CN111348661A - ETL molecular sieve, metal modified ETL molecular sieve and application thereof in carbonylation reaction - Google Patents
ETL molecular sieve, metal modified ETL molecular sieve and application thereof in carbonylation reaction Download PDFInfo
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Abstract
The invention relates to a metal modified ETL molecular sieve and application of the ETL molecular sieve and the metal modified ETL molecular sieve in converting dimethyl ether and/or methanol into methyl acetate and/or acetic acid in a carbonylation reaction. The novel molecular sieve catalyst with the ETL structure has excellent carbonylation performance, high activity, selectivity of methyl acetate, acetic acid or a mixture of methyl acetate and acetic acid higher than 95 percent, and single-pass stability of the molecular sieve catalyst higher than 2000 hours. In addition, after the molecular sieve metal is modified, the activity, selectivity and stability of the catalyst can be further obviously improved.
Description
Technical Field
The invention relates to a metal modified ETL molecular sieve and application of the ETL molecular sieve and the metal modified ETL molecular sieve in converting dimethyl ether and/or methanol into methyl acetate and/or acetic acid in a carbonylation reaction.
Background
Methyl acetate or acetic acid is widely used in the industries of spices, coatings, adhesives, medicines and the like, is a good environment-friendly solvent, can be used for replacing acetone, butanone, ethyl acetate, cyclopentane and the like, is an important organic raw material intermediate, and is mainly used as downstream products of acetic acid, ethanol, acetic anhydride, methyl acrylate, vinyl acetate, acetamide and the like. There is an increasing demand for methyl acetate or acetic acid at home and abroad. In recent years, methyl acetate has developed new applications, such as hydrogenation of ethanol. As a novel fuel, ethanol has the characteristics of cleanness and high efficiency. In addition, as an important basic raw material, ethanol has important application in the aspects of medicines, chemical engineering and the like.
At present, the industrial production method of ethanol mainly comprises a chemical synthesis method and a biological fermentation method. The chemical synthesis method mainly refers to a method for preparing ethanol from petroleum resources through an ethylene catalytic hydration method, and the method has the defects of serious pollution, high energy consumption and the like. The biological fermentation method is to prepare ethanol by fermenting biomass which is mainly corn, sugarcane, cassava and the like, but the route is easy to cause global food shortage and price fluctuation. Methyl acetate or acetic acid as an intermediate product, a high-efficiency clean and cheap path from non-petroleum-based carbon-containing resources to the preparation of clean energy ethanol is constructed. Therefore, the catalytic research for preparing methyl acetate or acetic acid by dimethyl ether or methanol carbonylation is a very significant subject.
Dimethyl ether or methanol carbonylA homogeneous catalysis path is mostly adopted in the traditional production process for preparing methyl acetate or acetic acid by means of methylation, but the method has the problems that products and a catalyst are difficult to separate, noble metals are used, the production cost is increased, and iodide is used, so that the method is relatively high in equipment corrosion and is not favorable for operating environment. Wegman et al (J Chem Soc Chem Comm1994, (8), 947-12PO4/SiO2Dimethyl ether carbonylation reaction is carried out for the catalyst, and the yield of 16 percent methyl acetate is obtained. Volkova et al (Catalyst Letters 2002, 80(3-4), 175-3-xPW12O40The dimethyl ether carbonylation reaction is studied, and a ratio of RhW is obtained12P(VSiO2) One order of magnitude higher reaction rate. However, the catalyst systems adopted all use noble metals, so that the preparation cost for producing the methyl acetate is increased. In addition, the catalyst system is easy to generate a large amount of hydrocarbons and carbon deposition in the dimethyl ether carbonylation reaction process, so that the production of the catalyst needs to be frequently stopped and the catalyst needs to be replaced in the methyl acetate preparation process. Good dimethyl ether carbonylation activity was reported by Iglesia et al (Angew. chem, int. Ed., 2006, (10), 1617-. Because the molecular sieve does not need to load noble metal and is easy to regenerate, the cost for preparing methyl acetate or acetic acid is effectively reduced, and the molecular sieve catalyst becomes a research hotspot for researching the preparation of methyl acetate or acetic acid by dimethyl ether or methanol carbonylation. However, the currently used mordenite and ZSM-35 molecular sieve which are not modified still have the characteristics of poor stability and easy inactivation, and the catalyst still needs to be frequently replaced in the carbonylation process of dimethyl ether or methanol, so that the aim of continuously preparing methyl acetate or acetic acid for a long time cannot be fulfilled. Therefore, the research on molecular sieve catalysts with high stability for preparing methyl acetate or acetic acid by dimethyl ether or methanol carbonylation is a very significant subject.
Disclosure of Invention
In view of the above-mentioned state of the art, the present inventors have conducted extensive and intensive studies on a molecular sieve catalyst for the carbonylation of dimethyl ether and/or methanol to produce methyl acetate and/or acetic acid in order to find a molecular sieve catalyst having an entirely new structure with stable carbonylation activity. The inventor finds that the novel molecular sieve catalyst with an ETL structure (such as EU-12) has excellent carbonylation performance, high activity and can realize the selectivity of methyl acetate, acetic acid or a mixture of the methyl acetate and the acetic acid to be higher than 95 percent, and the single-pass stability of the molecular sieve catalyst is larger than 2000 hours. In addition, after the molecular sieve metal is modified, the activity, selectivity and stability of the catalyst can be further obviously improved.
The present invention has been completed based on the above findings.
The invention aims to provide a metal modified ETL molecular sieve which has high activity, selectivity and stability in the preparation of methyl acetate and/or acetic acid by carbonylation of dimethyl ether and/or methanol.
It is another object of the present invention to provide a process for the preparation of methyl acetate and/or acetic acid via the carbonylation of dimethyl ether and/or methanol wherein an ETL molecular sieve and/or a metal-modified ETL molecular sieve is used as a catalyst, wherein the conversion of dimethyl ether and/or methanol is high, the selectivity of methyl acetate and/or acetic acid is high and the stability of the catalyst is high, particularly when a metal-modified ETL molecular sieve is used.
The technical scheme for achieving the purpose of the invention can be summarized as follows:
1. a metal modified ETL molecular sieve, wherein the metal is selected from one or more of the second main group, the third main group and the transition elements of the periodic table of elements.
2. A metal-modified ETL molecular sieve according to item 1, wherein said metal is selected from one or more elements of Cu, Ni, Zn, Co, Fe, Ga, Pt, Zr, Pd and Ag, more preferably from one or more elements of Cu, Zn, Co, Ni, Fe; particularly preferred are one or more elements of Cu, Co and Zn, and most preferred is Cu.
3. The metal-modified ETL molecular sieve according to item 1 or 2, wherein the amount of said metal is from 0.08 to 25 wt%, preferably from 0.1 to 20 wt%, more preferably from 0.5 to 10 wt%, such as from 0.5 to 5 wt%, 0.8 to 2.5 wt%, based on the total weight of the metal-modified ETL molecular sieve.
4. A metal-modified ETL molecular sieve according to any one of items 1-3, wherein said ETL molecular sieve is an EU-12 molecular sieve.
5. The metal-modified ETL molecular sieve according to any one of claims 1-4, wherein the ETL molecular sieve has a silica to alumina molar ratio of from 50:1 to 5:1, preferably from 30:1 to 10: 1.
6. A process for preparing a metal modified ETL molecular sieve according to any one of claims 1 to 5, comprising treating the ETL molecular sieve with an aqueous solution containing a salt of the metal, and then calcining the resulting treated ETL molecular sieve.
7. The method according to item 6, wherein the metal-containing salt is selected from one or more of nitrate, sulfate and chloride.
8. The method according to item 6 or 7, wherein the treatment is carried out by an impregnation method or an ion exchange method.
9. The process according to any one of items 6 to 8, wherein the calcination temperature is 250-550 ℃, preferably 280-450 ℃ and/or the calcination time is 1.2-10 hours, preferably 1.6-5 hours.
10. The process according to any one of claims 6 to 9, wherein the ETL molecular sieve is prepared by a hydrothermal method.
11. The process according to item 10, wherein the ETL molecular sieve is prepared with an optional organic base or choline species templating agent a, an optional inorganic base B, one or more silicon sources C, and one or more aluminum sources D in a molar ratio a: B: C: D ═ 0-2: 0-5: 0.1-5, preferably (0.1-1.1: 0.1-3: 1-5: 0.1-2.
12. The process according to item 11, wherein the solvent E in the hydrothermal process is deionized water, preferably the molar ratio of A: B: C: D: E is (0-2): 0-5): (0.1-5): 20-200, more preferably (0.1-1.1): 0.1-3): (1-5): (0.1-2): 40-180.
13. The method according to item 10 or 11, wherein the organic base is selected from one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide; and/or the choline substance is selected from one or more of choline chloride, acetylcholine or acetylcholine chloride; and/or the inorganic base is selected from sodium hydroxide, sodium hydroxideOne or more of potassium, rubidium hydroxide, cesium hydroxide or lithium hydroxide; and/or the silicon source is selected from SiO2One or more of white carbon black, silica sol, water glass or ethyl orthosilicate; and/or the aluminum source is one or more selected from aluminum hydroxide, aluminum nitrate, sodium metaaluminate, aluminum powder, aluminum isopropoxide or aluminum sulfate.
14. The process according to any one of claims 6 to 13, wherein the ETL molecular sieve, such as the sodium ETL molecular sieve, is converted to the hydrogen ETL molecular sieve prior to modifying the ETL molecular sieve with the metal, preferably the hydrogen ETL molecular sieve is prepared by treating the sodium ETL molecular sieve with one or more of ammonium nitrate, ammonium chloride, ammonium sulfate, aqueous ammonia, hydrochloric acid, nitric acid, or sulfuric acid solutions, optionally drying, and then calcining.
15. Use of a metal-modified ETL molecular sieve according to any one of items 1 to 5 and/or a metal-modified ETL molecular sieve obtained from a process according to any one of items 6 to 14 as a catalyst in the conversion of dimethyl ether and/or methanol to methyl acetate and/or acetic acid via a carbonylation reaction.
16. A process for the conversion of dimethyl ether and/or methanol to methyl acetate and/or acetic acid via a carbonylation reaction wherein an ETL molecular sieve, preferably the hydrogen ETL molecular sieve, and/or a metal-modified ETL molecular sieve according to any one of items 1 to 5 and/or a metal-modified ETL molecular sieve obtained from the process according to any one of items 6 to 14 is used as a catalyst.
17. The process according to item 16, wherein the carbonylation reaction temperature is 180 ℃ and 330 ℃, preferably 200 ℃ and 280 ℃; and/or the pressure of the carbonylation reaction is between 0.1 and 25.0MPa, preferably between 0.5 and 10MPa, and/or the gas space velocity of the carbonylation reaction is 200--1Preferably 500--1。
18. The process according to item 16 or 17, wherein in the carbonylation reaction CO is used in molar excess relative to dimethyl ether and/or methanol, preferably the molar ratio of CO to dimethyl ether and/or methanol is from 100:1 to 5:1, more preferably from 50:1 to 10:1, still more preferably from 25:1 to 12: 1.
19. The process according to any one of items 16 to 18, wherein at least one inert gas is used in the carbonylation reaction.
20. The process according to any one of claims 16 to 19, wherein when a metal-modified ETL molecular sieve according to any one of claims 1 to 5 and/or a metal-modified ETL molecular sieve obtained from the process according to any one of claims 6 to 14 is used as catalyst, the metal-modified ETL molecular sieve is reduced, preferably with a gas comprising hydrogen, prior to the carbonylation reaction.
Drawings
FIG. 1 is a comparison of the XRD spectrum and standard spectrum of ETL molecular sieve of EU-12 molecular sieve prepared in step 1 of example 1
Detailed Description
One aspect of the invention relates to a metal-modified ETL molecular sieve, wherein the metal is selected from one or more of the second main group, the third main group and the transition elements of the periodic table of elements.
According to one embodiment of the present invention, the metal used to modify the ETL molecular sieve may be selected from one or more elements of Cu, Ni, Zn, Co, Fe, Ga, Pt, Zr, Pd and Ag, more preferably from one or more elements of Cu, Zn, Co, Ni, Fe; particularly preferred are one or more elements of Cu, Co and Zn, and most preferred is Cu.
In the metal-modified ETL molecular sieve, the metal may be present in the form of an element or an oxide, or as a mixture of an element and a compound (e.g., an oxide). The presence of the metal makes the ETL molecular sieve catalyst have stronger carbonylation activity and stability.
According to the invention, the amount of the modifying metal is from 0.08 to 25 wt.%, preferably from 0.1 to 20 wt.%, more preferably from 0.5 to 10 wt.%, for example from 0.5 to 5 wt.%, from 0.8 to 2.5 wt.%, for example 1.0 wt.%, 1.5 wt.% or 2 wt.%, based on the total weight of the metal-modified ETL molecular sieve.
The source of the ETL molecular sieve is not particularly limited in the present invention. In one embodiment of the invention, the ETL molecular sieve is, for example, an EU-12 molecular sieve.
In one embodiment of the invention, the ETL molecular sieve has a silica to alumina molar ratio of from 50:1 to 5:1, preferably from 30:1 to 10: 1.
Another aspect of the invention relates to a method of making a metal-modified ETL molecular sieve comprising treating an ETL molecular sieve with an aqueous solution containing a salt of the metal and then calcining the resulting treated ETL molecular sieve.
According to the invention, the calcination temperature is generally 250-550 ℃, preferably 280-450 ℃. The calcination time is usually 1.2 to 10 hours, preferably 1.6 to 5 hours.
According to the invention, the salts of the metals may be selected from one or more of nitrates, sulfates and chlorides, such as iron nitrate, zinc chloride, copper nitrate and the like.
In a preferred embodiment of the present invention, wherein the treatment is carried out by an impregnation method or an ion exchange method.
According to the present invention, impregnation, preferably an equal volume impregnation (where equal volume means that the volume of solution impregnated is equal to the pore volume of the voids contained in the ETL molecular sieve) is generally performed as follows:
an aqueous solution of a salt of the metal is typically prepared and then the aqueous solution is impregnated drop-wise onto the ETL molecular sieve, followed by drying and calcination. The drying is generally carried out at from 50 to 150 ℃ and preferably at from 80 to 120 ℃. The drying time is generally from 3 to 12 hours, preferably from 4 to 8 hours. The calcination temperature is usually 250-550 ℃, preferably 280-450 ℃. The calcination time is usually 1.2 to 10 hours, preferably 1.6 to 5 hours.
The ion exchange method is a commonly used method for modifying the metal of a molecular sieve, and utilizes the cation (such as Na) in the molecular sieve+，NH4 +) With metal cations (ions of the metal to be exchanged such as: cu2+，Zn2+) Thereby achieving ion exchange.
According to the invention, the ion exchange process can be carried out as follows:
an aqueous solution of a salt of the metal is prepared, and the concentration of the aqueous solution can be 0.01-2.0mol/L, and preferably 0.02-1.5 mol/L. Adding ETL molecular sieve, and stirring at 40-120 deg.C, preferably 50-90 deg.C for 2-10 hr, preferably 3-8 hr. And after ion exchange is finished, carrying out suction filtration, drying and roasting. The drying is generally carried out at from 50 to 150 ℃ and preferably at from 80 to 120 ℃. The drying time is generally from 3 to 12 hours, preferably from 4 to 8 hours. The calcination temperature is usually 250-550 ℃, preferably 280-450 ℃. The calcination time is usually 1.2 to 10 hours, preferably 1.6 to 5 hours.
According to one embodiment of the invention, the ETL molecular sieve used in the invention, such as EU-12, can be prepared by a hydrothermal method.
In a preferred embodiment of the present invention, the ETL molecular sieve is prepared using an optional organic base or choline species templating agent a, an optional inorganic base B, one or more silicon sources C, and one or more aluminum sources D in a molar ratio a: B: C: D ═ 0-2: 0-5: 0.1-5, preferably (0.1-1.1: 0.1-3: 1-5: 0.1-2.
According to a preferred embodiment, the solvent E in the hydrothermal process is deionized water, preferably the molar ratio of A: B: C: D: E is (0-2): 0-5): 0.1-5): 20-200, more preferably (0.1-1.1): 0.1-3): 1-5): 0.1-2): 40-180.
According to the present invention, the ETL molecular sieve, such as the EU-12 molecular sieve, can be prepared as follows:
adding organic alkali or choline substance template agent A and one or more silicon sources C into inorganic alkali B solution, stirring for 0-5h, such as 0.2-2h, and then adding one or more aluminum sources D and deionized water E. Stirring is continued for 0.1 to 24 hours at room temperature, hydrothermal reaction is carried out for 2 to 10 days at the temperature of between 80 and 200 ℃, preferably hydrothermal treatment is carried out for 4 to 8 days at the temperature of between 100 and 180 ℃ in a hydrothermal reaction kettle, and then washing, drying and roasting are carried out to obtain the EU-12 molecular sieve.
The organic base can be one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide. The choline substance can be one or more of choline chloride, acetylcholine or acetylcholine chloride. The silicon source can be silica sol or SiO2One or more of tetraethoxysilane, white carbon black and the like. The inorganic base can be one or more of potassium hydroxide, sodium hydroxide, rubidium hydroxide, cesium hydroxide, lithium hydroxide and the like; the aluminum source can be one or more of sodium metaaluminate, aluminum hydroxide, aluminum sulfate, aluminum powder, aluminum isopropoxide or aluminum nitrate. The washing method is deionized water washing which is conventionally used. The drying is generally carried out at from 60 to 180 ℃ and preferably from 80 to 150 ℃. Drying time is usuallyIs 3-24h, preferably 5-15 h. Calcination is generally carried out at 400-650 deg.C, preferably at 450-620 deg.C. The calcination time is generally from 2 to 10 hours, preferably from 4 to 8 hours.
According to a preferred embodiment of the present invention, the ETL molecular sieve, such as the ETL molecular sieve produced, is converted to the hydrogen-form ETL molecular sieve prior to modifying the ETL molecular sieve with the metal, preferably the hydrogen-form ETL molecular sieve is prepared by treating the ETL molecular sieve with one or more of ammonium nitrate, ammonium chloride, ammonium sulfate, aqueous ammonia, hydrochloric acid, nitric acid, or sulfuric acid solutions, optionally drying, and then calcining.
In a preferred embodiment, the conversion of the ETL molecular sieve into the hydrogen-form ETL molecular sieve more preferably can be performed using an ion exchange process. The ion exchange process may be specifically carried out as follows: adding the ETL molecular sieve into an ammonium salt or an acidic aqueous solution, stirring for 2-12h at 80 ℃, filtering, washing, drying and roasting to obtain the hydrogen type molecular sieve. As the ammonium salt, one or more of ammonium nitrate, ammonium chloride, or ammonium sulfate may be used. The acidic aqueous solution can be one or more of nitric acid, hydrochloric acid or sulfuric acid. The concentration is 0.01-2.0mol/L, preferably 0.05-1.0 mol/L. The drying time is generally from 2 to 10 hours, preferably from 3 to 7 hours. The calcination temperature is typically 350-650 deg.C, preferably 450-600 deg.C. The calcination time is generally from 2 to 10 hours, preferably from 4 to 8 hours. In order to exchange the metal salt ions thoroughly in the ETL molecular sieve according to the present invention, the number of ion exchanges is preferably 1 to 5, more preferably 2 to 4, such as 3. According to the invention, the product obtained after each exchange is preferably washed with water, dried and then subjected to the next exchange. All the washing and drying modes expressed in the invention are conventional washing and drying modes.
According to one aspect of the invention, the invention relates to the use of a metal-modified ETL molecular sieve according to the invention and/or a metal-modified ETL molecular sieve obtained from the process of the invention as a catalyst in the conversion of dimethyl ether and/or methanol to methyl acetate and/or acetic acid via a carbonylation reaction.
According to another aspect of the present invention, the present invention relates to a process for the conversion of dimethyl ether and/or methanol to methyl acetate and/or acetic acid via a carbonylation reaction wherein an ETL molecular sieve (preferably the hydrogen-form ETL molecular sieve) and/or a metal-modified ETL molecular sieve according to the present invention and/or a metal-modified ETL molecular sieve obtained by the process according to the present invention is used as a catalyst.
According to the invention, the carbonylation reaction may be carried out either batchwise or continuously.
The catalyst may be used in any conventional form, preferably in the form of a fixed bed. In the carbonylation reaction, a reaction gas may be passed over a catalyst.
According to a preferred embodiment of the invention, the carbonylation reaction temperature is 180-. The pressure of the carbonylation reaction is 0.1-25.0MPa, preferably 0.5-10 MPa. The gas space velocity of the carbonylation reaction is 200-10000h-1Preferably 500--1E.g. 600-4000h-1，700-2500h-1，8-1500h-1。
According to the invention, CO is used in molar excess relative to dimethyl ether and/or methanol in the carbonylation reaction. Preferably the molar ratio of CO to dimethyl ether and/or methanol is from 100:1 to 5:1, for example from 80:1 to 8:1, from 50:1 to 10:1, from 40:1 to 12:1, from 30:1 to 12:1, from 20:1 to 14:1, more preferably from 50:1 to 10:1, still more preferably from 25:1 to 12: 1.
In one embodiment of the present invention, at least one inert gas, preferably argon, is used in the carbonylation reaction. Argon may be used as an internal standard. When dimethyl ether and methanol are used as raw materials, the molar ratio of the reaction gas is Ar: DME: MeOH: CO ═ 1 (0.1-20): (0.1-50): (1-50), preferably 1 (0.1-50): (10-50). When dimethyl ether or methanol is used as the raw material, the molar ratio of the reaction gas is Ar: DME/MeOH: CO ═ 1 (0.1-50) to (1-50), preferably 1 (0.1-50) to (10-50). Wherein Ar is argon as an internal standard, DME is dimethyl ether, and MeOH is methanol.
When methanol is used, the methanol can be passed to a gasification unit for preheating and gasification. The gasification apparatus may be a stainless steel tube-type fixed bed reactor packed with a material having no adsorption function and good heat conductivity, and is preferably quartz sand or glass beads. The preheating gasification temperature is 70-400 ℃, preferably 80-300 ℃.
According to a preferred embodiment of the present invention, when the metal-modified ETL molecular sieve according to the present invention and/or the metal-modified ETL molecular sieve obtained by the process according to the present invention is used as a catalyst, the metal-modified ETL molecular sieve is reduced, preferably with a gas comprising hydrogen, more preferably a mixed gas of hydrogen and an inert gas, prior to the carbonylation reaction. The inert gas is preferably N2Ar, He, more preferably N2. The volume proportion of hydrogen gas is 0.1 to 100%, preferably 0.5 to 20%, more preferably 1 to 10%, based on the total volume of the mixed gas. The reduction temperature is 150-380 ℃, and preferably 200-350 ℃. The flow rate may be 5-100mL/min, preferably 10-50 mL/min.
Examples
The technical solutions in the present invention are further described below with reference to specific examples in the present invention, but should not be construed as limiting the scope of the present invention. The embodiments described below are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments listed in the present invention, other embodiments proposed by others skilled in the art without any inventive work are within the scope of the present invention.
Example 1
Preparation of the catalyst
(1) Firstly, 0.25mol of aluminum hydroxide, 0.6mol of rubidium hydroxide and 0.14mol of sodium hydroxide are dissolved in 20mol of water, and the solution is stirred for 0.5 hour to obtain uniform and transparent solution. Then 2.0mol of choline chloride solution and 5mol of silica sol are added, stirred for 10 hours at room temperature and then put into a hydrothermal kettle. After hydrothermal reaction at 150 ℃ for 7 days, the obtained sample was washed, dried at 100 ℃ for 6 hours, and calcined at 600 ℃ for 5 hours to obtain 13 g of EU-12 molecular sieve (metal ion type). The XRD spectrum of the molecular sieve is aligned with the standard spectrum of the molecular sieve with an ETL structure, and the alignment is shown in figure 1.
The obtained 13 g EU-12 molecular sieve was added to 390mL of 0.2mol/L aqueous ammonium nitrate solution, ion-exchanged at a constant temperature of 80 ℃ for 5 hours, and then the resulting product was washed with deionized water and dried at 100 ℃ for 6 hours. Repeating the operation process for 2 times to obtain the ammonia type EU-12 molecular sieve. Then the ammonia-type moleculeThe sieve was calcined at 550 ℃ for 6h under air atmosphere. Obtaining the hydrogen EU-12(HEU-12) molecular sieve. Sodium ions and rubidium ions are not detected in the result of X-ray fluorescence spectrum analysis, so that the sodium ions and rubidium ions in the molecular sieve are NH4All the ammonia EU-12 is obtained by replacement, NH is released after roasting3HEU-12 was obtained.
Catalytic reaction by using a catalyst:
(2) 0.5g of HEU-12 molecular sieve is weighed and filled into a stainless steel tubular fixed bed reactor with the inner diameter of 8mm, and quartz wool is respectively filled at two ends of a catalyst bed layer. 100% N with a flow rate of 30mL/min was introduced from one end2And treating at 500 ℃ and normal pressure for 5h, wherein the pretreatment aims to remove the adsorbed water in the molecular sieve. When the temperature is reduced to 220 ℃, the gas is switched into reaction gas, the molar ratio of Ar to DME to CO is 1:6:93, and the space velocity of the reaction gas is 1000h-1Continuously reacting at the reaction temperature of 220 ℃ and the total gas pressure of 1.5MPa, and monitoring the conversion rate of reactants and the selectivity of products in real time. The results are shown in Table 1.
Example 2
The catalyst was prepared in the same manner as in example 1. The pretreatment procedure and reaction conditions in example 1 were repeated. Except that the reaction gas used was methanol. The molar ratio of the components of the reaction gas was Ar: MeOH: CO ═ 1:6: 93. The results are shown in Table 1.
Example 3
The catalyst preparation method is the same as in example 1. The pretreatment procedure and reaction conditions in example 1 were repeated. The difference is that the reaction gas is the mixed gas of methanol and dimethyl ether. The molar ratio of the components of the reaction gas was Ar: DME: MeOH: CO ═ 1:3:3: 93. The results are shown in Table 1.
Example 4
HEU-12 prepared using the method described in example 1.
Preparing a copper modified hydrogen type EU-12 molecular sieve:
adding 5g of the HEU-12 molecular sieve obtained in the step (1) into 200mL of 0.002mol/L copper nitrate aqueous solution, heating and stirring for 5h in a water bath at 80 ℃, then drying for 8h at 100 ℃ after filtering and washing, and then roasting for 2h at 300 ℃ in an air atmosphere. Obtaining the copper modified molecular sieve. The weight of copper was 0.1% of the total weight of the catalyst by X-ray fluorescence spectroscopy, indicating that copper had been loaded onto the molecular sieve, and was labeled as 0.1% Cu/EU-12
Reduction and catalytic reaction of catalyst
Weighing 0.5g of 0.1% Cu/EU-12 molecular sieve, placing into a stainless steel tubular fixed bed reactor with an inner diameter of 8mm, filling quartz wool at two ends of a catalyst bed layer, and introducing 5% H from one end2And N2The mixed gas of (2) was reduced at 300 ℃ under normal pressure for 5 hours at a flow rate of 30mL/min, and then switched to a reaction gas. The reaction conditions in example 1 were repeated. The results are shown in Table 1.
Example 5
HEU-12 prepared using the method described in example 1.
Adding 5g of the HEU-12 molecular sieve obtained in the step (1) into 200mL of 0.04mol/L copper nitrate aqueous solution, heating and stirring for 5h in a water bath at 80 ℃, then drying for 8h at 100 ℃ after filtering and washing, and then roasting for 2h at 300 ℃ in an air atmosphere. Obtaining the copper modified molecular sieve. The weight of copper was 1% of the total weight of the catalyst by X-ray fluorescence spectroscopy, indicating that copper had been loaded onto the molecular sieve, and was labeled as 1% Cu/EU-12.
The resulting 1% Cu/EU-12 was subjected to catalyst reduction and catalytic reaction in the same manner as described in example 4. The results are shown in Table 1.
Example 6
HEU-12 prepared using the method described in example 1.
Adding 5g of the HEU-12 molecular sieve obtained in the step (1) into 200mL of 0.8mol/L copper nitrate aqueous solution, heating and stirring for 5h in a water bath at 80 ℃, then drying for 8h at 100 ℃ after filtering and washing, and then roasting for 2h at 300 ℃ in an air atmosphere. Obtaining the copper modified molecular sieve. The weight of copper, analyzed by X-ray fluorescence spectroscopy, was 20% of the total weight of the catalyst, indicating that copper had been loaded onto the molecular sieve, labeled 20% Cu/EU-12.
The resulting catalyst reduction and catalytic reaction of 20% Cu/EU-12 was carried out in the same manner as described in example 4. The results are shown in Table 1.
Example 7
Example 5 was repeated, but the reaction gas composition used was the same as that described in example 2. The results are shown in Table 1.
Example 8
Example 5 was repeated, but the reaction gas composition used was the same as that described in example 3. The results are shown in Table 1.
Example 9
Example 5 was repeated with the following differences: the reaction time of preparing methyl acetate by the carbonylation reaction of dimethyl ether and carbon monoxide is prolonged to 800 h. The results are shown in FIG. 1.
Example 10
Example 5 was repeated with the following differences: the reaction temperature for preparing methyl acetate by the reaction of dimethyl ether and carbon monoxide is 240 ℃. The reaction results are shown in Table 1.
Comparative example 1
The EU-12 molecular sieve of hydrogen ETL structure in example 1 was replaced with a commercial hydrogen mordenite molecular sieve MOR (Tosoh Corp.). The reaction conditions were the same as in example 1. The results are shown in Table 1.
Comparative example 2
The EU-12 molecular sieve of hydrogen-type ETL structure in example 1 was replaced with commercial hydrogen-type ZSM-35(Tosoh Corp.). The reaction conditions were the same as in example 1. The results are shown in Table 1.
TABLE 1
The activity evaluation conditions of the above catalysts were as follows:
the reaction conditions of examples 1 to 8 and comparative examples 1 to 2 were: the reaction running time is 100h, 1.5MPa and 1000h at 220 DEG C-10.5g of catalyst; examples 1, 4-6 and 9-10 and comparative examples 1 and 2 had a reaction gas molar composition of Ar: DME: CO ═ 1:6: 93; reaction gases in examples 2 and 7The molar composition is Ar: MeOH: CO ═ 1:6: 93; the molar composition of the gases in examples 3 and 8 was Ar: DME: MeOH: CO ═ 1:3:3: 93. Wherein DME is dimethyl ether, MeOH is methanol, MA is methyl acetate, and CC is acetic acid.
The reaction conditions of example 9 were the same as those of example 5, but the reaction time was extended to 800 hours.
The reaction conditions of example 10 were the same as those of example 5, except that the temperature was 240 ℃.
The foregoing is only a preferred embodiment of this invention and it will be appreciated that those skilled in the art, upon attaining an understanding of the foregoing, may readily produce alterations to, variations of, and equivalents to these embodiments without departing from the spirit and scope of the present invention.
Claims (20)
1. A metal modified ETL molecular sieve, wherein the metal is selected from one or more of the second main group, the third main group and the transition elements of the periodic table of elements.
2. A metal-modified ETL molecular sieve according to claim 1, wherein said metal is selected from one or more elements of Cu, Ni, Zn, Co, Fe, Ga, Pt, Zr, Pd and Ag, more preferably from one or more elements of Cu, Zn, Co, Ni, Fe; particularly preferred are one or more elements of Cu, Co and Zn, and most preferred is Cu.
3. The metal-modified ETL molecular sieve according to claim 1 or 2, wherein the amount of said metal is from 0.08 to 25 wt. -%, preferably from 0.1 to 20 wt. -%, more preferably from 0.5 to 10 wt. -%, such as from 0.5 to 5 wt. -%, 0.8 to 2.5 wt. -%, based on the total weight of the metal-modified ETL molecular sieve.
4. The metal-modified ETL molecular sieve of any of claims 1-3, wherein said ETL molecular sieve is an EU-12 molecular sieve.
5. The metal-modified ETL molecular sieve of any of claims 1-4, wherein the ETL molecular sieve has a silica to alumina molar ratio of from 50:1 to 5:1, preferably from 30:1 to 10: 1.
6. A process for preparing a metal-modified ETL molecular sieve according to any one of claims 1 to 5, comprising treating the ETL molecular sieve with an aqueous solution containing a salt of said metal, and then calcining the resulting treated ETL molecular sieve.
7. A process according to claim 6, wherein the metal-containing salt is selected from one or more of the group consisting of nitrates, sulfates and chlorides.
8. A process according to claim 6 or 7, wherein the treatment is carried out by impregnation or ion exchange.
9. Process according to any one of claims 6 to 8, wherein the calcination temperature is 250-550 ℃, preferably 280-450 ℃ and/or the calcination time is 1.2-10 hours, preferably 1.6-5 hours.
10. The process of any of claims 6-9, wherein the ETL molecular sieve is prepared by a hydrothermal process.
11. The process of claim 10 wherein the ETL molecular sieve is prepared using an optional organic base or choline species templating agent a, an optional inorganic base B, one or more silicon sources C, and one or more aluminum sources D in a molar ratio a: B: C: D (0-2): (0-5): (0.1-5), preferably (0.1-1.1): (0.1-3): (1-5): 0.1-2).
12. The process of claim 11, wherein the E solvent in the hydrothermal process is deionized water, preferably the molar ratio of A: B: C: D: E is (0-2): 0-5): 0.1-5): 20-200, more preferably (0.1-1.1): 0.1-3): 1-5): 0.1-2): 40-180.
13. A process according to claim 10 or 11, wherein the organic base is selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxideOne or more of the above; and/or the choline substance is selected from one or more of choline chloride, acetylcholine or acetylcholine chloride; and/or the inorganic base is selected from one or more of sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide or lithium hydroxide; and/or the silicon source is selected from SiO2One or more of white carbon black, silica sol, water glass or ethyl orthosilicate; and/or the aluminum source is one or more selected from aluminum hydroxide, aluminum nitrate, sodium metaaluminate, aluminum powder, aluminum isopropoxide or aluminum sulfate.
14. The process of any of claims 6 to 13, wherein the ETL molecular sieve, such as the sodium ETL molecular sieve, is converted to the hydrogen ETL molecular sieve prior to modifying the ETL molecular sieve with the metal, preferably the hydrogen ETL molecular sieve is prepared by treating the sodium ETL molecular sieve with one or more of ammonium nitrate, ammonium chloride, ammonium sulfate, aqueous ammonia, hydrochloric acid, nitric acid, or sulfuric acid solutions, optionally drying, and then calcining.
15. Use of a metal-modified ETL molecular sieve according to any one of claims 1 to 5 and/or a metal-modified ETL molecular sieve obtained from a process according to any one of claims 6 to 14 as a catalyst in the conversion of dimethyl ether and/or methanol to methyl acetate and/or acetic acid via a carbonylation reaction.
16. A process for the conversion of dimethyl ether and/or methanol to methyl acetate and/or acetic acid via a carbonylation reaction wherein an ETL molecular sieve (preferably the hydrogen-form ETL molecular sieve) and/or a metal-modified ETL molecular sieve according to any one of claims 1 to 5 and/or a metal-modified ETL molecular sieve obtained from a process according to any one of claims 6 to 14 is used as a catalyst.
17. The process according to claim 16, wherein the carbonylation reaction temperature is 180-330 ℃, preferably 200-280 ℃; and/or the pressure of the carbonylation reaction is between 0.1 and 25.0MPa, preferably between 0.5 and 10MPa, and/or the gas space velocity of the carbonylation reaction is 200--1Preferably 500--1。
18. A process according to claim 16 or 17 wherein CO is used in molar excess to dimethyl ether and/or methanol in the carbonylation reaction, preferably at a molar ratio of CO to dimethyl ether and/or methanol of from 100:1 to 5:1, more preferably from 50:1 to 10:1, still more preferably from 25:1 to 12: 1.
19. A process according to any one of claims 16 to 18 wherein at least one inert gas is used in the carbonylation reaction.
20. The process according to any one of claims 16 to 19, wherein when a metal-modified ETL molecular sieve according to any one of claims 1 to 5 and/or a metal-modified ETL molecular sieve obtained by the process according to any one of claims 6 to 14 is used as catalyst, the metal-modified ETL molecular sieve is reduced, preferably with a gas comprising hydrogen, prior to the carbonylation reaction.
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| CN112844452A (en) * | 2021-02-23 | 2021-05-28 | 北京弗莱明科技有限公司 | Modified molecular sieve, preparation method thereof, catalyst for preparing methyl acetate by carbonylation of dimethyl ether and method |
| CN115138391A (en) * | 2021-03-29 | 2022-10-04 | 高化学株式会社 | Low temperature carbonylation molecular sieve catalyst and use thereof |
| WO2024083048A1 (en) * | 2022-10-17 | 2024-04-25 | 高化学株式会社 | Catalyst for preparing methyl acetate from dimethyl ether and/or methanol by means of carbonylation and use thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112844452A (en) * | 2021-02-23 | 2021-05-28 | 北京弗莱明科技有限公司 | Modified molecular sieve, preparation method thereof, catalyst for preparing methyl acetate by carbonylation of dimethyl ether and method |
| CN112844452B (en) * | 2021-02-23 | 2023-03-14 | 北京弗莱明科技有限公司 | Modified molecular sieve, preparation method thereof, catalyst for preparing methyl acetate by carbonylation of dimethyl ether and method |
| CN115138391A (en) * | 2021-03-29 | 2022-10-04 | 高化学株式会社 | Low temperature carbonylation molecular sieve catalyst and use thereof |
| WO2024083048A1 (en) * | 2022-10-17 | 2024-04-25 | 高化学株式会社 | Catalyst for preparing methyl acetate from dimethyl ether and/or methanol by means of carbonylation and use thereof |
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