CN111517955A - Method for producing methyl acetate by dimethyl ether carbonylation - Google Patents
Method for producing methyl acetate by dimethyl ether carbonylation Download PDFInfo
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Abstract
The application discloses a method for producing methyl acetate by dimethyl ether carbonylation, which comprises the following steps: dimethyl ether and feed gas containing carbon monoxide are reacted by a reactor filled with a solid acid catalyst to produce methyl acetate; wherein the molar ratio of the carbon monoxide to the dimethyl ether is 0.05: 1-0.5: 1. The method has the advantages of low molar ratio of carbon monoxide to dimethyl ether, high carbon monoxide conversion rate, small gas circulation amount, low operation cost and the like.
Description
Technical Field
The application relates to a method for producing methyl acetate by dimethyl ether carbonylation, 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 mainly comprise: (1) the synthesis gas is directly used for preparing ethanol, but a noble metal rhodium catalyst is needed, the cost of the catalyst is high, and the yield of rhodium is limited; (2) the synthetic gas is hydrogenated to prepare the ethanol through acetic acid, the synthetic gas is firstly subjected to methanol liquid phase carbonylation to prepare the acetic acid, and then the synthetic ethanol is hydrogenated. The process of the route is mature, but the equipment needs special alloy with corrosion resistance, so the cost is higher; (3) the synthesis gas is carbonylated with dimethyl ether to produce ethanol, and the synthesis gas is first carbonylated with dimethyl ether to produce methyl acetate, which is further hydrogenated to produce ethanol. The dimethyl ether carbonylation reaction and the methyl acetate hydrogenation reaction related to the process route respectively adopt a solid acidic molecular sieve catalyst and a copper-based catalyst which are non-noble metal catalysts, are cheap and easily available, have mild reaction conditions, do not have the acetic acid corrosion problem in the carbonylation and hydrogenation processes, greatly reduce the process cost and equipment cost, have high selectivity of target products, are a novel coal-to-ethanol new route, and have good market prospect.
The dimethyl ether carbonylation reaction is the core reaction of a route for preparing ethanol by dimethyl ether carbonylation of synthesis gas. In the research of dimethyl ether carbonylation, the proportion of carbon monoxide to dimethyl ether is relatively high. Patent US20070238897a1 discloses ether carbonylation catalysts and their use in the carbonylation of dimethyl ether, the ratio of carbon monoxide to dimethyl ether being 46.5: 1, and the catalyst is quickly deactivated; patent CN101613274A reports a mordenite molecular sieve modified by pyridine organic amine and its application in dimethyl ether carbonylation reaction, in the application process of its pyridine modified catalyst, the ratio of carbon monoxide and dimethyl ether is 10: 1, the conversion rate of dimethyl ether is 30 percent, and the conversion rate of carbon monoxide is about 3 percent. In the industrial application process, the ratio of carbon monoxide to dimethyl ether is too high, and a large amount of carbon monoxide cannot be converted and utilized. The excess carbon monoxide needs to be recycled after gas separation. The separation, compression and circulation of the gas inevitably results in high energy consumption and high operation cost.
Disclosure of Invention
According to one aspect of the application, a method for producing methyl acetate by carbonylation of dimethyl ether is provided, and the method has the advantages of low molar ratio of carbon monoxide to dimethyl ether, high carbon monoxide conversion rate, small gas circulation amount, low operation cost and the like.
The method for producing methyl acetate by carbonylation of dimethyl ether is characterized by comprising the following steps: dimethyl ether and feed gas containing carbon monoxide are reacted by a reactor filled with a solid acid catalyst to produce methyl acetate;
wherein the molar ratio of the carbon monoxide to the dimethyl ether is 0.05: 1-0.5: 1.
Alternatively, the upper limit of the molar ratio of carbon monoxide to dimethyl ether is selected from 0.06:1, 0.08:1, 0.1:1, 0.12:1, 0.15:1, 0.18:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.48:1, 0.498:1 or 0.5: 1; the lower limit is selected from 0.05, 0.06:1, 0.08:1, 0.1:1, 0.12:1, 0.15:1, 0.18:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.48:1, or 0.498: 1.
Optionally, the molar ratio of carbon monoxide to dimethyl ether is 0.08:1 to 0.5: 1.
Optionally, the molar ratio of carbon monoxide to dimethyl ether is 0.1:1 to 0.5: 1.
Optionally, the volume content of carbon monoxide in the feed gas containing carbon monoxide is 15-100%.
Optionally, the feed gas containing carbon monoxide comprises an inert gas; the volume content of the inactive gas is 0-85%.
Optionally, the inert gas is selected from at least one of hydrogen, nitrogen, inert gas, carbon dioxide, methane, ethane.
Optionally, the inactive gas is selected from any one or more of hydrogen, nitrogen, helium, argon, carbon dioxide, methane and ethane.
Optionally, the carbon monoxide-containing raw material gas further comprises at least one of hydrogen, nitrogen, helium, argon, carbon dioxide, methane and ethane.
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%.
Optionally, the solid acid catalyst is selected from at least one of dimethyl ether carbonylation catalysts.
Optionally, the solid acid catalyst is a dimethyl ether carbonylation catalyst.
Optionally, the solid acid catalyst is selected from at least one of a hydrogen zeolite molecular sieve and a modified hydrogen zeolite molecular sieve.
Optionally, the solid acid catalyst comprises at least one of a zeolite molecular sieve, a modified zeolite molecular sieve;
wherein the framework type of the zeolite molecular sieve is selected from one of FER, MFI, MOR, ETL, MFS, MTF and EMT;
the modification is at least one selected from element modification except zeolite molecular sieve framework elements, pyridine modification, organic amine modification, alkyl ammonium halide salt modification, acid treatment, water vapor treatment and ammonium ion exchange.
Optionally, the modification is selected from at least one of element modification other than zeolite molecular sieve framework constituent elements, pyridine modification, organic amine modification, (alkyl ammonium halide salt modification + acid treatment + water vapor treatment + ammonium ion exchange).
Optionally, the element in the element modification is selected from at least one of metal elements.
Optionally, at least one of the elements group VIII metal element, group IB metal element, group IIIA metal in the element modification.
Optionally, at least one of the elements Fe, Cu, Ag, Ga in the element modification.
Alternatively, the element modification, pyridine modification, organic amine modification, acid treatment, water vapor treatment, and ammonium ion exchange can be performed by methods known in the art.
As one embodiment thereof, the solid acid catalyst comprises one or more molecular sieves of: FER, MFI, MOR, ETL, MFS, MTF, EMT zeolite molecular sieves and molecular sieve products obtained by modifying elements except framework composition elements or pyridine, organic amine and alkyl ammonium chloride salt.
Optionally, the zeolitic molecular sieve is a hydrogen form molecular sieve.
Optionally, the hydrogen zeolite molecular sieve is present in the solid acid catalyst in an amount of 10 wt% to 100 wt%.
Optionally, the hydrogen zeolite molecular sieve is present in the solid acid catalyst in an amount of 10 wt% to 95 wt%.
Optionally, the hydrogen type zeolite molecular sieve has a silicon-aluminum atomic ratio of 4-100.
Optionally, the zeolite molecular sieve further comprises a matrix;
the matrix includes at least one of the binders.
Optionally, the solid acid catalyst comprises a matrix;
the matrix is at least one of alumina, silica, kaolin and magnesia.
Optionally, the content of the hydrogen-type zeolite molecular sieve in the solid acid catalyst is 10 wt% to 95 wt%.
Optionally, the upper limit of the content of the hydrogen-form zeolite molecular sieve in the solid acid catalyst is selected from 50%, 60%, 70%, 80%, 90% or 100%; the lower limit is selected from 50%, 60%, 70%, 80% or 90%.
As one embodiment, the solid acid catalyst is a hydrogen-type product of the zeolite molecular sieve, or is composed of 10 wt% to 95 wt% of the hydrogen-type product and the balance of a matrix, or is a molecular sieve product obtained by modifying the hydrogen-type product with elements except framework constituent elements or pyridine, organic amine and alkyl ammonium chloride salt, wherein the matrix is one or more selected from alumina, silica, kaolin and magnesia.
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.
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.
Alternatively, X is selected from F, Cl, Br or I.
Optionally, the alkyl ammonium halide salt is an alkyl ammonium chloride salt.
Alternatively, the conditions for the alkylhaloammonium salt exchange are: and (3) carrying out exchange treatment on the zeolite 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 alkylhaloammonium 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 alkylhaloammonium 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 alkyl ammonium halide salt aqueous solution is 0.05-1 mol/L.
Optionally, the volume ratio of the molecular sieve to the aqueous solution of alkyl ammonium halide salt is 1: 1-1: 15 (g/ml).
Optionally, the solid-to-liquid ratio of the alkyl ammonium halide salt exchange is 1g: 2-15 ml.
Alternatively, the upper concentration limit of the alkyl ammonium halide 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 exchanging the alkyl ammonium halide salt is 2-8;
the conditions for the exchange of the alkyl ammonium halide salt are as follows: exchange treatment is carried out for 2-6 hours at 30-80 ℃.
Optionally, the alkyl ammonium halide salt exchange comprises: carrying out exchange treatment on the solid containing the molecular sieve with an alkyl ammonium chloride solution at the temperature of 20-100 ℃ for 1-10 hours, and washing, filtering and drying the product; repeating the steps for 2-8 times.
The skilled person can select a suitable reactor according to the actual production needs. Preferably, the reactor is a fixed bed reactor.
Optionally, the reactor is selected from one of a fixed bed reactor, a moving bed reactor, a fluidized bed reactor.
Optionally, the reaction is a contact reaction with a catalyst.
Optionally, the reaction conditions are:
the reaction temperature is 150-300 ℃, the reaction pressure is 0.5-25.0 MPa, and the mass space velocity of dimethyl ether is 0.05-6 h-1。
The operating conditions of dimethyl ether and carbon monoxide in the raw material gas, reaction temperature, reaction pressure, space velocity and the like can be selected by those skilled in the art within the above range according to actual needs.
Optionally, the upper limit of the reaction temperature is selected from 160 ℃, 170 ℃, 200 ℃, 210 ℃, 230 ℃, 240 ℃, 260 ℃, 280 ℃ or 300 ℃; the lower limit is selected from 150 deg.C, 160 deg.C, 170 deg.C, 200 deg.C, 210 deg.C, 230 deg.C, 240 deg.C, 260 deg.C or 280 deg.C.
Optionally, the temperature of the reaction is 160-280 ℃.
Optionally, the temperature of the reaction is 170-260 ℃.
Optionally, the upper reaction pressure limit is selected from 1MPa, 6MPa, 10MPa, 15MPa, 20MPa, or 25 MPa; the lower limit is selected from 0.5MPa, 1MPa, 6MPa, 10MPa, 15MPa or 20 MPa.
Optionally, the reaction pressure is 0.5-20.0 MPa.
Optionally, the reaction pressure is 1.0-15.0 MPa.
Alternatively, the upper mass space velocity limit of dimethyl ether is selected from 0.1h-1、0.2h-1、0.3h-1、0.35h-1、0.5h-1、1h-1、1.50h-1、2.5h-1、3h-1、4h-1、5h-1Or 6h-1(ii) a The lower limit is selected from 0.05h-1、0.1h-1、0.2h-1、0.3h-1、0.35h-1、0.5h-1、1h-1、1.50h-1、2.5h-1、3h-1、4h-1Or 5h-1。
Optionally, the mass space velocity of the dimethyl ether is 0.2-6.0 h-1。
Optionally, the mass space velocity of the dimethyl ether is 0.05-5.0 h-1。
Optionally, the mass space velocity of the dimethyl ether is 0.1-4.0 h-1。
Optionally, the mass space velocity of the dimethyl ether is 0.2-4.0 h-1。
Optionally, the mass space velocity of the dimethyl ether is 0.35-4.0 h-1。
Optionally, the method comprises: the reaction temperature is 160-280 ℃, the 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 carbon monoxide to dimethyl ether is 0.08: 1-0.5: 1.
Optionally, the method comprises: the 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 the carbon monoxide to the dimethyl ether is 0.1: 1-0.5: 1.
As a specific embodiment, the method comprises: dimethyl ether and feed gas containing carbon monoxide are led to pass through a reactor filled with a solid acid catalyst, the reaction temperature is 150-300 ℃, the reaction pressure is 0.5-25.0 MPa, and the mass space velocity of the dimethyl ether is 0.2-6 h-1Reacting under the condition to produce methyl acetate; wherein the molar ratio of carbon monoxide to dimethyl ether in the feed gas is 0.05: 1-0.5: 1.
As a specific embodiment, the method comprises: the dimethyl ether and the raw material gas containing carbon monoxide pass through a reactor filled with a carbonylation catalyst containing dimethyl ether, the reaction temperature is 150-280 ℃, the reaction pressure is 0.5-25.0 MPa, and the space velocity of dimethyl ether is 0.2-4 h-1And reacting to produce methyl acetate under the condition that the molar ratio of the carbon monoxide to the dimethyl ether is 0.05: 1-0.5: 1.
Optionally, the carbon monoxide conversion in the process is up to 20% or more.
Optionally, the carbon monoxide conversion in the process is up to 30% or more.
Optionally, the conversion of carbon monoxide in the process reaches above 50%.
Optionally, the conversion of carbon monoxide in the process reaches above 80%.
Optionally, the conversion of carbon monoxide in the process reaches above 90%.
Optionally, the selectivity of methyl acetate in the process reaches over 90%.
Optionally, the selectivity of methyl acetate in the process reaches above 98%.
Optionally, the selectivity of methyl acetate in the process is greater than 99%.
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 application provides a method for producing methyl acetate by dimethyl ether carbonylation, which has the advantages of low molar ratio of carbon monoxide to dimethyl ether, high carbon monoxide conversion rate, small gas circulation amount, low operation cost and the like.
2) The application provides a method for producing methyl acetate by carbonylation of dimethyl ether, wherein raw material gas containing carbon monoxide can also contain any one or more of hydrogen, nitrogen, helium, argon, carbon dioxide, methane and ethane besides carbon monoxide; meanwhile, the volume content of the carbon monoxide is 15-100%, and the adjustment range is wide, so that the method has universality in 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 raw materials in the examples of the present application were all purchased commercially; wherein, the source of the molecular sieve raw material is shown in table 1.
In the experimental process, part of the molecular sieve raw materials can be directly obtained by commercial purchase; part of the molecular sieve raw materials can be synthesized according to the prior related documents, and the specific sources are shown in Table 1.
TABLE 1 sources and Si/Al ratios of different molecular sieve raw materials
| Molecular sieve raw material | Acquisition mode | Origin of origin | Atomic ratio of Si/Al |
| NaMOR (mordenite) | Purchasing | South China Kai catalyst plant | 6.5 |
| NaMOR (mordenite) | Purchasing | South China Kai catalyst plant | 15 |
| NaZSM-35 | Purchasing | Olympic catalyst plant | 79 |
| NaZSM-5 | Purchasing | South China Kai catalyst plant | 50 |
| NaEMT1 | Synthesis of | Dalian Institute Of Chemical Physics | 4 |
| NaEMT1 | Synthesis of | Dalian Institute Of Chemical Physics | 25 |
| Na-EU-122 | Synthesis of | Dalian Institute Of Chemical Physics | 10 |
| Na-MCM-653 | Synthesis of | Dalian Institute Of Chemical Physics | 50 |
| Na-MCM-353 | Synthesis of | Dalian Institute Of Chemical Physics | 100 |
| Na-M-MOR* | Synthesis of | Dalian Institute Of Chemical Physics | 16.5 |
The superscripts 1,2,3 in table 1 are used to indicate the different molecular sieve species.
NaEMT synthesis reference Science with silicon to aluminum atomic ratio of 4, 2012356 (6): 70-73.
For the synthesis and preparation of NaEMT with a silicon-aluminum atomic ratio of 25, reference is made to the preparation, secondary synthesis and modification of molecular sieves in the above documents and "molecular sieves and porous materials chemistry": 2004: 416-466.
For the synthesis of Na-EU-12, reference is made to Angew. chem. int. Ed.2016,55, 7369-7373.
Na-MCM-65 was synthesized by J.Phys.chem.B 2004,108, 15216-.
For the synthesis of Na-MCM-35, refer to chem.Mater.1999,11, 2919-2927.
Na-M-MOR represents mordenite modified by elements except framework component elements, wherein M represents modified metal atoms, which is prepared by in-situ synthesis, and molecular sieves modified by Fe, Ga, Cu and Ag metals are respectively prepared in the preparation process, wherein the content of the modified metal is 0.9 wt%, and the preparation method is referred to Catal.Sci.Technol, 2015015, 5, 1961-.
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 method for producing methyl acetate by carbonylation of dimethyl ether comprises the step of enabling dimethyl ether and feed gas containing carbon monoxide to pass through a reactor filled with a solid acid catalyst, and carrying out reaction at the temperature of 150-300 ℃, the reaction pressure of 0.5-25.0 MPa and the mass space velocity of dimethyl ether of 0.2-6 h-1Reacting under the condition to produce methyl acetate; wherein the molar ratio of carbon monoxide to dimethyl ether in the feed gas is 0.05: 1-0.5: 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%.
As one of the embodiments, the reactor may be a fixed bed reactor, a moving bed reactor, or a fluidized bed reactor.
As one embodiment, the solid acid catalyst is a dimethyl ether carbonylation catalyst.
As one embodiment thereof, the solid acid catalyst comprises one or more molecular sieves of: FER, MFI, MOR, ETL, MFS, MTF, EMT zeolite molecular sieves and molecular sieve products obtained by modifying elements except framework composition elements or pyridine, organic amine and alkyl ammonium chloride salt.
As one embodiment, the solid acid catalyst is a hydrogen-type product of the zeolite molecular sieve, or is composed of 10 wt% to 95 wt% of the hydrogen-type product and the balance of a matrix, or is a molecular sieve product obtained by modifying the hydrogen-type product with elements except framework constituent elements or pyridine, organic amine and alkyl ammonium chloride salt, wherein the matrix is one or more selected from alumina, silica, kaolin and magnesia.
As one embodiment, the reaction temperature is 160-280 ℃, the 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 carbon monoxide to dimethyl ether is 0.08: 1-0.5: 1.
As one embodiment, the 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 the carbon monoxide to the dimethyl ether is 0.1: 1-0.5: 1.
Example 1
The hydrogen form samples were prepared as follows:
passing the Na-type molecular sieve in Table 1 through NH4NO3Ion exchange, drying and roasting to obtain the hydrogen type molecular sieve. For example, a typical hydrogen form sample preparation procedure is as follows: in a hydrothermal synthesis kettle, adding NaMOR molecular sieve powder into pre-prepared 1mol/L NH4NO3In the aqueous solution, the solid-liquid mass ratio is 1:10, the exchange reaction is carried out for 2h at 80 ℃ under the stirring state, and the solution is subjected to vacuum filtration and washing by water. After 3 times of continuous exchange reaction, the product was dried at 120 ℃ overnight and calcined at 550 ℃ for 4 hours to obtain the desired catalyst sample HMOR.
The parameters for preparing the hydrogen form of the molecular sieve for the remaining samples in table 1 are the same as above, with only the molecular sieve being different.
The formed hydrogen type sample containing the matrix is prepared by adopting a strip extrusion forming method. For example, a typical shaped sample preparation procedure is as follows: 80g of Na-MOR and 20g of alumina are fully mixed, 10 wt% of nitric acid is added for kneading, and a sample kneaded into a dough shape is extruded into strips through a strip extruding machine for molding. Drying the extruded strip sample at 120 ℃, roasting at 550 ℃ for 4h, and preparing the formed hydrogen type sample containing the matrix by adopting a preparation method of the hydrogen type sample.
The parameters for preparing the matrix-containing molecular sieves for the remaining samples in Table 1 are the same as above, with only the molecular sieve and matrix being different.
Preparation of pyridine-modified hydrogen samples. A typical preparation procedure is as follows: 10g of hydrogen type sample is put into a reaction tube, the temperature is gradually raised to 550 ℃ under the nitrogen atmosphere of 100mL/min, the temperature is kept for 4 hours, then pyridine is carried by nitrogen, the pyridine is treated for 4 hours at 350 ℃, and a pyridine modified sample is prepared, and the sample is marked by H-M '-py, wherein M' represents the name of a molecular sieve.
The parameters for preparing pyridine modified molecular sieves for the remaining samples in Table 1 are the same as above, with only the molecular sieves being different.
The series of samples prepared according to the above method is detailed in table 2.
TABLE 2 preparation of sample numbers and sample compositions
Example 2
Respectively putting 100 g of Na-MOR (Si/Al ═ 15) molecular sieve into 1000ml of 0.5mol/L tetraethyl methyl ammonium chloride aqueous solution, phenyl trimethyl ammonium chloride aqueous solution, benzyl trimethyl ammonium bromide aqueous solution and benzyl trimethyl ammonium iodide aqueous solution, treating for 4 hours at 80 ℃, filtering, washing, drying and repeating the treatment steps for 5 times; then putting the prepared sample into 1000ml of oxalic acid water solution with the solubility of 0.7mol/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 an air atmosphere with the water vapor concentration of 10%; treating the sample obtained by high-temperature steam treatment with 1000ml of 1mol/L ammonium nitrate aqueous solution at 70 ℃ for 4 hours, washing and drying, and repeating the ammonium nitrate solution exchange treatment step for 3 times; the prepared sample is roasted for 4 hours at 550 ℃ in air atmosphere to prepare catalysts 17#, 18#, 19#, 20#, and 21 #.
Example 3
10g of each of the HMOR samples prepared in example 1 (Si/Al ═ 6.5) was gradually heated to 550 ℃ in a nitrogen atmosphere of 100mL/min for 4 hours, and then treated with nitrogen gas carrying trimethylamine and tetraethylamine at 200 ℃ for 4 hours to prepare organic amine-modified samples # 22 and # 23.
The catalysts of the above examples were examined for their 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 250 ℃ 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 is 0.45:1, the raw material gas of carbon monoxide does not contain other gases, the catalytic reaction is operated for 2 hours under the condition that the reaction temperature is 250 ℃, the reaction result is shown in a table 3, and the evaluation result of the dimethyl ether carbonylation catalyst of the 11# sample under different operation times is shown in a table 4.
TABLE 3 evaluation results of dimethyl ether carbonylation catalysts with different catalysts
| Catalyst and process for preparing same | CO conversion (%) | Conversion ratio of dimethyl ether (%) | Methyl acetate selectivity (%) | Other Material Selectivity (%) |
| 1# | 71.5 | 35.8 | 99.9 | 0.1 |
| 2# | 47.3 | 23.7 | 99.8 | 0.2 |
| 3# | 62.1 | 31.1 | 99.5 | 0.5 |
| 4# | 44.5 | 22.3 | 99.3 | 0.7 |
| 5# | 27.5 | 13.8 | 99.6 | 0.4 |
| 6# | 76.9 | 38.5 | 99.5 | 0.5 |
| 7# | 65.9 | 33.0 | 99.6 | 0.4 |
| 8# | 38.3 | 19.2 | 99.5 | 0.5 |
| 9# | 24.2 | 12.1 | 92.6 | 7.4 |
| 10# | 36.8 | 18.4 | 94.5 | 5.5 |
| 11# | 98.8 | 49.5 | 99.9 | 0.1 |
| 12# | 98.5 | 49.4 | 99.2 | 1.7 |
| 13# | 57.6 | 28.9 | 98.4 | 1.6 |
| 14# | 52.1 | 26.1 | 97.5 | 2.5 |
| 15# | 55.6 | 27.9 | 98.8 | 1.2 |
| 16# | 53.8 | 27.0 | 90.8 | 9.2 |
| 17# | 96.5 | 49.9 | 98.9 | 1.1 |
| 18# | 97.5 | 49.9 | 98.9 | 1.1 |
| 19# | 97.5 | 49.9 | 98.9 | 1.1 |
| 20# | 97.6 | 49.9 | 98.9 | 1.1 |
| 21# | 98.1 | 50.0 | 98.7 | 1.3 |
| 22# | 52.3 | 26.0 | 98.7 | 1.3 |
| 23# | 56.8 | 28.4 | 98.7 | 1.3 |
TABLE 4 evaluation results of dimethyl ether carbonylation catalyst for 11# samples at various run times
Example 4
Dimethyl ether carbonylation reaction result under different reaction temperatures
The catalyst used was a 17# sample, 10g of which was charged in 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 are from the topThen passes through the catalyst bed. 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 0.45:1, the raw material gas of carbon monoxide contains no other gas, and the reaction temperature is 150 ℃, 160 ℃, 170 ℃, 200 ℃, 230 ℃, 240 ℃, 260 ℃, 280 ℃ and 300 ℃ respectively. The results of the catalytic reaction run for 100 hours are shown in Table 5.
TABLE 5 results of reactions at different reaction temperatures
| Reactor inlet temperature (. degree.C.) | 150 | 160 | 170 | 200 | 230 | 240 | 260 | 280 | 300 |
| Conversion ratio of dimethyl ether (%) | 1.0 | 3.5 | 7.9 | 21.2 | 38.2 | 42.6 | 45.2 | 47.8 | 49.9 |
| CO conversion (%) | 2.0 | 7.0 | 15.7 | 42.1 | 76.0 | 85.2 | 90.4 | 95.6 | 99.9 |
| Methyl acetate selectivity (%) | 97.5 | 97.7 | 97.8 | 99.7 | 99.5 | 99.1 | 99.3 | 99.5 | 99.1 |
| Other Material Selectivity (%) | 2.5 | 2.3 | 2.2 | 0.3 | 0.5 | 0.9 | 0.7 | 0.5 | 0.9 |
Example 5
Dimethyl ether carbonylation reaction result under different reaction pressures
The catalyst used was sample No. 17, and 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, and then reduced to 220 ℃ under a nitrogen atmosphere, and the pressure of the reaction system was raised to the reaction pressure with CO. The reaction raw materials pass through the catalyst bed layer from top to bottom. Wherein the space velocity of dimethyl ether feeding is 1.50h-1(ii) a The molar ratio of carbon monoxide to dimethyl ether is 0.45:1, the raw material gas of carbon monoxide contains no other gas, and the reaction pressure is 0.5MPa, 1MPa, 6MPa, 10MPa, 15MPa, 20MPa and 25MPa respectively. The results of the catalytic reaction run for 100 hours are shown in Table 6.
TABLE 6 results of reactions at different reaction pressures
| Reaction pressure (MPa) | 0.5 | 1 | 6 | 10 | 15 | 20 | 25 |
| Conversion ratio of dimethyl ether (%) | 5.2 | 9.2 | 29.8 | 36.6 | 41.5 | 43.5 | 45.8 |
| CO conversion (%) | 10.4 | 18.3 | 59.3 | 72.8 | 82.3 | 87.0 | 92.0 |
| Methyl acetate selectivity (%) | 97.8 | 98.7 | 99.9 | 99.9 | 99.9 | 99.9 | 99.9 |
| Other Material Selectivity (%) | 2.2 | 1.3 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
Example 6
Dimethyl ether carbonylation reaction result under different dimethyl ether space velocities
The catalyst used was sample No. 17, 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 nitrogen atmosphere, held for 4 hours, then reduced to 235 ℃ under nitrogen atmosphere, and the pressure of the reaction system was raised to 8MPa with CO. The reaction raw materials pass through the catalyst bed layer from top to bottom. The molar ratio of carbon monoxide to dimethyl ether is 0.45:1, the feed gas of carbon monoxide does not contain other gases, and the space velocities of dimethyl ether feeding are respectively 0.05h-1、0.1h-1、0.2h-1、0.35h-1、1h-1、2.5h-1、4h-1And 6h-1The reaction results when the reaction was run for 100 hours are shown in Table 7.
TABLE 7 reaction results at different space velocities of dimethyl ether
| Dimethyl ether feed space velocity (h)-1) | 0.05 | 0.1 | 0.2 | 0.35 | 1 | 2.5 | 4 | 6 |
| Conversion ratio of dimethyl ether (%) | 50.0 | 50.0 | 50.0 | 50.0 | 47.9 | 27.8 | 12.5 | 6.3 |
| CO conversion (%) | 100 | 100 | 100 | 100 | 95.4 | 55.26 | 24.8 | 13.6 |
| Methyl acetate selectivity (%) | 97.6 | 98.6 | 99.2 | 99.9 | 99.8 | 99.2 | 98.7 | 98.5 |
| Other Material Selectivity (%) | 2.4 | 1.4 | 0.8 | 0.1 | 0.2 | 0.8 | 1.3 | 1.5 |
Example 7
Dimethyl ether carbonylation reaction result under different molar ratios of carbon monoxide to dimethyl ether
The catalyst used was sample No. 17, 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 nitrogen atmosphere, held for 4 hours, then reduced to 235 ℃ under nitrogen atmosphere, and the pressure of the reaction system was raised to 8MPa with CO. The reaction raw materials pass through the catalyst bed layer from top to bottom. The mass space velocity of dimethyl ether feeding is 1.0h-1The raw material gas of carbon monoxide contained no other gas, and the reaction results were shown in Table 8 when the reaction was run for 100 hours at molar ratios of carbon monoxide to dimethyl ether of 0.05:1, 0.08:1, 0.1:1, 0.2:1, 0.45:1, 0.48:1, 0.498:1, and 0.5:1, respectively.
TABLE 8 results of reactions with different volume ratios of dimethyl ether and carbon monoxide
| Carbon monoxide/dimethyl ether molar ratio | 0.05:1 | 0.08:1 | 0.1:1 | 0.2:1 | 0.45:1 | 0.48:1 | 0.498:1 | 0.5:1 |
| Carbon monoxide conversion (%) | 89.7 | 90.2 | 90.6 | 92.9 | 93.8 | 94.6 | 97.8 | 98.1 |
| Conversion ratio of dimethyl ether (%) | 4.5 | 7.2 | 9.06 | 18.6 | 42.1 | 45.5 | 48.7 | 49.0 |
| Methyl acetate selectivity (%) | 99.3 | 99.3 | 99.3 | 99.4 | 99.4 | 99.3 | 99.4 | 99.3 |
Example 8
Dimethyl ether carbonylation reaction result under the condition that raw gas containing carbon monoxide contains inert gas
The catalyst used was a 13# sample, 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 nitrogen atmosphere, held for 4 hours, then reduced to 235 ℃ under nitrogen atmosphere, and the pressure of the reaction system was raised to 10MPa with CO. The reaction raw materials pass through the catalyst bed layer from top to bottom. The mass space velocity of dimethyl ether feeding is 1.0h-1The raw material gas of carbon monoxide contained inert gas, wherein the ratio of DME/CO is shown in Table 9, the feeding amount of the carbon monoxide mixed gas was adjusted according to the ratio of DME/CO, and the reaction results are shown in Table 9 when the reaction was run for 100 hours with different inert gases.
TABLE 9 reaction results when the carbon monoxide-containing raw material gas contains an inert gas
Example 9
The catalyst used was a 17# sample, 10g of which was charged in a fluidized bed reactor and a moving bed reactor, respectively, and the temperature was raised to 550 ℃ at 5 ℃/min under nitrogen atmosphere, held for 4 hours, and then lowered to 240 ℃ under nitrogen atmosphere, and the pressure of the reaction system was raised to 8MPa with CO. The mass space velocity of dimethyl ether feeding is 1.50h-1(ii) a The molar ratio of carbon monoxide to dimethyl ether was 0.45:1, the feed gas for carbon monoxide contained no other gases, and the results of the catalytic reaction run for 100 hours are shown in table 10.
TABLE 10 reaction results for different reactor types
| Reactor type | Conversion ratio of dimethyl ether (%) | Carbon monoxide conversion (%) | Methyl acetate selectivity (%) |
| Fluidized bed reactor | 48.0 | 95.9 | 99.8 |
| Moving bed reactor | 46.9 | 93.8 | 99.8 |
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 (10)
1. A process for the carbonylation of dimethyl ether to produce methyl acetate, the process comprising: dimethyl ether and feed gas containing carbon monoxide are reacted by a reactor filled with a solid acid catalyst to produce methyl acetate;
wherein the molar ratio of the carbon monoxide to the dimethyl ether is 0.05: 1-0.5: 1.
2. The method according to claim 1, wherein the molar ratio of carbon monoxide to dimethyl ether is 0.08:1 to 0.5: 1;
preferably, the molar ratio of the carbon monoxide to the dimethyl ether is 0.1: 1-0.5: 1.
3. The method according to claim 1, wherein the volume content of carbon monoxide in the feed gas containing carbon monoxide is 15-100%.
4. The method of claim 1, wherein the carbon monoxide-containing feed gas further comprises at least one of hydrogen, nitrogen, helium, argon, carbon dioxide, methane, and ethane.
5. The process of claim 1 wherein the solid acid catalyst is selected from at least one of dimethyl ether carbonylation catalysts.
6. The method of claim 1, wherein the solid acid catalyst comprises at least one of a zeolitic molecular sieve, a modified zeolitic molecular sieve;
wherein the framework type of the zeolite molecular sieve is selected from one of FER, MFI, MOR, ETL, MFS, MTF and EMT; the modification is at least one selected from element modification except zeolite molecular sieve framework elements, pyridine modification, organic amine modification, alkyl ammonium halide salt modification, acid treatment, water vapor treatment and ammonium ion exchange.
7. The method of claim 6, wherein the zeolitic molecular sieve is a hydrogen-form zeolitic molecular sieve.
8. The method of claim 7, wherein the hydrogen zeolite molecular sieve is present in the solid acid catalyst in an amount of from 10 wt% to 100 wt%;
further preferably, the content of the hydrogen-type zeolite molecular sieve in the solid acid catalyst is 10 wt% to 95 wt%;
preferably, the solid acid catalyst comprises a substrate;
the matrix is at least one of alumina, silica, kaolin and magnesia.
9. The method of claim 1, wherein the reactor is selected from one of a fixed bed reactor, a moving bed reactor, and a fluidized bed reactor.
10. The process according to claim 1, characterized in that the reaction conditions are:
the reaction temperature is 150-300 ℃, the reaction pressure is 0.5-25.0 MPa, and the mass space velocity of dimethyl ether is 0.05-6 h-1；
Preferably, the reaction temperature is 160-280 ℃;
further preferably, the reaction temperature is 170-260 ℃;
preferably, the reaction pressure is 0.5-20.0 MPa;
further preferably, the reaction pressure is 1.0-15.0 MPa;
preferably, the mass space velocity of the dimethyl ether is 0.2-6.0 h-1；
Preferably, the mass space velocity of the dimethyl ether is 0.1-4.0 h-1；
Further preferably, the mass space velocity of the dimethyl ether is 0.35-4.0 h-1。
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