CN109438239B - Method for controllably synthesizing methyl acetate and acetic acid by dimethyl ether carbonylation - Google Patents
Method for controllably synthesizing methyl acetate and acetic acid by dimethyl ether carbonylation Download PDFInfo
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
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Abstract
The invention provides a method for controllably synthesizing methyl acetate and acetic acid by dimethyl ether carbonylation, belonging to the technical field of dimethyl ether carbonylation. The method adopts a moving bed reaction process, takes a spherical molecular sieve as a catalyst, synthesizes methyl acetate and acetic acid by dimethyl ether carbonylation, and regulates and controls the product proportion according to different raw material component proportions and operation conditions: continuously adding a spherical molecular sieve catalyst at the top of the carbonylation reactor, gradually moving the catalyst downwards along with the progress of the carbonylation reaction, continuously flowing out of the carbonylation reactor from the bottom, and entering a regeneration reactor for carbon burning regeneration; raw materials of carbon monoxide, dimethyl ether, hydrogen and water are vaporized and mixed, then enter a carbonylation reactor and pass through a catalyst bed layer from bottom to top, a chemical reaction is carried out on a catalyst, and a gas mixed product after the reaction flows out from the top of the reactor for separation. The invention adopts a moving bed reaction process, takes the spherical molecular sieve as the catalyst, and can controllably synthesize methyl acetate and acetic acid while realizing the regeneration of the catalyst.
Description
Technical Field
The invention belongs to the technical field of dimethyl ether carbonylation, and particularly relates to a method for controllably synthesizing methyl acetate and acetic acid through dimethyl ether carbonylation.
Background
With the increasing energy demand and the increasing contradiction of the shortage of petroleum supply and the increasing of the global environmental pressure, the fuel ethanol is generally concerned by countries in the world due to the cleanness and environmental protection of the fuel ethanol, the ethanol is used as an important clean energy source and is mixed with gasoline in a proportion of 10 percent, and the fuel ethanol gasoline can reduce the emission of carbon monoxide and hydrocarbon in automobile exhaust, thereby having important significance for solving the problem of atmospheric pollution in China and realizing sustainable development. China is a country rich in coal and less in oil, so that ethanol prepared by coal chemical industry conforms to the basic national conditions of China. In recent years, researchers at home and abroad explore an economic, environment-friendly and green process route of 'synthesis gas → methanol → dimethyl ether → methyl acetate → ethanol'. At present, the total yield of the domestic dimethyl ether device can reach about 1400 million tons, but the operating rate is only 38%, and the problem that the dimethyl ether capacity is seriously excessive is solved by the route.
Early studies on the carbonylation of dimethyl ether focused on a noble metal catalyst supported by a heteropoly acid, and the Volkovad topic group (J.Am.chem.Soc.131(2009) 13054-13061) obtained more than 30% of dimethyl ether conversion rate and about 95% of methyl acetate selectivity on Rh/CsxH3-xPW12O40 (473K, 1.0 MPa). However, these catalytic systems still use noble metals such as Rh, and hydrocarbons and a large amount of hard carbon deposit exist in the carbonylation process of dimethyl ether, which seriously affects the service life of the catalyst. In the patent CN104338553A, the activity and stability of the dimethyl ether carbonylation reaction can be improved by treating the ZSM-35 molecular sieve with microwave acid and alkali. The patent CN103896766A can improve the one-way service life of the mordenite catalyst to more than 1000 hours by adding organic amine such as pyridine and the like into the feed.
Acetic acid is an important organic chemical product and is mainly used for producing vinyl acetate, acetic ester, acetic anhydride, terephthalic acid, chloroacetic acid and other products. Currently, the typical processes for producing acetic acid mainly comprise a process adopting a rhodium/methyl iodide catalytic system developed by Monsanto company and a Cativa process adopting an iridium/methyl iodide catalytic system, wherein methyl iodide has strong corrosion to equipment by an auxiliary agent, so that the whole reaction system has high requirement on the corrosion resistance of the equipment. Patent CN1762596A develops an additive rhodium/methyl iodide catalyst containing morpholine compounds, morpholine salt derivatives and the like, which has high activity and high stability.
Disclosure of Invention
The invention aims to provide a method for controllably synthesizing methyl acetate and acetic acid by dimethyl ether carbonylation. The purpose of the invention is realized by the following technical scheme:
a method for controllable synthesis of methyl acetate and acetic acid by dimethyl ether carbonylation adopts a moving bed reaction process, takes a spherical molecular sieve as a catalyst, synthesizes methyl acetate and acetic acid by dimethyl ether carbonylation, and regulates and controls the proportion of two products according to different raw material component proportions and operation conditions, and comprises the following specific steps:
continuously adding a spherical molecular sieve catalyst at the top of the carbonylation reactor, gradually moving the catalyst downwards along with the progress of the carbonylation reaction, continuously flowing out of the carbonylation reactor from the bottom, and entering a regeneration reactor for carbon burning regeneration;
raw materials of carbon monoxide, dimethyl ether, hydrogen and water are vaporized and mixed, then enter a carbonylation reactor and pass through a catalyst bed layer from bottom to top, a chemical reaction is carried out on a catalyst, and a gas mixed product after the reaction flows out from the top of the reactor for separation.
Furthermore, the regenerated spherical molecular sieve catalyst continuously enters the carbonylation reactor through the top of the reactor.
Further, the total volume space velocity of the carbon monoxide, the dimethyl ether, the hydrogen and the water is 2000-8000 h-1More preferably 5200h-1The molar ratio of carbon monoxide, dimethyl ether, hydrogen and water is (5.0-50): 1.0, (0.5-5.0): 0-1.0.
Further, the temperature of the carbonylation reactor is 200-500 ℃, and preferably 250-400 ℃; the reaction pressure is 1.0 to 10.0MPa, preferably 4.0 to 6.0 MPa.
Further, the temperature of the regeneration reactor is 300-600 ℃, and preferably 450-550 ℃; the regeneration pressure is 1.0 to 10.0MPa, preferably 4.0 to 6.0 MPa.
Further, the spherical molecular sieve catalyst is prepared by carrying out metal modification on molecular sieve raw powder with MOR, MFI or FER crystal forms and then forming the modified molecular sieve raw powder with an aluminum-containing binder into a spherical catalyst with the particle size of 1-3 mm.
Further, the metal loading amount in the spherical molecular sieve catalyst is 0-5.0 wt.%; the metal is one or the combination of more of Cu, Zn, Fe, Ga and the like.
Further, the content of the binder is 5-30 wt.%; the binder is one or more of kaolin, alumina sol, silica sol and pseudo-boehmite.
Further, the preparation process of the spherical molecular sieve catalyst is as follows:
1) performing H ion exchange on zeolite molecular sieve raw powder to obtain hydrogen type zeolite molecular sieve raw powder;
2) preparing hydrogen type zeolite molecular sieve raw powder into metal modified hydrogen type zeolite molecular sieve raw powder after metal ion exchange and roasting;
3) mixing the metal modified hydrogen type zeolite molecular sieve raw powder with a binder, and preparing the mixture into a spherical molecular sieve catalyst with the particle size of 1-3 mm by adopting a rolling ball forming technology.
Further, the zeolite molecular sieve is a sodium type molecular sieve, and specifically is one of MOR, MFI and FER.
Compared with the prior art, the invention has the following beneficial effects:
the invention aims at the characteristics of dimethyl ether and carbon monoxide carbonylation reaction on a molecular sieve catalyst, adopts a moving bed reaction process, takes a spherical molecular sieve as the catalyst to controllably synthesize methyl acetate and acetic acid, and can adjust the proportion of methyl acetate and acetic acid in the product according to the feeding proportion of carbon monoxide, dimethyl ether, hydrogen and water and the change of operation conditions.
The invention provides a moving bed reaction process method aiming at the problems that the molecular sieve catalyst is easy to deposit carbon and deactivate, and needs to repeat the regeneration process for many times.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1: preparation of carbonylation catalyst
Sodium MOR molecular sieve raw powder (SiO)2/Al2O324.2) at 8And (3) exchanging for 3 times by adopting an ammonium nitrate solution (1.0mol/L) in a water bath at the temperature of 5 ℃, drying in a drying oven at the temperature of 110 ℃ after exchanging, and roasting in a muffle furnace at the temperature of 550 ℃ for 4 hours to obtain the H-MOR molecular sieve raw powder.
Exchanging the H-MOR molecular sieve raw powder in a water bath at 80 ℃ by using a copper nitrate solution (1.0mol/L) for 1 time, drying in a baking oven at 110 ℃ after exchange, and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain Cu-H-MOR molecular sieve raw powder.
38.5kg of Cu-H-MOR molecular sieve raw powder and 33.2kg of alumina sol (30.5 wt.% Al) are weighed2O3) Mixing with proper amount of deionized water, rolling ball to form 2mm ball catalyst to obtain Cu-H-MOR-Al2O3The spherical molecular sieve catalyst is numbered as CuM-03.
Example 2: evaluation of Activity of carbonylation reaction on catalyst
The carbonylation reaction was carried out on a moving bed using the catalyst numbered CuM-03 in example 1 under the following reaction conditions: the loading of the catalyst is 1.0kg, the inventory of the carbonylation reactor is 0.5kg, fresh carbonylation catalyst and regenerated catalyst are added from the top of the reactor, a catalyst bed layer moves downwards very slowly along with the reaction, the carbon-deposited catalyst slowly flows out from the bottom of the carbonylation reactor and enters a regeneration reactor for carbon burning regeneration, and the catalyst is 0.15 kg/day. The carbonylation reaction temperature and pressure were 300 ℃ and 5MPa, and the regeneration reaction temperature and pressure were 450 ℃ and 5 MPa. Carbon monoxide/dimethyl ether/hydrogen/water in the raw material is 10/1/1/0.1, and the total volume space velocity of the raw material gas is 5200h-1The raw materials are preheated and gasified and then fed from the bottom of the carbonylation reactor, and the product flows out from the top of the carbonylation reactor. The composition and content of the product were analyzed on-line by gas chromatography, and the results are shown in Table 1.
TABLE 1
When the carbonylation reaction time is respectively 30 hours, 100 hours and 260 hours, the conversion rate of the dimethyl ether is respectively 96.89 percent, 94.66 percent and 95.13 percent. The selectivity to methyl acetate in the product was 85.46%, 82.67%, 84.18%, respectively, and the selectivity to acetic acid was 13.15%, 15.89%, 14.14%, respectively, with the balance being small amounts of methanol and hydrocarbons (CHx).
Under the above conditions, the catalyst was replaced at intervals of 90 days in an amount of 1kg per catalyst replacement. Compared with the common fixed bed reaction, the moving bed catalytic reaction can save 30 wt.%/year.
Example 3: evaluation of Activity of carbonylation reaction on catalyst
The carbonylation reaction was carried out on a moving bed using the catalyst numbered CuM-03 in example 1 under the following reaction conditions: the loading of the catalyst is 1.0kg, the inventory of the carbonylation reactor is 0.5kg, fresh carbonylation catalyst and regenerated catalyst are added from the top of the reactor, a catalyst bed layer moves downwards very slowly along with the reaction, the carbon-deposited catalyst slowly flows out from the bottom of the carbonylation reactor and enters a regeneration reactor for carbon burning regeneration, and the catalyst is 0.15 kg/day. The carbonylation reaction temperature and pressure were 320 ℃ and 5.5MPa, and the regeneration reaction temperature and pressure were 500 ℃ and 5.5 MPa. Carbon monoxide/dimethyl ether/hydrogen/water in the raw material is 10/1/1.5/0.1, and the total volume space velocity of the raw material gas is 5200h-1The raw materials are preheated and gasified and then fed from the bottom of the carbonylation reactor, and the product flows out from the top of the carbonylation reactor. The composition and content of the product were analyzed on-line by gas chromatography, and the results are shown in Table 2.
TABLE 2
When the carbonylation reaction time is respectively 30 hours, 100 hours and 260 hours, the conversion rate of the dimethyl ether is respectively 98.74 percent, 96.58 percent and 97.69 percent. The selectivity to methyl acetate in the product was 78.55%, 74.46%, 76.32%, respectively, and the selectivity to acetic acid was 20.21%, 23.81%, 21.98%, respectively, with the balance being small amounts of methanol and hydrocarbons (CHx).
Under the above conditions, the catalyst was replaced at intervals of 65 days in an amount of 1kg per replacement. Compared with the common fixed bed reaction, the moving bed catalytic reaction can save 24 wt.%/year.
Example 4: evaluation of Activity of carbonylation reaction on catalyst
The carbonylation reaction was carried out on a moving bed using the catalyst numbered CuM-03 in example 1 under the following reaction conditions: the loading of the catalyst is 1.0kg, the inventory of the carbonylation reactor is 0.5kg, fresh carbonylation catalyst and regenerated catalyst are added from the top of the reactor, a catalyst bed layer moves downwards very slowly along with the reaction, the carbon-deposited catalyst slowly flows out from the bottom of the carbonylation reactor and enters a regeneration reactor for carbon burning regeneration, and the catalyst is 0.15 kg/day. The carbonylation reaction temperature and pressure were 350 ℃ and 6MPa, and the regeneration reaction temperature and pressure were 550 ℃ and 6 MPa. Carbon monoxide/dimethyl ether/hydrogen/water in the raw material is 10/1/1.5/0.2, and the total volume space velocity of the raw material gas is 5200h-1The raw materials are preheated and gasified and then fed from the bottom of the carbonylation reactor, and the product flows out from the top of the carbonylation reactor. The composition and content of the product were analyzed on-line by gas chromatography, and the results are shown in Table 3.
TABLE 3
When the carbonylation reaction time is 30 hours, 100 hours and 260 hours respectively, the conversion rate of the dimethyl ether is 99.45 percent, 98.99 percent and 99.35 percent respectively. The selectivity to methyl acetate in the product was 54.26%, 52.79%, 53.49%, respectively, and the selectivity to acetic acid was 40.25%, 41.84%, 40.29%, respectively, with the balance being small amounts of methanol and hydrocarbons (CHx).
Under the above conditions, the catalyst was replaced at intervals of 38 days in an amount of 1kg per replacement. Compared with the common fixed bed reaction, the moving bed catalytic reaction can save 14 wt.%/year.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (1)
1. A method for controllably synthesizing methyl acetate and acetic acid by dimethyl ether carbonylation is characterized by comprising the following steps of catalyst preparation and moving bed reaction processes:
preparation of the catalyst:
mixing SiO2/Al2O3Exchanging sodium MOR molecular sieve raw powder with the molar ratio of 24.2 in a water bath at 85 ℃ for 3 times by adopting 1.0mol/L ammonium nitrate solution, drying in a drying oven at 110 ℃ after exchanging, and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain H-MOR molecular sieve raw powder;
exchanging the H-MOR molecular sieve raw powder in a water bath at 80 ℃ by adopting a 1.0mol/L copper nitrate solution for 1 time, drying in a drying oven at 110 ℃ after exchanging, and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain Cu-H-MOR molecular sieve raw powder;
weighing 38.5kg of Cu-H-MOR molecular sieve raw powder containing 30.5 wt.% of Al2O333.2kg of alumina sol and a proper amount of deionized water are mixed, and after uniform mixing, the ball is rolled to form a 2mm ball catalyst to obtain Cu-H-MOR-Al2O3A spherical molecular sieve catalyst;
moving bed reaction process:
the loading of the catalyst is 1.0kg, the inventory of the carbonylation reactor is 0.5kg, fresh carbonylation catalyst and regenerated catalyst are added from the top of the reactor, a catalyst bed layer moves downwards along with the reaction, the carbon-deposited catalyst flows out from the bottom of the carbonylation reactor and enters a regeneration reactor for carbon burning regeneration, the catalyst is 0.15 kg/day, the carbonylation reaction temperature and pressure are 300 ℃ and 5MPa, and the regeneration reaction temperature and pressure are 450 ℃ and 5 MPa; the molar ratio of carbon monoxide/dimethyl ether/hydrogen/water in the raw material is 10/1/1/0.1, and the total volume space velocity of the raw material gas is 5200h-1The raw materials are preheated and gasified and then fed from the bottom of the carbonylation reactor, and the product flows out from the top of the carbonylation reactor.
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