3-、C6H5CH2-any of;
wherein n and m are independently selected from 1, 2, 3 or 4.
Optionally, the Na-MOR molecular sieve has a silicon-aluminum atomic ratio of 6-50.
Optionally, the Na-MOR molecular sieve has an upper limit on the silica to alumina ratio selected from 6.5, 10, 15, 20, 30, 40 or 50; the lower limit is selected from 6, 6.5, 10, 15, 20, 30 or 40.
Optionally, the dealumination treatment comprises at least one of a high temperature roasting treatment and an acid treatment.
Optionally, the high-temperature roasting treatment is roasting in an atmosphere with a water vapor concentration of 0-100%.
Optionally, the atmosphere with the water vapor concentration of 0-100% comprises water vapor, an atmosphere A and a mixed atmosphere of the water vapor and the atmosphere A;
wherein, the atmosphere A is at least one of air, nitrogen and argon.
As one specific embodiment, dimethyl ether carbonylation to produce methyl acetate catalyst is carried out by passing samples containing Na-MOR molecular sieve successively (R)1)(R2)(R3)(R4) The H-MOR molecular sieve prepared by NCl (alkyl ammonium chloride salt) exchange and acid and/or steam treatment is used as an active component, and a new catalyst system for producing methyl acetate from dimethyl ether can be provided.
Alternatively, the catalyst is a catalyst of the formula (I) or (II)1)(R2)(R3)(R4) NCl (alkyl ammonium chloride salt) exchange, acid and/or steam treatment of the prepared catalyst.
In another aspect of the present application, there is provided a method for preparing a molecular sieve catalyst as described in any one of the above, comprising: and (3) carrying out organic ammonium salt exchange, dealumination treatment, ammonium ion exchange and roasting on the Na-MOR molecular sieve to obtain the molecular sieve catalyst.
Alternatively, the method of preparing the molecular sieve catalyst comprises:
(1) exchanging organic ammonium salt with a Na-MOR molecular sieve to obtain a precursor I;
(2) carrying out acid treatment on the precursor I to obtain a precursor II;
(3) carrying out high-temperature roasting treatment on the precursor II to obtain a precursor III;
(4) performing ammonium ion exchange on the precursor III to obtain a precursor IV;
(5) and roasting the precursor IV to obtain the molecular sieve catalyst.
Optionally, the organic ammonium salt exchange conditions in step (1) are: and (3) carrying out exchange treatment on the Na-MOR molecular sieve in an organic ammonium salt solution at the temperature of 20-100 ℃ for 1-10 hours.
Optionally, the upper temperature limit of the organic ammonium salt exchange treatment is selected from 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃; the lower limit is selected from 20 deg.C, 30 deg.C, 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C or 90 deg.C.
Alternatively, the upper limit of time for the organoammonium salt exchange treatment is selected from 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours.
Optionally, the concentration of the organic ammonium salt solution is 0.05-1 mol/L.
Optionally, the volume ratio of the Na-MOR molecular sieve to the organic ammonium salt solution is 1: 1-1: 15 (g/ml).
Optionally, the organic ammonium salt exchange solid-to-liquid ratio is 1 g: 2-15 ml.
Optionally, the upper concentration limit of the organic ammonium salt solution is selected from 0.08mol/L, 0.1mol/L, 0.3mol/L, 0.5mol/L, 0.8mol/L or 1 mol/L; the lower limit is selected from 0.05mol/L, 0.08mol/L, 0.1mol/L, 0.3mol/L, 0.5mol/L or 0.8 mol/L.
Optionally, the number of times of the organic ammonium salt exchange is 2-8;
the organic ammonium salt exchange conditions are as follows: exchange treatment is carried out for 2-6 hours at 30-80 ℃.
Optionally, the step (1) comprises: carrying out exchange treatment on a sample containing Na-MOR for 1-10 hours at 20-100 ℃ by using an organic ammonium salt solution, and washing, filtering and drying a product; repeating the above steps for 2-8 times.
Optionally, the acid treatment in step (2) is performed by using an acid selected from at least one of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and citric acid.
Optionally, the acid treatment conditions in step (2) are: treating in an acid solution at 30-100 ℃ for 1-10 hours.
Optionally, the concentration of the acidic solution is 0.05-1.5 mol/L.
Optionally, the upper temperature limit of the acid treatment is selected from 40 ℃, 50 ℃, 60 ℃, 80 ℃ or 100 ℃; the lower limit is selected from 30 deg.C, 40 deg.C, 50 deg.C, 60 deg.C or 80 deg.C.
Optionally, the upper limit of time for the acid treatment is selected from 2 hours, 3 hours, 5 hours, 8 hours, or 10 hours; the lower limit is selected from 1 hour, 2 hours, 3 hours, 5 hours, or 8 hours.
Optionally, the number of acid treatments is 2-10;
the acid treatment conditions are as follows: treating in an acid solution at 30-80 ℃ for 2-8 hours.
Optionally, the step (2) comprises: treating the sample obtained in the step (1) with an acid solution at 30-100 ℃ for 1-10 hours, washing, filtering and drying the product; repeating the above steps for 2-10 times.
Optionally, the conditions of the high-temperature roasting treatment in the step (3) are as follows: treating for 1-10 hours at 300-800 ℃ in an atmosphere with water vapor concentration of 0-100%.
Optionally, the upper limit of the concentration of water vapor in the high temperature calcination atmosphere is selected from 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%; the lower limit is selected from 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%.
Optionally, the upper temperature limit of the high temperature roasting treatment is selected from 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃ or 800 ℃; the lower limit is selected from 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C, 700 deg.C or 750 deg.C.
Optionally, the upper limit of time of the high temperature calcination treatment is selected from 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours; the lower limit is selected from 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, or 9 hours.
Optionally, the conditions of the high-temperature roasting treatment are as follows: treating for 2-6 hours at 350-750 ℃ in an atmosphere with the water vapor concentration of 0-100%.
Optionally, the step (3) comprises: and (3) treating the sample obtained in the step (2) for 1-10 hours at 300-800 ℃ in an atmosphere with the water vapor concentration of 0-100%.
Alternatively, the conditions for ammonium ion exchange in step (4) are: exchange treatment at 20-100 ℃ for 1-10 hours.
Optionally, the upper temperature limit of the ammonium ion exchange is selected from 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃; the lower limit is selected from 20 deg.C, 30 deg.C, 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C or 90 deg.C.
Alternatively, the upper limit of time for the ammonium ion exchange is selected from 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours; the lower limit is selected from 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, or 9 hours.
Optionally, the number of ammonium ion exchanges is 2-5;
the ammonium ion exchange condition is that the exchange treatment is carried out for 2-6 hours at the temperature of 30-90 ℃;
the ammonium ion exchange is carried out in a solution containing ammonium ions; the ammonium ion-containing solution is at least one selected from ammonium nitrate solution, ammonium chloride solution, ammonium sulfate solution and ammonium acetate solution.
Optionally, the step (4) comprises: performing exchange treatment on the sample obtained in the step (3) in an ammonium ion-containing solution at the temperature of 20-100 ℃ for 1-10 hours, and washing, filtering and drying the product; repeating the steps for 2-5 times.
Optionally, the roasting conditions in step (5) are: roasting for 2-8 hours at 300-800 ℃ in air atmosphere.
Optionally, the upper temperature limit of the roasting is selected from 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃ or 800 ℃; the lower limit is selected from 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C, 700 deg.C or 750 deg.C.
Optionally, the upper time limit for the calcination is selected from 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, or 8 hours; the lower limit is selected from 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, or 7 hours.
Optionally, the roasting conditions are: roasting for 4-6 hours at 400-750 ℃ in an air atmosphere.
Optionally, the step (5) comprises: and (4) roasting the sample obtained in the step (4) for 2-8 hours at the temperature of 300-800 ℃ in air to prepare the catalyst.
Alternatively, the method of preparing the molecular sieve catalyst comprises:
a) exchanging the solid containing the Na-MOR molecular sieve for 1-10 hours at 20-100 ℃ by using a solution containing alkyl ammonium halide salt, wherein the exchange times are 2-8 times, and obtaining a precursor I;
b) treating the precursor I with an acid solution at 30-100 ℃ for 1-10 hours for 2-10 times to obtain a precursor II;
c) treating the precursor II for 1-10 hours at 300-800 ℃ in an atmosphere with the water vapor concentration of 0-100% to obtain a precursor III;
d) performing exchange treatment on the precursor III in an ammonium nitrate aqueous solution at the temperature of 20-100 ℃ for 1-10 hours, wherein the exchange times are 2-5 times, and obtaining a precursor IV;
e) and roasting the precursor IV for 2-8 hours at the temperature of 300-800 ℃ in air to prepare the molecular sieve catalyst.
As a specific embodiment, the preparation method of the molecular sieve catalyst comprises the following steps:
(S1) applying (R) to the sample containing Na-MOR1)(R2)(R3)(R4) Carrying out exchange treatment on NCl salt solution at the temperature of 20-100 ℃ for 1-10 hours, and washing, filtering and drying a product; repeating the steps for 2-8 times;
(S2) treating the sample obtained in the step (S1) with an acid solution at 30-100 ℃ for 1-10 hours, and washing, filtering and drying the product; repeating the steps for 2-10 times;
(S3) treating the sample obtained in the step (S2) for 1-10 hours under the conditions of water vapor atmosphere and 300-800 ℃;
(S4) performing exchange treatment on the sample obtained in the step (S3) in an ammonium nitrate aqueous solution at the temperature of 20-100 ℃ for 1-10 hours, and washing, filtering and drying the product; repeating the steps for 2-5 times;
(S5) roasting the sample obtained in the step (S4) for 2-8 hours at the temperature of 300-800 ℃ in air to prepare the catalyst.
In another aspect of the present application, there is provided the use of at least one of the molecular sieve catalyst described in any one of the above, and the molecular sieve catalyst prepared according to any one of the above methods, as a catalyst for the carbonylation of dimethyl ether to produce methyl acetate.
In another aspect of the present application, there is provided a process for the carbonylation of dimethyl ether to produce methyl acetate, comprising: introducing dimethyl ether and feed gas containing carbon monoxide into a reactor loaded with a catalyst bed layer, and carrying out contact reaction with the catalyst to produce methyl acetate;
wherein the catalyst is selected from at least one of the molecular sieve catalyst described in any one of the preceding claims, the molecular sieve catalyst prepared according to the process described in any one of the preceding claims.
The operating conditions such as the ratio of dimethyl ether to carbon monoxide in the feed 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 the actual needs.
The skilled person can select a suitable reactor according to the actual production needs.
Optionally, the reaction conditions are:
the reaction temperature is 150-280 ℃, the reaction pressure is 0.5-25.0 MPa, and the mass space velocity of dimethyl ether feeding is 0.05-5 h-1；
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 160 ℃, 170 ℃, 180 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃ or 280 ℃; the lower limit is selected from 150 deg.C, 160 deg.C, 170 deg.C, 180 deg.C, 200 deg.C, 210 deg.C, 220 deg.C, 230 deg.C, 240 deg.C, 250 deg.C, 260 deg.C or 270 deg.C.
Optionally, the upper reaction pressure limit is selected from 1MPa, 2MPa, 5MPa, 6MPa, 8MPa, 10MPa, 12MPa, 15MPa, 18MPa, 20MPa, or 25 MPa; the lower limit is selected from 0.5MPa, 1MPa, 2MPa, 5MPa, 6MPa, 8MPa, 10MPa, 12MPa, 15MPa, 18MPa or 20 MPa.
Alternatively, the mass space velocity of the dimethyl ether feed is selected from 0.1h-1、0.2h-1、0.25h-1、0.35h-1、0.5h-1、1h-1、1.2h-1、1.5h-1、2h-1、2.5h-1、4h-1、4.5h-1Or 5h-1(ii) a The lower limit is selected from 0.05h-1、0.1h-1、0.2h-1、0.25h-1、0.35h-1、0.5h-1、1h-1、1.2h-1、1.5h-1、2h-1、2.5h-1、4h-1Or 4.5h-1。
Optionally, the upper limit of the molar ratio of carbon monoxide to dimethyl ether is selected from 0.2:1, 0.5:1, 1:1, 2:1, 4:1, 6:1, 8:1, 12:1, 15:1, 18:1, 20:1, 25:1 or 30: 1; the lower limit is selected from 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 4:1, 6:1, 8:1, 12:1, 15:1, 18:1, 20:1 or 25: 1.
Optionally, the reaction conditions are:
the reaction temperature is 160-280 ℃, the reaction force is 0.5-20.0 MPa, and the mass space velocity of dimethyl ether feeding is 0.2-4.0 h-1；
The molar ratio of the carbon monoxide to the dimethyl ether is 0.1: 1-20: 1.
Optionally, the reaction conditions are:
the reaction temperature is 170-260 ℃, the reaction pressure is 1.0-15.0 MPa, and the mass space velocity of dimethyl ether feeding is 0.1-4.0 h-1；
The molar ratio of the carbon monoxide to the dimethyl ether is 0.2: 1-15: 1.
Optionally, the reaction conditions are:
the reaction temperature is 160-280 ℃, the reaction pressure is 0.5-20.0 MPa, and the mass space velocity of dimethyl ether feeding is 0.05-5 h-1The molar ratio of the carbon monoxide to the dimethyl ether is 0.1: 1-20: 1.
Optionally, the volume content of carbon monoxide in the feed gas containing carbon monoxide is 15-100%.
Optionally, the feed gas comprising carbon monoxide further comprises an inert gas.
Optionally, the inert gas is selected from at least one of inert gas, hydrogen, nitrogen, carbon dioxide, methane, ethane.
Optionally, the carbon monoxide-containing feed gas further comprises at least one of hydrogen, nitrogen, helium, argon, carbon dioxide, methane, ethane.
Optionally, the volume content of other gases (except carbon monoxide) in the feed gas containing carbon monoxide is 0-85%.
Optionally, the reactor is a fixed bed reactor.
Alternatively, the process for the carbonylation of dimethyl ether to produce methyl acetate results in a selectivity to methyl acetate in the product of greater than 90%.
Alternatively, the process for the carbonylation of dimethyl ether to produce methyl acetate results in a selectivity to methyl acetate in the product of greater than 98%.
Optionally, the space-time yield of methyl acetate in the product obtained by the method for producing methyl acetate by carbonylation of dimethyl ether is high and can reach more than or equal to 1g of MAc/(gcat.h).
In the present application, "C1～C10”，“C6～C10"and the like" each refer to the number of carbon atoms contained in a group.
In the present application, "aryl" refers to a group formed by the loss of any hydrogen atom from an aromatic hydrocarbon compound molecule.
In the present application, "alkyl" refers to a group formed by the loss of any one hydrogen atom from the molecule of an alkane compound.
The beneficial effects that this application can produce include:
1) the catalyst for one-step production of methyl acetate from dimethyl ether has high activity, high space-time yield of methyl acetate, high stability, long service life of over 8000 hr and high industrial application value.
2) The invention provides a preparation method of a catalyst, which can realize directional elimination and protection of an acid site of the catalyst and provides a new method for preparing 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 specified, the feedstocks in the examples of this application were all purchased commercially, with Na-MOR from Nankai catalyst plants.
The analysis method in the examples of the present application is as follows:
the reacted gas is led into an on-line chromatograph through a heated pipeline for on-line analysis. The chromatograph is Agilent 7890A and is provided with a PLOT Q capillary column and a TDX-1 packed column, the outlet of the PLOT-Q capillary column is connected with a FID detector, and the outlet of the TDX-1 packed column is connected with a TCD detector.
The conversion, selectivity, in the examples of the present application were calculated as follows:
in the examples of the present application, the conversion of dimethyl ether, the conversion of carbon monoxide and the selectivity of methyl acetate were calculated by:
in the examples, the conversion of dimethyl ether and the selectivity to methyl acetate were calculated based on the carbon moles of dimethyl ether:
conversion of dimethyl ether [ (mole number of dimethyl ether carbon in raw material gas) - (mole number of dimethyl ether carbon in product) ]/(mole number of dimethyl ether carbon in raw material gas) × (100%)
Methyl acetate selectivity (2/3) × (methyl acetate carbon moles in product) ÷ [ (dimethyl ether carbon moles in feed gas) - (dimethyl ether carbon moles in product) ] × (100%)
Carbon monoxide conversion rate ═ mole number of CO before reaction) - (mole number of CO after reaction) ]/(mole number of CO before reaction) × (100%)
According to one embodiment of the application, the dimethyl ether carbonylation catalyst for producing methyl acetate is a catalyst containing a modified Na-MOR molecular sieve as an active component.
As one embodiment, the modified Na-MOR molecular sieve is successively passed (R)1)(R2)(R3)(R4) NCl (alkyl ammonium chloride salt) exchange, acid and/or water vapor treatment, and ammonium nitrate exchange.
As one embodiment, the Na-MOR molecular sieve has a silicon-aluminum atomic ratio of 6-50.
As one embodiment thereof, the (R)1)(R2)(R3)(R4) R in NCl (alkyl ammonium chloride) salt1、R2、R3Is CH3-、CH3CH2-、CH3(CH2)nCH2- (where 0 ≦ n ≦ 4), (CH)3)2CH-、(CH3)2CHCH2-、CH3CH2(CH3) Any one of CH-groups; r4Is CH3-、CH3-、CH3CH2-、CH3(CH2)nCH2- (where 0 ≦ n ≦ 4), (CH)3)2CH-、(CH3)2CHCH2-、CH3CH2(CH3)CH-、C6H5-、CH3C6H4-、(CH3)2C6H3-、C6H5CH2Any one of the above-mentioned.
As one embodiment thereof, the (R)1)(R2)(R3)(R4) The NCl salt is preferably one or a mixture of more of tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, ethyltrimethylammonium chloride, diethyldimethylammonium chloride, triethylmethylammonium chloride, phenyltrimethylammonium chloride and benzyltrimethylammonium chloride.
As one embodiment, the method for preparing the catalyst for the carbonylation of dimethyl ether to produce methyl acetate is characterized by comprising the following steps:
a) the Na-MOR-containing sample is used as (R)1)(R2)(R3)(R4) Carrying out exchange treatment on NCl salt solution at the temperature of 20-100 ℃ for 1-10 hours, and washing, filtering and drying a product; repeating the steps for 2-8 times;
b) treating the sample obtained in the step a) with an acid solution at 30-100 ℃ for 1-10 hours, and washing, filtering and drying the product; repeating the steps for 2-10 times;
c) treating the sample obtained in the step b) for 1-10 hours under the conditions of water vapor atmosphere and 300-800 ℃;
d) exchanging the sample obtained in the step c) in an ammonium nitrate aqueous solution at the temperature of 20-100 ℃ for 1-10 hours, and washing, filtering and drying the product; repeating the steps for 2-5 times;
e) roasting the sample obtained in the step d) for 2-8 hours at the temperature of 300-800 ℃ in air to prepare the catalyst.
In one embodiment, the concentration of the salt solution in the step a) is 0.05-1 mol/L.
In one embodiment, the exchange temperature in step a) is 30-80 ℃ and the time is 2-6 hours.
As one embodiment, the acid solution in step b) is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, and citric acid.
In one embodiment, the temperature of the acid treatment in step b) is 30 to 80 ℃ and the time is 2 to 8 hours.
In one embodiment, the step c) is performed in a steam atmosphere at 350-750 ℃ for 2-6 hours.
In one embodiment, the temperature of the exchange treatment in step d) is 30 to 90 ℃ and the time is 2 to 6 hours.
As one embodiment, the sample obtained in the step e) is roasted for 4 to 6 hours under the conditions of air and 400 to 750 ℃.
As one embodiment thereof, the process for the carbonylation of dimethyl ether to produce methyl acetate comprises: introducing dimethyl ether and a feed gas containing carbon monoxide into a reactor, contacting the dimethyl ether and the catalyst with the methyl acetate produced by carbonylation of dimethyl ether prepared by any one of the methods, 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 0.2-4 h-1Reacting under the condition to produce methyl acetate;
in the feed gas, the molar ratio of dimethyl ether to carbon monoxide is 0.1: 1-30: 1.
As one embodiment, the carbonylation reaction is carried out at the temperature of 160-280 ℃, the pressure of 0.5-20.0 MPa and the mass space velocity of dimethyl ether feeding of 0.05-5 h-1The molar ratio of carbon monoxide to dimethyl ether is 0.1: 1-20: 1.
As one embodiment, the reaction temperature is 170-260 ℃, the pressure is 1.0-15.0 MPa, and the mass space velocity of dimethyl ether feeding is 0.1-4.0 h-1And the molar ratio of carbon monoxide to dimethyl ether is 0.2: 1-15: 1.
As one embodiment, the raw gas containing carbon monoxide may contain any one or more of hydrogen, nitrogen, helium, argon, carbon dioxide, methane and ethane in addition to carbon monoxide; preferably, based on the total volume of the raw gas containing carbon monoxide, the volume content of carbon monoxide is 15-100%, and the volume content of any one or more of other gases such as hydrogen, nitrogen, helium, argon, carbon dioxide, methane and ethane is 0-85%.
Example 1
Putting 100 g of Na-MOR (Si/Al ═ 15) molecular sieve into 1000ml of 0.5mol/L phenyltrimethylammonium chloride aqueous solution, treating at 80 ℃ for 4 hours, filtering, washing, drying, and repeating the above phenyltrimethylammonium chloride exchange treatment process for 5 times; then putting the prepared sample into 1000ml of oxalic acid water solution with the solubility of 0.5mol/L, processing for 3 hours at 60 ℃, filtering and washing, drying, and repeating the acid processing process for 3 times; the prepared sample is treated for 4 hours at 650 ℃ in a dry air atmosphere; treating the sample obtained by high-temperature treatment with 500ml of ammonium nitrate aqueous solution with the concentration of 1mol/L at 70 ℃ for 4 hours, washing and drying, and repeating the step of ammonium nitrate solution exchange treatment for 3 times; and roasting the prepared sample at 550 ℃ for 4 hours in an air atmosphere to prepare the catalyst No. 1.
Example 2
Respectively converting phenyltrimethyl ammonium chloride into tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, ethyltrimethyl ammonium chloride, diethyldimethyl ammonium chloride, triethylmethylammonium chloride, benzyltrimethyl ammonium chloride and ammonium chloride, and mixing; all preparation procedures are consistent with those of example 1, and catalysts No. 2, No. 3, No. 4, No. 5, No. 6, No. 7 and No. 8 are prepared in sequence.
Example 3
The solubility of phenyltrimethylammonium chloride was changed to 0.05mol/L, 0.1mol/L, 0.3mol/L, 1mol/L, and all preparation procedures were kept the same as in example 1, and catalysts # 9, # 10, # 11, and # 12 were prepared in this order.
Example 4
The oxalic acid is respectively changed into hydrochloric acid, nitric acid, sulfuric acid, acetic acid, citric acid and mixed acid of the above acids, other conditions are kept consistent with the embodiment 1, and the catalysts 13#, 14#, 15#, 16#, 17#, and 18# are prepared in sequence.
Example 5
The air atmosphere with 10% water vapor concentration, the air atmosphere with 40% water vapor concentration, and the atmosphere with 100% water vapor concentration were respectively replaced with the dry air atmosphere, and the other conditions were kept the same as in example 1, and catalysts # 19, # 20, and # 21 were prepared in this order.
Example 6
When the dry air atmosphere was changed to an air atmosphere having a steam concentration of 20%, the treatment temperatures were 350 ℃, 500 ℃, 600 ℃, 750 ℃, 800 ℃ and 300 ℃, respectively, and the other conditions were kept the same as in example 1, and catalysts # 22, # 23, # 24, # 25, # 26 and # 27 were prepared in this order.
Example 7
Na-MOR was treated with an aqueous solution of phenyltrimethylammonium chloride and then separately treated with an aqueous solution of oxalic acid by the following procedure (1); (2) roasting in dry air; (3) catalysts No. 28, No. 29 and No. 30 were prepared by treating in an air atmosphere having a water vapor concentration of 10% under the same conditions as those of the corresponding procedures in example 1 and then treating with an aqueous ammonium nitrate solution under the same conditions as those of the corresponding procedures in example 1.
Example 8
When the molar ratio of Si to Al atoms of Na-MOR is changed to 6.5, 10, 20, 30 and 50 respectively, other conditions are kept consistent with those of example 1, and catalysts 31#, 32#, 33#, 34# and 35# are prepared in sequence.
Example 9
The treatment temperature of the phenyltrimethylammonium chloride solution was changed to 20 ℃, 60 ℃, 100 ℃, and the other conditions were kept the same as in example 1, and catalysts # 36, # 37, and # 38 were prepared in this order.
The treatment time of the phenyltrimethylammonium chloride solution was changed to 1 hour, 2 hours, 6 hours and 10 hours, and the other conditions were kept the same as in example 1, thereby preparing catalysts # 39, # 40, # 41 and # 42 in this order.
The treatment times of the phenyltrimethylammonium chloride solution were changed to 2 times and 8 times, and other conditions were kept the same as in example 1, and catalysts # 43 and # 44 were prepared in this order.
Example 10
The temperature of the acid treatment was changed to 30 ℃, 80 ℃, 100 ℃, and other conditions were kept the same as in example 1, and catalysts # 45, # 46, and # 47 were prepared in this order.
The acid treatment time was changed to 1 hour, 2 hours, 8 hours, and 10 hours, and the other conditions were kept the same as in example 1, thereby preparing catalysts # 48, # 49, # 50, and # 51 in this order.
Catalysts # 52 and # 53 were prepared by changing the number of acid treatments to 2 and 10 times under otherwise identical conditions as in example 1.
Example 11
Catalysts 54#, 55#, 56#, and 57# were prepared by changing the treatment time in the dry air atmosphere to 1 hour, 2 hours, 6 hours, and 10 hours, and keeping the other conditions the same as in example 1.
Example 12
The temperature of ammonium nitrate solution treatment is changed to 20 ℃, 30 ℃, 90 ℃ and 100 ℃, and other conditions are kept consistent with those of the example 1, and then catalysts 58#, 59#, 60# and 61# are prepared in sequence.
The time for treating the ammonium nitrate aqueous solution is changed to 1 hour, 2 hours, 6 hours and 10 hours, other conditions are kept consistent with those of the example 1, and the catalysts 62#, 63#, 64#, and 65# are prepared in sequence.
Example 13
The calcination time was changed to 2 hours, 6 hours, and 8 hours, and other conditions were kept the same as in example 1, and catalysts # 66, # 67, and # 68 were prepared in this order.
The calcination temperature was changed to 300 ℃, 400 ℃, 750 ℃, 800 ℃, and other conditions were kept the same as in example 1, and catalysts 69#, 70#, 71#, and 72# were prepared in this order.
Example 14
Catalysts 73#, 74#, 75# were prepared by replacing ammonium nitrate aqueous solution with ammonium chloride aqueous solution, ammonium sulfate aqueous solution, and ammonium acetate aqueous solution, respectively, and keeping the other conditions the same as in example 1.
Example 15
The above catalyst was examined for performance under the following conditions.
10g of the catalyst was charged into a fixed bed reactor having an inner diameter of 28 mm, heated to 550 ℃ at 5 ℃/min under a nitrogen atmosphere, held for 4 hours, then lowered to a reaction temperature of 220 ℃ under a nitrogen atmosphere, and the pressure of the reaction system was raised to 5MPa with CO. The reaction raw materials pass through the catalyst bed layer from top to bottom. Wherein the mass space velocity of dimethyl ether feeding is 1.50h-1(ii) a The molar ratio of carbon monoxide to dimethyl ether was 2:1, the feed gas of carbon monoxide contained no other gas, and the catalytic reaction was carried out at 220 ℃ for 100 hours, with the reaction results shown in Table 1.
TABLE 1 evaluation results of dimethyl ether carbonylation catalysts with different catalysts
Through the evaluation of the catalyst performance of the system, the implementation of the technical scheme can selectively eliminate the reaction side reaction activity, and obtain the catalyst with high activity and high stability under the condition of pyridine pre-adsorption poisoning when not in use.
Example 16
Dimethyl ether carbonylation reaction result under different reaction temperatures
The catalyst used was sample No. 1, 10g of the catalyst was charged into a fixed bed reactor having an inner diameter of 28 mm, heated to 550 ℃ at 5 ℃/min under a nitrogen atmosphere, held for 4 hours, then lowered to the reaction temperature under a nitrogen atmosphere, and the pressure of the reaction system was raised to 5MPa with CO. The reaction raw materials pass through the catalyst from top to bottomAnd (4) a bed layer. Wherein the mass space velocity of dimethyl ether feeding is 1.50h-1(ii) a The molar ratio of carbon monoxide to dimethyl ether is 1:1, the raw material gas of carbon monoxide does not contain other gases, and the reaction temperatures are 170 ℃, 200 ℃, 230 ℃, 240 ℃ and 260 ℃ 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 | 200 | 230 | 240 | 260 |
| Conversion ratio of dimethyl ether (%) | 15.7 | 42.1 | 76.0 | 87.8 | 95.8 |
| CO conversion (%) | 15.7 | 42.1 | 76.0 | 87.8 | 95.8 |
| Methyl acetate selectivity (%) | 97.8 | 99.7 | 99.5 | 99.1 | 96.3 |
| Other Material Selectivity (%) | 2.2 | 0.3 | 0.5 | 0.9 | 3.7 |
Example 17
Dimethyl ether carbonylation reaction result under different reaction pressures
The catalyst used was sample No. 1, the reaction pressures were 1, 6, 10 and 15MPa, the reaction temperature was 220 ℃ and the other conditions were the same as in example 16. At 100 hours of operation, the results are shown in Table 3.
TABLE 3 results of reactions at different reaction pressures
Example 18
Dimethyl ether carbonylation reaction result under different dimethyl ether space velocities
The catalyst used is 1# sample, and the mass space velocities of dimethyl ether feeding are respectively 0.35h-1、1h-1、2.5h-1And 4h-1The reaction temperature was 200 ℃ and the other conditions were the same as in example 15. In the reaction run, the reaction time is 100 hoursThe 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) | 0.35 | 1 | 2.5 | 4 |
| Conversion ratio of dimethyl ether (%) | 92.5 | 63.39 | 25.26 | 14.8 |
| CO conversion (%) | 92.5 | 63.39 | 25.26 | 14.8 |
| Methyl acetate selectivity (%) | 99.9 | 99.8 | 99.2 | 98.7 |
| Other Material Selectivity (%) | 0.1 | 0.2 | 0.8 | 1.3 |
Example 19
Dimethyl ether carbonylation reaction result under different molar ratios of carbon monoxide to dimethyl ether
The catalyst used is a 1# sample, and the mass space velocity of dimethyl ether feeding is 1.5h-1The reaction temperature was 210 ℃ when the molar ratios of carbon monoxide and dimethyl ether were 0.2:1, 0.5:1, 2:1, 4:1, 8:1 and 12:1, respectively, and the other conditions were the same as in example 16. At 100 hours of operation, the 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 | 12:1 | 8:1 | 4:1 | 2:1 | 0.5:1 | 0.2:1 |
| Carbon monoxide conversion (%) | 8.13 | 10.7 | 18.45 | 32.9 | 90.6 | 97.5 |
| Conversion ratio of dimethyl ether (%) | 97.5 | 85.6 | 73.8 | 65.8 | 45.32 | 19.5 |
| Methyl acetate selectivity (%) | 97.8 | 98.1 | 99.5 | 99.4 | 99.3 | 99.3 |
Example 20
Dimethyl ether carbonylation reaction result under the condition that raw gas containing carbon monoxide contains inert gas
The catalyst used is 23# sample, and the mass space velocity of dimethyl ether feeding is 0.5h-1The conditions of the carbon monoxide raw material gas containing an inert gas, the molar ratio of the carbon monoxide-containing raw material gas to dimethyl ether being 4:1 and the reaction temperature being 225 ℃ were otherwise the same as in example 16. At 4000 hours of operation, the results are shown in Table 6.
TABLE 6 reaction results when the carbon monoxide-containing feed gas contains an inert gas
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 (25)
1. A molecular sieve catalyst, characterized in that said molecular sieve catalyst comprises a modified Na-MOR molecular sieve;
the modification comprises the following steps: sequentially carrying out organic ammonium salt exchange, dealumination treatment and ammonium ion exchange;
the organic ammonium salt is selected from at least one of alkyl ammonium halide salt and alkyl ammonium nitrate salt;
the dealuminization treatment comprises at least one of high-temperature roasting treatment and acid treatment.
2. The molecular sieve catalyst of claim 1, wherein the alkyl ammonium halide salt is at least one selected from compounds having the formula shown in formula I:
wherein R is1，R2，R3Independently selected from C1～C10One of the alkyl groups of (a);
R4is selected from C1～C10Alkyl of (C)6～C10One of the aryl groups of (a);
x is selected from at least one of F, Cl, Br or I.
3. The molecular sieve catalyst of claim 2, wherein R in formula I1，R2，R3Independently selected from CH3-、CH3CH2-、CH3(CH2)nCH2-、(CH3)2CH-、(CH3)2CHCH2-、CH3CH2(CH3) Any one of CH-groups;
R4is CH3-、CH3-、CH3CH2-、CH3(CH2)mCH2-、(CH3)2CH-、(CH3)2CHCH2-、CH3CH2(CH3)CH-、C6H5-、CH3C6H4-、(CH3)2C6H3-、C6H5CH2-any of;
wherein n and m are independently selected from 1, 2, 3 or 4.
4. The molecular sieve catalyst of claim 1, wherein the Na-MOR molecular sieve has a silicon to aluminum atomic ratio of 6 to 50.
5. A method of preparing the molecular sieve catalyst of any of claims 1 to 4, comprising: sequentially carrying out organic ammonium salt exchange, dealumination treatment, ammonium ion exchange and roasting on the Na-MOR molecular sieve to obtain the molecular sieve catalyst;
the organic ammonium salt is selected from at least one of alkyl ammonium halide salt and alkyl ammonium nitrate salt;
the dealuminization treatment comprises at least one of high-temperature roasting treatment and acid treatment.
6. The method of preparing a molecular sieve catalyst according to claim 5, comprising:
(1) exchanging organic ammonium salt with a Na-MOR molecular sieve to obtain a precursor I;
(2) carrying out acid treatment on the precursor I to obtain a precursor II;
(3) carrying out high-temperature roasting treatment on the precursor II to obtain a precursor III;
(4) performing ammonium ion exchange on the precursor III to obtain a precursor IV;
(5) and roasting the precursor IV to obtain the molecular sieve catalyst.
7. The method of claim 6, wherein the organic ammonium salt exchange conditions in step (1) are as follows: and (3) carrying out exchange treatment on the Na-MOR molecular sieve in an organic ammonium salt solution at the temperature of 20-100 ℃ for 1-10 hours.
8. The method for preparing the molecular sieve catalyst according to claim 7, wherein the concentration of the organic ammonium salt solution is 0.05-1 mol/L.
9. The method for preparing the molecular sieve catalyst according to claim 7, wherein the number of times of the organic ammonium salt exchange is 2-8;
the organic ammonium salt exchange conditions are as follows: exchange treatment is carried out for 2-6 hours at 30-80 ℃.
10. The method for preparing a molecular sieve catalyst according to claim 6, wherein the acid used in the acid treatment in step (2) is at least one selected from hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and citric acid;
the acid treatment conditions in the step (2) are as follows: treating in an acid solution at 30-100 ℃ for 1-10 hours.
11. The method for preparing the molecular sieve catalyst according to claim 10, wherein the acid treatment is performed 2 to 10 times;
the acid treatment conditions are as follows: treating in an acid solution at 30-80 ℃ for 2-8 hours.
12. The method for preparing the molecular sieve catalyst according to claim 6, wherein the conditions of the high-temperature calcination treatment in the step (3) are as follows: treating for 1-10 hours at 300-800 ℃ in an atmosphere with water vapor concentration of 0-100%.
13. The method for preparing the molecular sieve catalyst according to claim 12, wherein the conditions of the high-temperature calcination treatment are as follows: treating for 2-6 hours at 350-750 ℃ in an atmosphere with the water vapor concentration of 0-100%.
14. The method for preparing a molecular sieve catalyst according to claim 6, wherein the conditions for ammonium ion exchange in step (4) are as follows: exchange treatment at 20-100 ℃ for 1-10 hours.
15. The method for preparing the molecular sieve catalyst according to claim 14, wherein the number of ammonium ion exchanges is 2 to 5;
the ammonium ion exchange condition is that the exchange treatment is carried out for 2-6 hours at the temperature of 30-90 ℃;
the ammonium ion exchange is carried out in a solution containing ammonium ions; the ammonium ion-containing solution is at least one selected from ammonium nitrate solution, ammonium chloride solution, ammonium sulfate solution and ammonium acetate solution.
16. The method of claim 6, wherein the calcination conditions in step (5) are as follows: roasting for 2-8 hours at 300-800 ℃ in air atmosphere.
17. The method of claim 16, wherein the calcining conditions are: roasting for 4-6 hours at 400-750 ℃ in an air atmosphere.
18. The method of preparing a molecular sieve catalyst according to claim 6, comprising:
a) exchanging the solid containing the Na-MOR molecular sieve for 1-10 hours at 20-100 ℃ by using a solution containing alkyl ammonium halide salt, wherein the exchange times are 2-8 times, and obtaining a precursor I;
b) treating the precursor I with an acid solution at 30-100 ℃ for 1-10 hours for 2-10 times to obtain a precursor II;
c) treating the precursor II for 1-10 hours at 300-800 ℃ in an atmosphere with the water vapor concentration of 0-100% to obtain a precursor III;
d) performing exchange treatment on the precursor III in an ammonium nitrate aqueous solution at the temperature of 20-100 ℃ for 1-10 hours for 2-5 times to obtain a precursor IV;
e) and roasting the precursor IV for 2-8 hours at the temperature of 300-800 ℃ in air to prepare the molecular sieve catalyst.
19. Use of at least one of the molecular sieve catalyst of any one of claims 1 to 4, the molecular sieve catalyst produced by the process of any one of claims 5 to 18, as a catalyst for the carbonylation of dimethyl ether to produce methyl acetate.
20. A process for the carbonylation of dimethyl ether to produce methyl acetate comprising: introducing dimethyl ether and feed gas containing carbon monoxide into a reactor loaded with a catalyst bed layer, and carrying out contact reaction with the catalyst to produce methyl acetate;
wherein the catalyst is selected from at least one of the molecular sieve catalyst of any one of claims 1 to 4, the molecular sieve catalyst produced by the process of any one of claims 5 to 18.
21. The carbonylation of dimethyl ether to produce methyl acetate according to claim 20 wherein the reaction conditions are:
the reaction temperature is 150-280 ℃, the reaction pressure is 0.5-25.0 MPa, and the mass space velocity of dimethyl ether feeding is 0.05-5 h-1；
The molar ratio of carbon monoxide to dimethyl ether is 0.1: 1-30: 1.
22. The carbonylation of dimethyl ether to produce methyl acetate according to claim 21 wherein the reaction conditions are:
the reaction temperature is 160-280 ℃, the reaction force is 0.5-20.0 MPa, and the mass space velocity of dimethyl ether feeding is 0.2-4.0 h-1；
The molar ratio of the carbon monoxide to the dimethyl ether is 0.1: 1-20: 1.
23. The carbonylation of dimethyl ether to produce methyl acetate according to claim 21 wherein the reaction conditions are:
the reaction temperature is 170-260 ℃, the reaction pressure is 1.0-15.0 MPa, and the mass space velocity of dimethyl ether feeding is 0.1-4.0 h-1；
The molar ratio of the carbon monoxide to the dimethyl ether is 0.2: 1-15: 1.
24. The method for carbonylation production of methyl acetate by dimethyl ether according to claim 20, wherein the volume content of carbon monoxide in the feed gas containing carbon monoxide is 15-100%.
25. The carbonylation of dimethyl ether to produce methyl acetate according to claim 24 wherein the carbon monoxide-containing feed gas further comprises at least one of hydrogen, nitrogen, helium, argon, carbon dioxide, methane and ethane.
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