CN108586247B - Method for preparing methyl acetate by carbonylation of dimethyl ether - Google Patents

Method for preparing methyl acetate by carbonylation of dimethyl ether Download PDF

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CN108586247B
CN108586247B CN201810706946.8A CN201810706946A CN108586247B CN 108586247 B CN108586247 B CN 108586247B CN 201810706946 A CN201810706946 A CN 201810706946A CN 108586247 B CN108586247 B CN 108586247B
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dimethyl ether
clinoptilolite
methyl acetate
hydrogen
carbonylation
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CN108586247A (en
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樊卫斌
许静
闫文付
魏渝伟
李俊汾
王建国
董梅
于吉红
徐如人
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Luoyang Jianlong Micro Nano New Materials Co ltd
Shanxi Institute of Coal Chemistry of CAS
Jilin University
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Luoyang Jianlong Micro Nano New Materials Co ltd
Shanxi Institute of Coal Chemistry of CAS
Jilin University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange

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Abstract

The invention provides a method for preparing methyl acetate by carbonylation of dimethyl ether, which comprises the following steps: and (2) carrying out dimethyl ether carbonylation reaction on the mixed gas of dimethyl ether and carbon monoxide through activated hydrogen clinoptilolite to obtain methyl acetate, wherein the hydrogen clinoptilolite has an HEU topological structure. The invention takes hydrogen clinoptilolite with HEU topological structure as the catalyst, the catalyst has 8-element pore canal structure and lower silicon-aluminum ratio, and can keep higher activity for a long time in the dimethyl ether carbonylation reaction process, thereby realizing the continuity and stability of preparing methyl acetate by dimethyl ether carbonylation and simultaneously having higher initial activity.

Description

Method for preparing methyl acetate by carbonylation of dimethyl ether
Technical Field
The invention relates to the technical field of preparation of methyl acetate by carbonylation of dimethyl ether, in particular to a method for preparing methyl acetate by carbonylation of dimethyl ether.
Background
Methyl acetate is also called methyl acetate, is one of the most widely used fatty acid esters at present, has excellent organic matter dissolving performance, and is widely used in the fields of synthetic intermediates of coatings, adhesives, medicines, printing inks and pesticides. Under normal temperature and pressure, the methyl acetate has extremely strong volatility, and can be used as a quick-drying solvent to dissolve various organic matters and resins such as acrylic acid, vinyl, nitrocellulose, polyurethane, phenolic resin, epoxy polyester and the like. The demand for methyl acetate is increasing at home and abroad.
Acetic acid and methanol are mostly adopted as raw materials in the traditional production process of methyl acetate, concentrated sulfuric acid is used as a catalyst, but the process has serious corrosion to equipment and environmental pollution, and because the concentrated sulfuric acid has strong oxidizing property and dehydration function, a series of side reactions occur in the reaction, the post-treatment of products is difficult, and the cost is high. In recent years, researchers have developed new processes for methanol dehydrocarbonylation synthesis using methanol as a raw material, methanol carbonylation one-step synthesis using methanol and CO as raw materials, synthesis of methyl formate by homologous reaction, and carbonylation of dimethyl ether. The raw material of the dimethyl ether carbonylation method can be prepared by a biomass synthesis gas one-step method, and the dimethyl ether is environment-friendly and convenient to store and transport, so that the dimethyl ether carbonylation method is considered to be a preparation process with great industrial value and application prospect.
Early research on the carbonylation of dimethyl ether to produce methyl acetate focused on noble metal catalysts supported on heteropolyacids, such as Wegman et al at RhW12PO4/SiO2The catalyst is used for catalyzing the carbonylation of dimethyl ether to prepare methyl acetate, Volkvad and the like by Rh/CsxH3-xPW12O40Methyl acetate was obtained for the catalyst. However, the dimethyl ether carbonylation reaction carried out by adopting the catalytic system can improve the preparation cost of methyl acetate due to the use of noble metal as the catalyst, and simultaneously, the production of the dimethyl ether is accompanied by the generation of hydrocarbons and a large amount of carbon deposition in the reaction processThe catalyst needs to be replaced frequently in the process of preparing methyl acetate. In 2006, Iglesia and the like report that dimethyl ether carbonylation reaction is carried out on a molecular sieve catalytic material for the first time, and because the molecular sieve catalyst does not need to load noble metal, the production cost of methyl acetate is effectively reduced, so that the molecular sieve catalyst becomes a research hotspot for preparing methyl acetate by a dimethyl ether carbonylation method. Currently, a mordenite molecular sieve is mainly adopted for preparing methyl acetate by a dimethyl ether carbonylation method, although the cost for producing the methyl acetate is reduced, the mordenite molecular sieve has the disadvantages of fast inactivation and poor stability, and the catalyst still needs to be frequently replaced in the process of preparing the methyl acetate, so that the methyl acetate cannot be continuously produced for a long time.
Disclosure of Invention
The invention aims to provide a method for preparing methyl acetate by carbonylation of dimethyl ether. The method provided by the invention can be stably and continuously carried out.
In order to achieve the above object, the present invention provides a method for preparing methyl acetate by carbonylation of dimethyl ether, comprising the steps of: and (2) carrying out dimethyl ether carbonylation reaction on the mixed gas of dimethyl ether and carbon monoxide through activated hydrogen clinoptilolite to obtain methyl acetate, wherein the hydrogen clinoptilolite has an HEU topological structure.
Preferably, the activating atmosphere is nitrogen atmosphere, the activating temperature is 480-520 ℃, and the activating time is 1.5-2.5 h.
Preferably, the particle size of the hydrogen clinoptilolite is 1-10 μm.
Preferably, the hydrogen clinoptilolite has a silicon-aluminum atomic ratio of 4-8: 1.
Preferably, the hydrogen clinoptilolite is a modified hydrogen clinoptilolite, and the modification comprises the following steps: and (3) placing the hydrogen clinoptilolite in an acidic aqueous solution for acid treatment, and then roasting to obtain the modified hydrogen clinoptilolite.
Preferably, the acidic aqueous solution is an aqueous solution of nitric acid, hydrochloric acid or oxalic acid, and the concentration of the acidic aqueous solution is 0.5-8 mol/L.
Preferably, the temperature of the acid treatment is 40-80 ℃, and the time of the acid treatment is 1-10 h.
Preferably, the roasting temperature is 530-550 ℃, and the roasting time is 5-7 h.
Preferably, the temperature of the dimethyl ether carbonylation reaction is 180-300 ℃, and the pressure of the dimethyl ether carbonylation reaction is 0.5-15 MPa.
Preferably, the space velocity of the mixed gas in the dimethyl ether carbonylation reaction is 1000-6000 mL/(g.h).
The invention provides a method for preparing methyl acetate by carbonylation of dimethyl ether, which comprises the following steps: and (2) carrying out dimethyl ether carbonylation reaction on the mixed gas of dimethyl ether and carbon monoxide through activated hydrogen clinoptilolite to obtain methyl acetate, wherein the hydrogen clinoptilolite has an HEU topological structure. The invention takes hydrogen clinoptilolite with HEU topological structure as the catalyst, the catalyst has 8-element pore canal structure and lower silicon-aluminum ratio, and can keep higher activity for a long time in the dimethyl ether carbonylation reaction process, thereby realizing the continuity and stability of preparing methyl acetate by dimethyl ether carbonylation and simultaneously having higher initial activity. Experimental results show that by adopting the method for preparing methyl acetate by carbonylation of dimethyl ether provided by the application, higher dimethyl ether conversion rate and methyl acetate selectivity can be achieved at the initial stage of reaction, the continuous reaction time can reach 100h, and the selectivity of methyl acetate is always kept above 97%.
Drawings
FIG. 1 is a graph showing the trend of the conversion of dimethyl ether in the production of methyl acetate by example 1 and comparative example 1;
FIG. 2 is a graph showing the selectivity profile of methyl acetate during the preparation of methyl acetate by example 1 and comparative example 1;
FIG. 3 shows the results of the measurement of the conversion of dimethyl ether and the selectivity of methyl acetate in the production of methyl acetate in example 2;
FIG. 4 shows the results of the measurement of the conversion of dimethyl ether and the selectivity of methyl acetate in the production of methyl acetate in example 3;
FIG. 5 shows the results of the measurement of the conversion of dimethyl ether and the selectivity of methyl acetate in the production of methyl acetate in example 4;
FIG. 6 shows the results of measuring the conversion of dimethyl ether and the selectivity of methyl acetate in the production of methyl acetate in example 5.
Detailed Description
The invention provides a method for preparing methyl acetate by carbonylation of dimethyl ether, which comprises the following steps: the dimethyl ether carbonylation reaction of a mixed gas of dimethyl ether (abbreviated as DME) and carbon monoxide is carried out by passing the mixed gas through activated hydrogen clinoptilolite having HEU topology to obtain methyl acetate (abbreviated as MA).
The invention activates hydrogen clinoptilolite to obtain activated hydrogen clinoptilolite.
In the present invention, the activation is preferably performed by calcining hydrogen clinoptilolite in a nitrogen atmosphere; the activation temperature is preferably 480-520 ℃, and more preferably 500 ℃; the activation time is preferably 1.5-2.5 h, and more preferably 2 h. In the invention, the activation can remove water and other impurity molecules adsorbed on the catalyst so as to ensure that the catalyst is fresh.
In the present invention, the particle size of the hydrogen clinoptilolite (i.e., H-type clinoptilolite) is preferably 1 to 10 μm, more preferably 2 to 5 μm.
In the invention, the hydrogen clinoptilolite preferably has a silicon-aluminum atomic ratio of 4-8: 1, more preferably 5-7: 1.
The source of the hydrogen clinoptilolite is not particularly limited in the invention, and in the embodiment of the invention, the preparation method of the hydrogen clinoptilolite preferably comprises the following steps:
(1) soaking sodium-potassium clinoptilolite in ammonium nitrate water solution for ion exchange to obtain ammonium clinoptilolite;
(2) and drying and roasting the ammonium clinoptilolite in sequence to obtain the hydrogen clinoptilolite.
In the present invention, preferably, the ammonium clinoptilolite is obtained by immersing sodium-potassium clinoptilolite in an aqueous ammonium nitrate solution and performing ion exchange. In the present invention, the equilibrium positive in clinoptilolite sodium-potassium form is present in the ion exchange processIon (Na)+、K+) And NH4 +And exchanging to obtain the ammonium clinoptilolite.
In the invention, the particle size of the sodium-potassium clinoptilolite is preferably 1-10 μm, and more preferably 2-5 μm; the preferred atomic ratio of silicon to aluminum of the sodium-potassium clinoptilolite is 4-6: 1.
The source of the sodium-potassium clinoptilolite is not specially required, and the sodium-potassium clinoptilolite sold in the market is adopted, and in the embodiment of the invention, the sodium-potassium clinoptilolite is preferably the sodium-potassium clinoptilolite with the model number of H-06 produced by Luoyangjianlong sodium new material GmbH.
In the invention, the concentration of the ammonium nitrate aqueous solution is preferably 0.5-1.2 mol/L, and more preferably 0.8-1 mol/L.
In the present invention, the ratio of the mass of the sodium-potassium clinoptilolite to the volume of the ammonium nitrate aqueous solution is preferably 1g:25 to 35mL, and more preferably 1g:30 mL.
In the invention, the ion exchange frequency is preferably 1-3 times, and more preferably 3 times; the temperature of each ion exchange is preferably 75-85 ℃ independently, and more preferably 80 ℃; the time of each ion exchange is preferably 3-6 h independently, and more preferably 5 h; the time of the ion exchange is preferably started when the system temperature reaches the temperature required for the ion exchange; according to the invention, preferably, products obtained after each ion exchange are sequentially washed and dried, and then the next ion exchange is carried out; the method for washing and drying is not particularly limited, and a conventional washing and drying method can be adopted.
After the ion exchange is completed, the present invention preferably filters the resulting product to obtain the ammonium clinoptilolite.
After obtaining the ammonium clinoptilolite, the ammonium clinoptilolite is preferably dried and roasted in sequence to obtain the hydrogen clinoptilolite. In the calcination process, clinoptilolite is converted from the ammonium form to the hydrogen form.
The drying condition is not specially limited, and a product with constant weight can be obtained; in the embodiment of the invention, the drying temperature is preferably 90-110 ℃, and the drying time is preferably 11-13 h.
In the present invention, the calcination of the ammonium clinoptilolite is preferably performed in an air atmosphere; the roasting temperature is preferably 530-550 ℃, and more preferably 540 ℃; the roasting time is preferably 5-7 hours, and more preferably 6 hours.
In the present invention, the hydrogen clinoptilolite is preferably a modified hydrogen clinoptilolite, and the modification preferably comprises the steps of: and (3) placing the hydrogen clinoptilolite in an acidic aqueous solution for acid treatment, and then roasting to obtain the modified hydrogen clinoptilolite. In the invention, the acid treatment can remove part of framework aluminum in the molecular sieve, reduce the acidity of the molecular sieve, reduce side reaction active sites and further improve the catalytic stability of the hydrogen clinoptilolite.
In the present invention, the acidic aqueous solution is preferably an aqueous solution of nitric acid, hydrochloric acid or oxalic acid; the concentration of the acidic aqueous solution is preferably 0.5-8 mol/L, more preferably 2-6 mol/L, and most preferably 4-5 mol/L.
In the present invention, the ratio of the mass of the hydrogen clinoptilolite to the volume of the acidic aqueous solution is preferably 1 g/25 to 35mL, and more preferably 1 g/30 mL.
In the invention, the temperature of the acid treatment is preferably 40-80 ℃, and more preferably 50-70 ℃; the time of the acid treatment is preferably 1-10 hours, and more preferably 4-6 hours.
After the acid treatment is completed, the invention preferably sequentially filters, washes and dries the product obtained by the acid treatment to obtain a dried acid-treated product.
The filtration and washing method is not particularly limited in the present invention, and a filtration and washing method which is conventional in the art may be used.
The drying condition is not specially limited, and a product with constant weight can be obtained; in the embodiment of the invention, the drying temperature is preferably 90-110 ℃, and the drying time is preferably 11-13 h.
After obtaining the dried acid-treated product, the present invention preferably roasts the dried acid-treated product to obtain the modified hydrogen clinoptilolite. In the present invention, the calcination of the acid-treated product is preferably performed in an air atmosphere; the roasting temperature is preferably 530-550 ℃, and more preferably 540 ℃; the roasting time is preferably 5-7 hours, and more preferably 6 hours.
In the invention, the molar ratio of dimethyl ether to carbon monoxide is preferably 1: 5-50, more preferably 1: 10-35, and most preferably 1: 20-30.
In the invention, the temperature of the dimethyl ether carbonylation reaction is preferably 180-300 ℃, and more preferably 230-280 ℃; the pressure of the dimethyl ether carbonylation reaction is preferably 0.5-15 MPa, and more preferably 3-10 MPa.
In the invention, the space velocity of the mixed gas in the dimethyl ether carbonylation reaction is preferably 1000-6000 mL/(g.h), and more preferably 2500-4000 mL/(g.h).
In the invention, the reactor used for the dimethyl ether carbonylation reaction is preferably a fixed bed reactor, a moving bed reactor or a fluidized bed reactor, and more preferably a moving bed reactor or a fluidized bed reactor.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Adding 50g sodium-potassium clinoptilolite (LONGYANGGANLONGMINI New Material Co., Ltd., model number H-06) into 1500mL NH with concentration of 1mol/L4NO3Ion exchange is carried out for 5 hours at the constant temperature of 80 ℃ in the water solution, then the obtained product is washed by deionized water and dried in sequence, and the ion exchange process is repeated twice to obtain ammonium clinoptilolite; drying the ammonium clinoptilolite at 100 ℃ for 12h, and then roasting at 540 ℃ for 6h in an air atmosphere to obtain hydrogen clinoptilolite; the hydrogen clinoptilolite has an 8-element pore channel structure, and the average particle size is 3 mu m;
(2) putting the hydrogen clinoptilolite obtained in the step (1) as a catalyst into a fixed bed reactor, and roasting for 2h at 500 ℃ in a nitrogen atmosphere to obtain activated hydrogen clinoptilolite; reducing the temperature of the bed layer to 190 ℃, controlling the pressure to be 2MPa, introducing mixed gas with the molar ratio of dimethyl ether to carbon monoxide being 1:10, maintaining the pressure to be 2MPa, controlling the space velocity of the mixed gas to be 1375 mL/(g.h), and carrying out dimethyl ether carbonylation reaction to prepare methyl acetate.
The reaction process of the preparation method of this example is detected, and the obtained results are shown in fig. 1 and fig. 2, in the preparation method provided in this example, the initial conversion rate of dimethyl ether can reach 2.5%, the initial maximum conversion rate is 8.1%, the initial selectivity of methyl acetate can reach 95%, after 40 hours of reaction, the conversion rate of dimethyl ether can still be maintained at 5%, and the selectivity of methyl acetate is always above 95%.
Example 2
(1) Clinoptilolite hydrogen form was prepared using the procedure described in example 1;
(2) putting the hydrogen clinoptilolite obtained in the step (1) as a catalyst into a fixed bed reactor, and roasting for 2h at 500 ℃ in a nitrogen atmosphere to obtain activated hydrogen clinoptilolite; reducing the temperature of the bed layer to 190 ℃, controlling the pressure to be 1MPa, introducing mixed gas with the molar ratio of dimethyl ether to carbon monoxide being 1:10, maintaining the pressure to be 1MPa, controlling the space velocity of the mixed gas to be 1000 mL/(g.h), and carrying out dimethyl ether carbonylation reaction to prepare methyl acetate.
The results of examining the reaction process of the preparation method of this example are shown in fig. 3, and the preparation method provided in this example has an initial maximum conversion of dimethyl ether of 13.21% and an initial maximum selectivity of methyl acetate of 97.43%, and when the reaction time reaches 60 hours, the conversion of dimethyl ether begins to decrease and the catalyst begins to deactivate.
Example 3
(1) Clinoptilolite hydrogen form was prepared using the procedure described in example 1;
(2) putting the hydrogen clinoptilolite obtained in the step (1) as a catalyst into a fixed bed reactor, and roasting for 2h at 500 ℃ in a nitrogen atmosphere to obtain activated hydrogen clinoptilolite; reducing the temperature of the bed layer to 190 ℃, controlling the pressure to be 10MPa, introducing mixed gas with the molar ratio of dimethyl ether to carbon monoxide being 1:10, maintaining the pressure to be 10MPa, controlling the space velocity of the mixed gas to be 1000 mL/(g.h), and carrying out dimethyl ether carbonylation reaction to prepare methyl acetate.
The results of examining the reaction process of the preparation method of this example are shown in fig. 4, and the preparation method provided in this example has an initial maximum conversion of dimethyl ether of 25.89% and an initial maximum selectivity of methyl acetate of 98.75%, and when the reaction time reaches 60 hours, the conversion of dimethyl ether begins to decrease and the catalyst begins to deactivate.
Example 4
(1) Clinoptilolite hydrogen form was prepared using the procedure described in example 1;
(2) putting the hydrogen clinoptilolite obtained in the step (1) as a catalyst into a fixed bed reactor, and roasting for 2h at 500 ℃ in a nitrogen atmosphere to obtain activated hydrogen clinoptilolite; reducing the temperature of the bed layer to 260 ℃, controlling the pressure to be 1MPa, introducing mixed gas with the molar ratio of dimethyl ether to carbon monoxide being 1:30, maintaining the pressure to be 1MPa, controlling the space velocity of the mixed gas to be 3000 mL/(g.h), and carrying out dimethyl ether carbonylation reaction to prepare methyl acetate.
The results of examining the reaction process of the preparation method of this example are shown in fig. 5, and the preparation method provided in this example has an initial highest conversion of dimethyl ether of 28.66% and an initial highest selectivity of methyl acetate of 98.80%, and when the reaction time reaches 70 hours, the conversion of dimethyl ether is still maintained above 20%, and then it starts to decrease rapidly, and the catalyst starts to deactivate.
Example 5
(1) Clinoptilolite hydrogen form was prepared using the procedure described in example 1;
(2) putting the hydrogen clinoptilolite obtained in the step (1) as a catalyst into a fixed bed reactor, and roasting for 2h at 500 ℃ in a nitrogen atmosphere to obtain activated hydrogen clinoptilolite; reducing the temperature of the bed layer to 210 ℃, controlling the pressure to be 3MPa, introducing mixed gas with the molar ratio of dimethyl ether to carbon monoxide of 1:30, maintaining the pressure to be 3MPa, controlling the space velocity of the mixed gas to be 1375 mL/(g.h), and carrying out dimethyl ether carbonylation reaction to prepare methyl acetate.
The results of examining the reaction process of the preparation method of this example are shown in fig. 5, and the preparation method provided in this example has an initial maximum conversion of dimethyl ether of 40.85%, an initial maximum selectivity of methyl acetate of 99.17%, and a conversion of dimethyl ether of more than 35% still maintained at 80 hours, after which it starts to decrease rapidly and the catalyst starts to deactivate.
Example 6
(1) Clinoptilolite hydrogen form was prepared using the procedure described in example 1;
(2) adding 5g of hydrogen clinoptilolite obtained in the step (1) into 150ml of HNO with the concentration of 0.5mol/L3Heating and stirring in water bath at 80 ℃ for 10h in an aqueous solution, then sequentially filtering, washing with deionized water, drying at 100 ℃ for 12h, and then roasting at 540 ℃ for 6h in an air atmosphere to obtain modified hydrogen clinoptilolite;
(3) taking the modified hydrogen clinoptilolite obtained in the step (2) as a catalyst, putting the catalyst into a fixed bed reactor, and roasting the catalyst for 2 hours at 500 ℃ in a nitrogen atmosphere to obtain activated hydrogen clinoptilolite; reducing the temperature of the bed layer to 210 ℃, controlling the pressure to be 3MPa, introducing mixed gas with the molar ratio of dimethyl ether to carbon monoxide of 1:30, maintaining the pressure to be 3MPa, controlling the space velocity of the mixed gas to be 1375 mL/(g.h), and carrying out dimethyl ether carbonylation reaction to prepare methyl acetate.
The reaction process of the preparation method of this embodiment is detected, and in the preparation method provided by this embodiment, when reacting for 4 hours, the conversion rate of dimethyl ether is 39.92%, and the selectivity of methyl acetate is 99.25%; when the reaction is carried out for 50 hours, the conversion rate of the dimethyl ether is 37.80 percent, and the selectivity of the methyl acetate is 99.18 percent; when the reaction is carried out for 100 hours, the conversion rate of the dimethyl ether can still reach 25.22 percent, and the selectivity of the methyl acetate is 98.97 percent.
Example 7
(1) Clinoptilolite hydrogen form was prepared using the procedure described in example 1;
(2) 5g of hydrogen type clinoptilolite obtained in step (1)Adding the stone into 150ml of HNO with the concentration of 2mol/L3Heating and stirring in water bath at 80 ℃ for 10h in an aqueous solution, then sequentially filtering, washing with deionized water, drying at 100 ℃ for 12h, and then roasting at 540 ℃ for 6h in an air atmosphere to obtain modified hydrogen clinoptilolite;
(3) taking the modified hydrogen clinoptilolite obtained in the step (2) as a catalyst, putting the catalyst into a fixed bed reactor, and roasting the catalyst for 2 hours at 500 ℃ in a nitrogen atmosphere to obtain activated hydrogen clinoptilolite; reducing the temperature of the bed layer to 210 ℃, controlling the pressure to be 3MPa, introducing mixed gas with the molar ratio of dimethyl ether to carbon monoxide of 1:30, maintaining the pressure to be 3MPa, controlling the space velocity of the mixed gas to be 1375 mL/(g.h), and carrying out dimethyl ether carbonylation reaction to prepare methyl acetate.
The reaction process of the preparation method provided by the embodiment is detected, and in the preparation method provided by the embodiment, when the reaction is carried out for 4 hours, the conversion rate of dimethyl ether is 34.23%, and the selectivity of methyl acetate is 99.10%; when the reaction is carried out for 50 hours, the conversion rate of the dimethyl ether is 32.47 percent, and the selectivity of the methyl acetate is 99.02 percent; when the reaction is carried out for 100 hours, the conversion rate of the dimethyl ether can still reach 23.88 percent, and the selectivity of the methyl acetate is 98.89 percent.
Example 8
(1) Clinoptilolite hydrogen form was prepared using the procedure described in example 1;
(2) adding 5g of hydrogen clinoptilolite obtained in the step (1) into 150ml of HNO with the concentration of 6mol/L3Heating and stirring in water bath at 80 ℃ for 10h in an aqueous solution, then sequentially filtering, washing with deionized water, drying at 100 ℃ for 12h, and then roasting at 540 ℃ for 6h in an air atmosphere to obtain modified hydrogen clinoptilolite;
(3) taking the modified hydrogen clinoptilolite obtained in the step (2) as a catalyst, putting the catalyst into a fixed bed reactor, and roasting the catalyst for 2 hours at 500 ℃ in a nitrogen atmosphere to obtain activated hydrogen clinoptilolite; reducing the temperature of the bed layer to 210 ℃, controlling the pressure to be 3MPa, introducing mixed gas with the molar ratio of dimethyl ether to carbon monoxide of 1:30, maintaining the pressure to be 3MPa, controlling the space velocity of the mixed gas to be 1375 mL/(g.h), and carrying out dimethyl ether carbonylation reaction to prepare methyl acetate.
The reaction process of the preparation method of this embodiment is detected, and in the preparation method provided by this embodiment, when reacting for 4 hours, the conversion rate of dimethyl ether is 29.55%, and the selectivity of methyl acetate is 99.88%; when the reaction is carried out for 50 hours, the conversion rate of the dimethyl ether is 28.97 percent, and the selectivity of the methyl acetate is 98.53 percent; when the reaction is carried out for 100 hours, the conversion rate of the dimethyl ether can still reach 24.37 percent, and the selectivity of the methyl acetate is 98.10 percent.
Example 9
(1) Clinoptilolite hydrogen form was prepared using the procedure described in example 1;
(2) adding 5g of hydrogen clinoptilolite obtained in the step (1) into 150ml of HNO with the concentration of 8mol/L3Heating and stirring in water bath at 40 ℃ for 1h in an aqueous solution, then sequentially filtering, washing with deionized water, drying at 100 ℃ for 12 hours, and then roasting at 540 ℃ for 6 hours in an air atmosphere to obtain modified hydrogen clinoptilolite;
(3) taking the modified hydrogen clinoptilolite obtained in the step (2) as a catalyst, putting the catalyst into a fixed bed reactor, and roasting the catalyst for 2 hours at 500 ℃ in a nitrogen atmosphere to obtain activated hydrogen clinoptilolite; reducing the temperature of the bed layer to 210 ℃, controlling the pressure to be 3MPa, introducing mixed gas with the molar ratio of dimethyl ether to carbon monoxide of 1:30, maintaining the pressure to be 3MPa, controlling the space velocity of the mixed gas to be 1375 mL/(g.h), and carrying out dimethyl ether carbonylation reaction to prepare methyl acetate.
The reaction process of the preparation method provided by the embodiment is detected, and in the preparation method provided by the embodiment, when the reaction is carried out for 4 hours, the conversion rate of dimethyl ether is 30.80%, and the selectivity of methyl acetate is 98.87%; when the reaction is carried out for 50 hours, the conversion rate of the dimethyl ether is 27.34 percent, and the selectivity of the methyl acetate is 98.43 percent; when the reaction is carried out for 100 hours, the conversion rate of the dimethyl ether can still reach 20.42 percent, and the selectivity of the methyl acetate is 97.98 percent.
Example 10
(1) Clinoptilolite hydrogen form was prepared using the procedure described in example 1;
(2) adding 5g of the hydrogen clinoptilolite obtained in the step (1) into 150ml of hydrochloric acid aqueous solution with the concentration of 0.5mol/L, heating and stirring in a water bath at 80 ℃ for 10h, then sequentially filtering, washing with deionized water, drying at 100 ℃ for 12h, and then roasting at 540 ℃ for 6h in an air atmosphere to obtain modified hydrogen clinoptilolite;
(3) taking the modified hydrogen clinoptilolite obtained in the step (2) as a catalyst, putting the catalyst into a fixed bed reactor, and roasting the catalyst for 2 hours at 500 ℃ in a nitrogen atmosphere to obtain activated hydrogen clinoptilolite; reducing the temperature of the bed layer to 210 ℃, controlling the pressure to be 3MPa, introducing mixed gas with the molar ratio of dimethyl ether to carbon monoxide of 1:30, maintaining the pressure to be 3MPa, controlling the space velocity of the mixed gas to be 1375 mL/(g.h), and carrying out dimethyl ether carbonylation reaction to prepare methyl acetate.
The reaction process of the preparation method of this embodiment is detected, and in the preparation method provided in this embodiment, when reacting for 4 hours, the conversion rate of dimethyl ether is 52.61%, and the selectivity of methyl acetate is 99.46%; when the reaction is carried out for 50 hours, the conversion rate of the dimethyl ether is 40.60 percent, and the selectivity of the methyl acetate is 99.18 percent; when the reaction is carried out for 100 hours, the conversion rate of the dimethyl ether can still reach 27.84 percent, and the selectivity of the methyl acetate is 98.77 percent.
Example 11
(1) Clinoptilolite hydrogen form was prepared using the procedure described in example 1;
(2) adding 5g of hydrogen clinoptilolite obtained in the step (1) into 150ml of oxalic acid aqueous solution with the concentration of 0.5mol/L, heating and stirring in a water bath at 80 ℃ for 10h, then sequentially filtering, washing with deionized water, drying at 100 ℃ for 12h, and then roasting at 540 ℃ for 6h in an air atmosphere to obtain modified hydrogen clinoptilolite;
(3) taking the modified hydrogen clinoptilolite obtained in the step (2) as a catalyst, putting the catalyst into a fixed bed reactor, and roasting the catalyst for 2 hours at 500 ℃ in a nitrogen atmosphere to obtain activated hydrogen clinoptilolite; reducing the temperature of the bed layer to 210 ℃, controlling the pressure to be 3MPa, introducing mixed gas with the molar ratio of dimethyl ether to carbon monoxide of 1:30, maintaining the pressure to be 3MPa, controlling the space velocity of the mixed gas to be 1375 mL/(g.h), and carrying out dimethyl ether carbonylation reaction to prepare methyl acetate.
The reaction process of the preparation method of this embodiment is detected, and in the preparation method provided in this embodiment, when reacting for 4 hours, the conversion rate of dimethyl ether is 47.54%, and the selectivity of methyl acetate is 99.43%; when the reaction is carried out for 50 hours, the conversion rate of the dimethyl ether is 38.27 percent, and the selectivity of the methyl acetate is 99.02 percent; when the reaction is carried out for 100 hours, the conversion rate of the dimethyl ether can still reach 25.32 percent, and the selectivity of the methyl acetate is 98.54 percent.
Example 12
(1) Clinoptilolite hydrogen form was prepared using the procedure described in example 1;
(2) putting the hydrogen clinoptilolite obtained in the step (1) as a catalyst into a fluidized bed reactor, and roasting for 2h at 500 ℃ in a nitrogen atmosphere to obtain activated hydrogen clinoptilolite; reducing the temperature of the bed layer to 210 ℃, controlling the pressure to be 3MPa, introducing mixed gas with the molar ratio of dimethyl ether to carbon monoxide of 1:30, maintaining the pressure to be 3MPa, controlling the space velocity of the mixed gas to be 1375 mL/(g.h), and carrying out dimethyl ether carbonylation reaction to prepare methyl acetate.
The reaction process of the preparation method of this embodiment is detected, and in the preparation method provided by this embodiment, when reacting for 4 hours, the conversion rate of dimethyl ether is 58.70%, and the selectivity of methyl acetate is 99.89%; when the reaction is carried out for 50 hours, the conversion rate of the dimethyl ether is 51.33 percent, and the selectivity of the methyl acetate is 99.76 percent; when the reaction is carried out for 100 hours, the conversion rate of the dimethyl ether can still reach 18.90 percent, and the selectivity of the methyl acetate is 99.13 percent.
Example 13
(1) Clinoptilolite hydrogen form was prepared using the procedure described in example 1;
(2) the hydrogen clinoptilolite obtained in the step (1) is used as a catalyst and is put into a moving bed reactor, and the hydrogen clinoptilolite is roasted for 2 hours at 500 ℃ in the nitrogen atmosphere to obtain activated hydrogen clinoptilolite; reducing the temperature of the bed layer to 210 ℃, controlling the pressure to be 3MPa, introducing mixed gas with the molar ratio of dimethyl ether to carbon monoxide of 1:30, maintaining the pressure to be 3MPa, controlling the space velocity of the mixed gas to be 1375 mL/(g.h), and carrying out dimethyl ether carbonylation reaction to prepare methyl acetate.
The reaction process of the preparation method provided by the embodiment is detected, and in the preparation method provided by the embodiment, when the reaction is carried out for 4 hours, the conversion rate of dimethyl ether is 65.7%, and the selectivity of methyl acetate is 99.50%; when the reaction is carried out for 50 hours, the conversion rate of the dimethyl ether is 54.4 percent, and the selectivity of the methyl acetate is 99.35 percent; when the reaction is carried out for 100 hours, the conversion rate of the dimethyl ether can still reach 16.22 percent, and the selectivity of the methyl acetate is 98.76 percent.
Example 14
1) Adding 50g sodium-potassium clinoptilolite (LONGYANGGANLONGMINI New Material Co., Ltd., model number H-06) into 1500mL NH with concentration of 0.5mol/L4NO3Ion exchange is carried out for 5 hours at the constant temperature of 80 ℃ in the water solution, then the obtained product is washed by deionized water and dried in sequence, and the ion exchange process is repeated for three times to obtain ammonium clinoptilolite; drying the ammonium clinoptilolite at 100 ℃ for 12h, and then roasting at 540 ℃ for 6h in an air atmosphere to obtain hydrogen clinoptilolite;
(2) putting the hydrogen clinoptilolite obtained in the step (1) as a catalyst into a fixed bed reactor, and roasting for 2h at 500 ℃ in a nitrogen atmosphere to obtain activated hydrogen clinoptilolite; reducing the temperature of the bed layer to 210 ℃, controlling the pressure to be 3MPa, introducing mixed gas with the molar ratio of dimethyl ether to carbon monoxide of 1:30, maintaining the pressure to be 3MPa, controlling the space velocity of the mixed gas to be 1375 mL/(g.h), and carrying out dimethyl ether carbonylation reaction to prepare methyl acetate.
The reaction process of the preparation method provided by the embodiment is detected, and in the preparation method provided by the embodiment, when the reaction is carried out for 4 hours, the conversion rate of dimethyl ether is 42.54%, and the selectivity of methyl acetate is 99.03%; when the reaction is carried out for 50 hours, the conversion rate of the dimethyl ether is 39.42 percent, and the selectivity of the methyl acetate is 99.07 percent; when the reaction time is 100 hours, the conversion rate of the dimethyl ether is reduced to 15.33 percent, and the selectivity of the methyl acetate is 96.50 percent.
Example 15
(1) Clinoptilolite hydrogen form was prepared using the procedure described in example 1;
(2) adding 5g of the hydrogen clinoptilolite obtained in the step (1) into 150ml of 2mol/L HCl aqueous solution, heating and stirring in a water bath at 80 ℃ for 10h, then sequentially filtering, washing with deionized water, drying at 100 ℃ for 12h, and roasting at 540 ℃ for 6h in an air atmosphere to obtain modified hydrogen clinoptilolite;
(3) taking the modified hydrogen clinoptilolite obtained in the step (2) as a catalyst, putting the catalyst into a fixed bed reactor, and roasting the catalyst for 2 hours at 500 ℃ in a nitrogen atmosphere to obtain activated hydrogen clinoptilolite; reducing the temperature of the bed layer to 200 ℃, controlling the pressure to be 3MPa, introducing mixed gas with the molar ratio of dimethyl ether to carbon monoxide being 1:30, maintaining the pressure to be 3MPa, controlling the space velocity of the mixed gas to be 1375 mL/(g.h), and carrying out dimethyl ether carbonylation reaction to prepare methyl acetate.
The reaction process of the preparation method provided by the embodiment is detected, and in the preparation method provided by the embodiment, when the reaction is carried out for 4 hours, the conversion rate of dimethyl ether is 45.72%, and the selectivity of methyl acetate is 99.40%; when the reaction is carried out for 50 hours, the conversion rate of the dimethyl ether is 38.80 percent, and the selectivity of the methyl acetate is 99.0 percent; when the reaction is carried out for 100 hours, the conversion rate of the dimethyl ether can still reach 28.42 percent, and the selectivity of the methyl acetate is 98.77 percent.
Example 16
(1) Hydrochloric acid modified hydrogen clinoptilolite was prepared as described in steps (1) and (2) of example 15;
(2) taking the modified hydrogen clinoptilolite obtained in the step (1) as a catalyst, putting the catalyst into a fixed bed reactor, and roasting the catalyst for 2 hours at 500 ℃ in a nitrogen atmosphere to obtain activated hydrogen clinoptilolite; reducing the temperature of the bed layer to 220 ℃, controlling the pressure to be 3MPa, introducing mixed gas with the molar ratio of dimethyl ether to carbon monoxide of 1:30, maintaining the pressure to be 3MPa, controlling the space velocity of the mixed gas to be 1375 mL/(g.h), and carrying out dimethyl ether carbonylation reaction to prepare methyl acetate.
The reaction process of the preparation method provided by the embodiment is detected, and in the preparation method provided by the embodiment, when the reaction is carried out for 4 hours, the conversion rate of dimethyl ether is 60.02%, and the selectivity of methyl acetate is 99.00%; when the reaction is carried out for 50 hours, the conversion rate of the dimethyl ether is 48.80 percent, and the selectivity of the methyl acetate is 99.10 percent; when the reaction is carried out for 100 hours, the conversion rate of the dimethyl ether can still reach 28.82 percent, and the selectivity of the methyl acetate is 98.63 percent.
Comparative example 1
Methyl acetate was prepared by dimethyl ether carbonylation reaction replacing hydrogen clinoptilolite with hydrogen mordenite molecular sieve in example 1 under the same reaction conditions as in example 1. As shown in fig. 1 and 2, the initial conversion rate of dimethyl ether was close to 0, the initial maximum conversion rate was 10.5%, the initial selectivity of methyl acetate was also close to 0, the initial maximum selectivity was 91.8% in the preparation method provided in comparative example 1, and the conversion rate of dimethyl ether and the selectivity of methyl acetate rapidly decreased during the reaction. Compared with example 1, the initial activity and stability are significantly poorer.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. A method for preparing methyl acetate by dimethyl ether carbonylation comprises the following steps:
carrying out dimethyl ether carbonylation reaction on the mixed gas of dimethyl ether and carbon monoxide through activated hydrogen clinoptilolite to obtain methyl acetate, wherein the hydrogen clinoptilolite has an HEU topological structure:
the hydrogen clinoptilolite is modified hydrogen clinoptilolite;
the modification step is as follows: and (3) putting the hydrogen clinoptilolite into an acidic aqueous solution for acid treatment, and then sequentially filtering, washing, drying and roasting to obtain the modified hydrogen clinoptilolite.
2. The method for preparing methyl acetate by carbonylation of dimethyl ether according to claim 1, wherein the activating atmosphere is nitrogen atmosphere, the activating temperature is 480-520 ℃, and the activating time is 1.5-2.5 h.
3. The method for preparing methyl acetate by carbonylation of dimethyl ether according to claim 1, wherein the hydrogen clinoptilolite has a particle size of 1 to 10 μm.
4. The carbonylation process for producing methyl acetate from dimethyl ether according to claim 1, wherein the hydrogen clinoptilolite has a silica to alumina atomic ratio of 4 to 8: 1.
5. The method for preparing methyl acetate by carbonylation of dimethyl ether according to claim 1, wherein the acidic aqueous solution is an aqueous solution of nitric acid, hydrochloric acid or oxalic acid, and the concentration of the acidic aqueous solution is 0.5-8 mol/L.
6. The method for preparing methyl acetate by carbonylation of dimethyl ether according to claim 1, wherein the acid treatment temperature is 40 to 80 ℃ and the acid treatment time is 1 to 10 hours.
7. The method for preparing methyl acetate by carbonylation of dimethyl ether according to claim 1, wherein the roasting temperature is 530 to 550 ℃, and the roasting time is 5 to 7 hours.
8. The method for preparing methyl acetate by carbonylation of dimethyl ether according to claim 1, wherein the temperature of the carbonylation of dimethyl ether is 180 to 300 ℃, and the pressure of the carbonylation of dimethyl ether is 0.5 to 15 MPa.
9. The method for preparing methyl acetate by carbonylation of dimethyl ether according to claim 1, wherein the space velocity of the mixed gas in the carbonylation of dimethyl ether is 1000-6000 mL/(g-h).
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