CN112250573B - Method for preparing methyl acetate by dimethyl ether carbonylation - Google Patents

Method for preparing methyl acetate by dimethyl ether carbonylation Download PDF

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CN112250573B
CN112250573B CN202011122825.2A CN202011122825A CN112250573B CN 112250573 B CN112250573 B CN 112250573B CN 202011122825 A CN202011122825 A CN 202011122825A CN 112250573 B CN112250573 B CN 112250573B
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carbonylation
dimethyl ether
reactor
catalyst
methyl acetate
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CN112250573A (en
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刘亚华
李扬
刘芃
叶秋云
胡玉容
王科
李文龙
夏伟
宋元江
李楠锌
许红云
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Southwest Research and Desigin Institute of Chemical Industry
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Southwest Research and Desigin Institute of Chemical Industry
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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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J29/90—Regeneration or reactivation
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • B01J38/14—Treating with free oxygen-containing gas with control of oxygen content in oxidation gas
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a method for preparing methyl acetate by dimethyl ether carbonylation, belonging to the field of preparing methyl acetate by dimethyl ether carbonylation. The method is a continuous reaction regeneration process for preparing methyl acetate by carbonylation of dimethyl ether, and comprises the following steps: dimethyl ether and carbon monoxide are respectively preheated to a preheating temperature through a feeding system, then mixed with hydrogen and then enter a reactor, and are contacted with a catalyst in the reactor to react at a reaction temperature and a reaction pressure; as the catalyst activity decreases, the feed is switched to another reactor. And (3) regenerating by 3 steps under the condition of keeping the temperature and the pressure of the reactor to be regenerated unchanged, treating and circularly regenerating the regenerated tail gas, and recovering the performance of the regenerated catalyst to the level of a fresh catalyst. The method for preparing methyl acetate by dimethyl ether carbonylation provided by the invention can realize continuous production, and has low requirements on equipment grade at a lower regeneration temperature (less than 190 ℃) under a high-pressure condition, thereby reducing the investment cost. The method has simple process flow and good industrial application prospect.

Description

Method for preparing methyl acetate by dimethyl ether carbonylation
Technical Field
The invention belongs to the field of dimethyl ether carbonylation for preparing methyl acetate, and particularly relates to a method for preparing methyl acetate by 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. After the global fuel ethanol yield is increased rapidly in 2006-2010, the global fuel ethanol yield is influenced by grain consumption disputes, and the global fuel ethanol yield is increased and slowed down in 2011-2013 and is maintained at the level of 830-857 hundred million liters per year. In 2014, the fuel ethanol market has been recovered to a certain extent, and the fuel ethanol market is increased by 5 percent on a par. The worldwide demand for fuel ethanol will reach 17753 million tons in 2025 as predicted by the united states energy information center.
At present, fuel ethanol is mainly divided into grain ethanol, non-grain ethanol and cellulosic ethanol. Grain ethanol is prepared from grains such as corn and wheat, and the production of grain ethanol and non-grain ethanol occupies more farmlands, so that the grain ethanol has the problem of competing for grains with people and livestock, and is gradually limited or prohibited by relevant policies of governments of various countries. 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.
At present, a technical route of 'dimethyl ether → methyl acetate → ethanol' is developed domestically, dimethyl ether and carbon monoxide are subjected to carbonylation reaction to generate methyl acetate, and methyl acetate and hydrogen are subjected to hydrogenation reaction to generate ethanol, wherein the technology for preparing ethanol by methyl acetate hydrogenation is mature, and industrial application is realized.
In the patent CN 104338553A, 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. In patent CN 101613274A, organic amine such as pyridine is used to modify mordenite molecular sieve catalyst, the selectivity of methyl acetate is more than 99%, and the stability of catalyst life is greatly improved to more than 50 hours. The patent CN 103896766A improves that the one-way service life of the mordenite catalyst can be prolonged to more than 1000 hours by adding organic amine such as pyridine and the like in the feed, and the problem of short service life of the mordenite catalyst can be well solved by the pyridine modification method. In patent CN 106311336A, methyl or acetyl organic matter is used to selectively modify the pore canal of the silk molecular sieve, so that the single-pass service life of the catalyst for the dimethyl ether carbonylation reaction is prolonged to more than 600 hours. Liu Yahua et al (report in chemical engineering, 2017, 68 (10): 3816-3822.) optimize the carbon burning condition of the hydrogen-type mordenite molecular sieve catalyst after the carbonylation reaction, almost completely recover the activity of the regenerated catalyst, but the carbon burning regeneration temperature far exceeds the reaction temperature, have high requirements on equipment and increase the equipment investment.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing methyl acetate by carbonylation of dimethyl ether. The method can effectively realize the regeneration process of the catalyst after reaction by a multi-step regeneration means and matching with the molecular sieve catalyst, thereby continuously carrying out the carbonylation reaction. In the regeneration process, the reaction temperature is low (less than 190 ℃), the equipment investment is reduced, and the method is simple and easy to operate and has good industrial application prospect.
In order to realize the purpose, the invention adopts the technical scheme that:
a method for preparing methyl acetate by dimethyl ether carbonylation comprises the following steps:
preheating dimethyl ether and carbon monoxide respectively, mixing with hydrogen, feeding into a reactor, and carrying out carbonylation reaction in the reactor filled with a catalyst; switching the raw material to another reactor to continue reacting with the reduction of the activity of the catalyst, and regenerating the catalyst in the original reactor; when the activity of the catalyst in the other reactor is reduced and needs to be regenerated, the catalyst is switched back to the original reactor.
Further, the catalyst regeneration process in the reactor comprises the steps of:
(1) h in the raw material gas at the original reaction temperature and reaction pressure2The partial pressure is unchanged, the CO partial pressure is increased, the DME partial pressure is reduced, and the reaction is continued for a period of time;
(2) increasing H gradually2Reducing the partial pressure of the dimethyl ether to 0 while the partial pressure is maintained, and continuing to react for a period of time;
(3) by containing O2The gas mixed with the inert gas regenerates the catalyst, and the oxygen concentration gradually rises; and 3, the regenerated tail gas obtained in the step is subjected to cooling, alkali washing, drying and water removal treatment in sequence and then enters the original reactor for recycling.
As a preferred embodiment of the present application, the reactor type is a fixed bed reactor or a fluidized bed reactor.
As a preferred embodiment of the present application, the catalyst type in the carbonylation reaction is modified catalyst containing eight-membered ring or ten-membered ring channel molecular sieve such as MOR, FER or ZSM-5 or metal such as Cu, Zn, Fe supported by molecular sieve.
As a preferred embodiment of the present application, the temperature of the carbonylation reaction is 140-190 ℃, and the reaction pressure is 1.0-10.0 MPa.
As a preferred embodiment of the present application, CO, DME and H are present in the carbonylation feed gas2The volume ratio of (A) to (B) is 3-30: 0.5-5: 0.5 to 5; the airspeed is 1000~10000 h－1。
As a preferred embodiment of the present application, the volume ratio of CO to DME in step (1) is 30-100: 1, preferably 40 to 60: 1; the continuous reaction time is 10-30 h.
As a preferred embodiment of the present application, CO and H are used in step (2)2Is 1:1 to 10, preferablySelecting 1: 2-4; the continuous reaction time is 10-30 h.
As a preferred embodiment of the present application, the step (3) contains O2A gas mixed with an inert gas, the inert gas being N2Any one or a mixture of He and Ar, wherein O2The concentration is 1-500ppm, preferably 50-150 ppm.
As a preferred embodiment of the present application, O2The concentration raising rate is (0.5-2) ppm/h, and the constant temperature time is 1-10 h.
In a preferred embodiment of the present application, the regeneration gas cooling gas in step (3) is cooled to below 70 ℃ by using circulating water.
As a preferred embodiment of the present application, the alkali washing in step (3) adopts a bubbling manner, the alkali is specifically one or a combination of more of Ca (OH)2, KOH and NaOH, and the concentration of the alkali liquor is 0.3-2.0 mol/L. When the concentration of the alkali liquor is less than 0.3mol/L, the alkali liquor needs to be replaced.
As a preferred embodiment of the application, the water removal agent in the step (3) adopts a molecular sieve or activated carbon, the molecular sieve is any one or a combination of 3A, 4A or 5A, and the water content in the gas after drying and water removal treatment is less than or equal to 10ppm, preferably 0-5 ppm. When the water content in the gas after the drying and water removal treatment is more than 10ppm, the water removal agent needs to be replaced.
The invention selects the molecular sieve catalyst containing eight-membered ring or ten-membered ring channels as the dimethyl ether carbonylation catalyst, can realize the on-line low-temperature regeneration of the molecular sieve catalyst, ensures the continuous dimethyl ether carbonylation reaction, and simultaneously reduces the requirement on equipment grade.
Compared with the prior art, the positive effects of the invention are as follows:
the method greatly reduces the regeneration temperature of the catalyst, reduces the requirement on equipment level, reduces the operation cost and has good industrial application prospect.
And secondly, the method has the characteristics of high conversion rate, high selectivity and the like of the traditional process, realizes catalyst regeneration while the carbonylation reaction is carried out, and ensures the continuous operation of the whole reaction.
Drawings
FIG. 1 is a schematic diagram of the reaction and regeneration process flow for the carbonylation of dimethyl ether to produce methyl acetate according to the embodiment of the present invention.
Description of reference numerals: 1 a: preheating raw materials DME and CO and then mixing the raw materials; 1 b: hydrogen gas; 1# reactor; 2# reactor; 2: a carbonylation product; 3: a gas-liquid separation tank; 4: gas phase in a gas-liquid separation tank; 5: liquid phase in a gas-liquid separation tank; 6: a methyl acetate refining tower; 7: refining the column liquid phase product; 8: dimethyl ether circulates at the top of the refining tower; 9: regenerating tail gas; 10: alkali washing; 11: waste liquor; 12: removing water from the recycled regeneration gas; 13: and (4) regenerating gas.
Detailed Description
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
In the present invention, some conventional operation devices, apparatuses and components are omitted or simply described.
The process comprises the following steps: FIG. 1 is a schematic diagram of a process flow for preparing methyl acetate by carbonylation of dimethyl ether and regeneration, and two reactors are taken as an example.
2 reactors (respectively No. 1 reactor and No. 2 reactor) are filled with catalyst, and raw materials of CO, DME and H2The liquid phase enters a No. 1 reactor according to a certain proportion, passes through a catalyst bed layer in the reactor, and is subjected to carbonylation reaction under the conditions of certain reaction temperature, pressure and space velocity, the product of the carbonylation reaction enters a gas-liquid separator 3 after heat exchange and cooling, a gas phase is subjected to a circulating system, and a liquid phase enters a rectifying tower for refining 6. Dimethyl ether circulates at the top of the refining tower, and methyl acetate is produced at the bottom of the refining tower.
After reacting for a certain time (about 1500h), the activity of the catalyst in the No. 1 reactor is reduced, at the moment, the raw material gas is switched to the No. 2 reactor to continue the carbonylation reaction, and the catalyst in the No. 1 reactor is regenerated; and when the activity of the catalyst in the No. 2 reactor is reduced, switching the raw material gas to the No. 1 reactor to continue the carbonylation reaction, and regenerating the catalyst in the No. 2 reactor, so that the continuous reaction for preparing the methyl acetate by the carbonylation of the dimethyl ether is realized.
The specific steps of the catalyst regeneration in the reactor No. 1 are as follows:
step (1): maintaining H in the # 1 reactor system while maintaining the temperature and pressure of the carbonylation reaction2The partial pressure is unchanged, the ratio of CO/DME is adjusted, the gas is subjected to heat exchange and cooling after passing through a bed layer, is subjected to alkali washing in an alkali washing device 10, the discharged gas phase is subjected to dehydration and drying treatment 12, and the treated gas circularly enters a No. 1 reactor for 15 hours.
Step (2): gradually reducing DME content to 0 and increasing H2Partial pressure, CO/H adjustment2The gas is subjected to heat exchange and cooling after passing through a bed layer, is subjected to alkaline washing in an alkaline washing device 10, the discharged gas phase is subjected to dehydration and drying treatment, and the treated gas circularly enters a No. 1 reactor for 20 hours.
And (3): replacing the whole system with inert gas, and introducing trace O into the system2In the system, make O2The content was 60 ppm. And (3) performing heat exchange and cooling on the gas after passing through the bed layer, performing alkali washing in an alkali washing device 10, performing dehydration and drying treatment on the gas phase discharged from the alkali washing device 12, performing dehydration and drying treatment on the gas phase, and circulating the treated gas into a No. 1 reactor for 60 hours. Finally using N2The regeneration process of the catalyst can be finished after the whole system is replaced by gas. And when the reaction time of the 2# reactor reaches 1500h, cutting the reaction feed gas into the 1# reactor, and repeating the regeneration process of the catalyst in the 2# reactor, so as to realize the continuous preparation of the methyl acetate by the carbonylation of the dimethyl ether.
Example 1:
the embodiment provides a method for preparing methyl acetate by carbonylation of dimethyl ether, the process flow also adopts the figure 1, and the specific process steps are the same as the specific embodiment. In this example, MOR molecular sieve was used as the catalyst in both reactor No. 1 and reactor No. 2, and CO, DME and H in the reaction gas feed2Is 7: 1: the temperature, the pressure and the space velocity of the dimethyl ether carbonylation reaction in the 1, 1# reactor are respectively 150 ℃, 5MPa and 3000h－1. After the No. 1 reactor reacts for 1500 hours, the activity of the catalyst is reduced, and regeneration is needed, at the moment, the raw material gas is switched to 2 through a control valveThe # reactor is continuously used for carrying out dimethyl ether carbonylation reaction under the same reaction conditions as the # 1 reactor. The catalyst of the No. 1 reactor is regenerated, and the specific regeneration steps are as follows:
step (1): under the condition of keeping the temperature and the pressure of the carbonylation reaction, the space velocity of the regeneration reaction system is 400h－1Keeping H in the 1# reactor system2The partial pressure is unchanged, the ratio of CO/DME is adjusted, and the volume ratio of CO to DME is from 7: 1 is increased to 40: 1, gas is subjected to heat exchange and cooling after passing through a bed layer, alkali washing is carried out in an alkali washing device 10, the discharged gas phase is subjected to dehydration and drying treatment 12, the gas with the water content of less than or equal to 10ppm after the dehydration treatment circularly enters a reactor No. 1, and the duration time is 15 hours.
Step (2): gradually reducing DME content to 0 and increasing H2Partial pressure, CO/H adjustment2The ratio is 1:2, gas is subjected to heat exchange and cooling after passing through a bed layer, is subjected to alkali washing in an alkali washing device 10, the discharged gas phase is subjected to dehydration and drying treatment, and the gas with the water content of less than or equal to 10ppm after the dehydration treatment circularly enters a No. 1 reactor for 20 hours.
And (3): by containing O2Regenerating the catalyst with the gas mixed with the inert gas, i.e. replacing the whole system with the inert gas and introducing a trace amount of O into the system2In the system, make O2The content was 60ppm and the inert gas was N2. And (3) performing heat exchange and cooling on the gas after passing through the bed layer, performing alkali washing in an alkali washing device 10, performing dehydration drying treatment on the gas phase obtained from the step (12), and circulating the gas with the water content of less than or equal to 10ppm after the dehydration treatment into a No. 1 reactor for 60 hours.
Finally using N2The regeneration process of the catalyst of the No. 1 reactor can be finished after the whole system is replaced by gas. When the activity of the catalyst in the No. 2 reactor is reduced and regeneration is needed, the raw material gas is switched to the No. 1 reactor to continue the dimethyl ether carbonylation reaction, the No. 2 reactor catalyst is regenerated, the regeneration step is the same as the regeneration step of the No. 1 reactor catalyst, and the steps are repeated, so that the continuous preparation of methyl acetate by dimethyl ether carbonylation is completed.
The regenerated catalyst is continuously used for the subsequent dimethyl ether carbonylation reaction, and the dimethyl ether carbonylation reaction is carried out at the temperature of 150 ℃, the pressure of 5MPa and the content of CO in the raw material gas: DME: h2The proportion is 7: 1:1, airspeed 3000h－1Under the condition of the reaction. The results of the activity test of the regenerated catalyst are shown in Table 1. After regeneration, a small amount of the regenerated catalyst was taken out for carbon content determination, and the results are shown in Table 2.
Example 2:
this example provides a method for preparing methyl acetate by carbonylation of dimethyl ether, the preparation steps in this example are the same as the specific embodiments, in this example, the conditions are changed only, FER molecular sieves are used as catalysts in the 1# reactor and the 2# reactor, CO, DME and H in the raw materials of the reaction gas2Is 7: 1:1, the carbonylation temperature, pressure and space velocity of the dimethyl ether are 185 ℃, 5MPa and 2500h respectively－1. And regenerating after reacting for 1000 h. The regeneration steps are as follows:
the space velocity of the regeneration reaction system in the step (1) is 500h－1The volume ratio of CO to DME is from 7: 1 is increased to 50: 1, circulating the gas with the water content less than or equal to 10ppm after water removal treatment into a No. 1 reactor for 15 h.
Lifting H in step (2)2Partial pressure, CO/H2The volume ratio of (a) to (b) is adjusted to 1: 3, circulating the gas with the water content less than or equal to 10ppm after the water removal treatment into the No. 1 reactor for 20 hours.
O in the reactor System in step (3)2The content is 65ppm, He is inert gas, and the gas with the water content less than or equal to 10ppm after the water removal treatment is circulated into the No. 1 reactor for 60 hours.
Finally using N2The regeneration process of the catalyst can be finished after the whole system is replaced by gas.
The regenerated catalyst is continuously used for reaction, and the dimethyl ether carbonylation reaction is carried out at the temperature of 185 ℃, the pressure of 5MPa and the ratio of CO in raw material gas: DME: h2The proportion is 7: 1:1, airspeed 2500h－1Under the condition of the reaction. The results of the activity test of the regenerated catalyst are shown in Table 1. After regeneration, a small amount of the regenerated catalyst was taken out for carbon content determination, and the results are shown in Table 2.
Example 3:
this example provides a method for preparing methyl acetate by carbonylation of dimethyl ether according to the present invention, the preparation steps of this example are the same as those of the specific embodiment, and in this example, only the modification is madeChanging the following conditions, selecting a ZSM-5 molecular sieve catalyst for loading Cu as the catalyst in the No. 1 reactor and the No. 2 reactor, and selecting CO, DME and H in the reaction gas raw material2Is 6.5: 1: 1.1, the carbonylation temperature, pressure and space velocity of the dimethyl ether are respectively 180 ℃, 4.5MPa and 3500h－1. The catalyst needs to be regenerated after 1600h reaction in the No. 1 reactor. The regeneration steps of the catalyst of the No. 1 reactor are as follows:
the space velocity of the regeneration reaction system in the step (1) is 300h－1The CO/DME ratio was from 7: 1 is increased to 45: 1, circulating the gas with the water content less than or equal to 10ppm after water removal treatment into a No. 1 reactor for 20 hours.
Increasing the partial pressure of H2 in the step (2), and adjusting the ratio of CO/H2 to 1: 3, circulating the gas with the water content less than or equal to 10ppm after the water removal treatment into the No. 1 reactor for 25 hours.
O in the reactor System in step (3)2The content is 60ppm, Ar is inert gas, and the gas with the water content less than or equal to 10ppm after the water removal treatment is circulated into the No. 1 reactor for 75 hours.
Finally using N2The regeneration process of the catalyst can be finished after the whole system is replaced by gas.
The regenerated catalyst is continuously used for reaction, and the dimethyl ether carbonylation reaction is carried out at the temperature of 180 ℃, the pressure of 4.5MPa and the content of CO in raw material gas: DME: h2The ratio is 6.5: 1: 1.1, space velocity 3500h－1Under the condition of the reaction. The results of the activity test of the regenerated catalyst are shown in Table 1. After regeneration, a small amount of the regenerated catalyst was taken out for carbon content determination, and the results are shown in Table 2.
Example 4
This example provides a method for preparing methyl acetate by carbonylation of dimethyl ether, the preparation steps in this example are the same as the specific embodiments, in this example, the conditions are changed only, MOR molecular sieve is used as the catalyst in the 1# reactor and the 2# reactor, CO, DME and H in the reaction gas raw material2Is 8: 1: 1.2, the carbonylation temperature, pressure and space velocity of the dimethyl ether are respectively 180 ℃, 5MPa and 3500h－1. After the reaction time of the No. 1 reactor is 1700h, the catalyst needs to be regenerated. The regeneration steps of the catalyst of the No. 1 reactor are as follows:
the space velocity of the regeneration reaction system in the step (1) is 400h－1The CO/DME ratio was from 8: 1 is increased to 80: 1, circulating the gas with the water content less than or equal to 5ppm after water removal treatment into a No. 1 reactor for 18 h.
Increasing the partial pressure of H2 in the step (2), and adjusting the ratio of CO/H2 to 1: 4, circulating the gas with the water content less than or equal to 8ppm after the water removal treatment into the No. 1 reactor for 20 hours.
O in the reactor System in step (3)2The content is 100ppm, N2 is inert gas, the gas with the water content less than or equal to 6ppm after the water removal treatment is circulated into the No. 1 reactor, and the duration is 60 hours.
Finally using N2The regeneration process of the catalyst can be finished after the whole system is replaced by gas.
The regenerated catalyst is continuously used for reaction, and the dimethyl ether carbonylation reaction is carried out at the temperature of 180 ℃, the pressure of 5MPa and the content of CO in raw material gas: DME: h2The proportion is 8: 1: 1.2, space velocity 3500h－1Under the condition of the reaction. The results of the activity test of the regenerated catalyst are shown in Table 1. After regeneration, a small amount of the regenerated catalyst was taken out for carbon content determination, and the results are shown in Table 2.
Comparative example 1
This example provides a process for the carbonylation of dimethyl ether to produce methyl acetate in accordance with the invention and this example corresponds to example 1 except that step (3) of example 1 is not carried out and that after step (2) has been completed, N is used as the catalyst2The regeneration process of the catalyst can be finished after the whole system is replaced by gas.
The regenerated catalyst is continuously used for reaction, and the dimethyl ether carbonylation reaction conditions are the same as those of the example 1. The results of the activity test of the regenerated catalyst are shown in Table 1. A small amount of the regenerated catalyst was taken out for carbon content measurement, and the results are shown in Table 2.
Comparative example 2:
in this embodiment, the dimethyl ether carbonylation catalyst is MOR molecular sieve, and the dimethyl ether carbonylation reaction is carried out at 180 ℃ and 5MPa under the conditions of CO: DME: h2The proportion is 8: 1: 1.2, space velocity 3500h－1Under the conditions that the specific regeneration steps are as follows：
At the reaction temperature of 185 ℃, the pressure of 5MPa and the reaction time of 400h－1Under the condition of O in the reactor system2The content is 100ppm, N2 is inert gas, the gas with the water content less than or equal to 6ppm after the water removal treatment is circulated into the No. 1 reactor, and the duration is 60 hours. Finally using N2The regeneration process of the catalyst can be finished after the whole system is replaced by gas.
The regenerated catalyst is continuously used for reaction, and the dimethyl ether carbonylation reaction is carried out at the temperature of 180 ℃, the pressure of 5MPa and the content of CO in raw material gas: DME: h2The proportion is 8: 1: 1.2, space velocity 3500h－1Under the condition of the reaction. The results of the activity test of the regenerated catalyst are shown in Table 1. A small amount of the regenerated catalyst was taken out for carbon content measurement, and the results are shown in Table 2.
Comparative example 3
This example provides a process for the carbonylation of dimethyl ether to produce methyl acetate in accordance with the present invention and corresponds to comparative example 2 except that O is used in step (3)2The concentration is increased to 5%.
The regenerated catalyst is continuously used for reaction, and the reaction conditions of the carbonylation of the dimethyl ether are the same as those of the comparative example 2. The results of the activity test of the regenerated catalyst are shown in Table 1. A small amount of the regenerated catalyst was taken out for carbon content measurement, and the results are shown in Table 2.
Comparative example 4
This example provides a process for the carbonylation of dimethyl ether to produce methyl acetate in accordance with the present invention and corresponds to comparative example 2 except that O is used in step (3)2The concentration is increased to 20%.
The regenerated catalyst is continuously used for reaction, and the reaction conditions of the carbonylation of the dimethyl ether are the same as those of the comparative example 2. The results of the activity test of the regenerated catalyst are shown in Table 1. A small amount of the regenerated catalyst was taken out for carbon content measurement, and the results are shown in Table 2.
TABLE 1
Figure BDA0002732609080000121
TABLE 2
Figure BDA0002732609080000122
The activity test results in table 1 show that, in the reaction of preparing methyl acetate by carbonylation of dimethyl ether, the carbonylation molecular sieve catalyst is regenerated by the method of the invention, and the yield of methyl acetate of the regenerated catalyst can be recovered to the activity of the fresh catalyst at the initial reaction stage. Other methods do not allow complete recovery of catalyst activity.
As shown in Table 2, the C content of the regenerated catalyst is 0.0% when the carbonylation molecular sieve catalyst is regenerated by the method of the present invention. While other methods still leave a certain amount of carbon deposits on the regenerated catalyst. The method greatly reduces the regeneration temperature of the catalyst, reduces the requirement on equipment level, reduces the cost investment and has good industrial application prospect on the premise of effectively achieving the regeneration standard of 100 percent of the activity of the molecular sieve catalyst in the reaction of preparing the methyl acetate by carbonylation of dimethyl ether.
Although the present invention has been described in detail with respect to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims.

Claims (10)

1. The method for preparing methyl acetate by carbonylation of dimethyl ether is characterized by comprising the following steps:
preheating dimethyl ether and carbon monoxide respectively, mixing with hydrogen, feeding into a reactor, and carrying out carbonylation reaction in the reactor filled with a catalyst; with the activity of the catalyst being reduced, the raw material is switched to another reactor to continue the carbonylation reaction, and the catalyst in the original reactor is regenerated; when the activity of the catalyst in the other reactor is reduced and needs to be regenerated, the catalyst is switched back to the original reactor; the process for regenerating the catalyst in the reactor comprises the steps of:
(1) h in the raw material gas at the original reaction temperature and reaction pressure2The partial pressure is unchanged, the CO partial pressure is increased, the DME partial pressure is reduced, and the reaction is continued for a period of time;
(2) increasing H gradually2Reducing the partial pressure of the dimethyl ether to 0 while the partial pressure is maintained, and continuing to react for a period of time;
(3) by containing O2The gas mixed with the inert gas regenerates the catalyst, and the oxygen concentration gradually rises; and 3, the regenerated tail gas obtained in the step is subjected to cooling, alkali washing, drying and water removal treatment in sequence and then enters the original reactor for recycling.
2. The method for preparing methyl acetate by carbonylation of dimethyl ether according to claim 1, wherein the reactor is a fixed bed reactor or a fluidized bed reactor.
3. The process of carbonylation of dimethyl ether to produce methyl acetate according to claim 1 wherein the carbonylation catalyst is MOR, FER or ZSM-5 molecular sieve containing eight or ten membered ring channels and Cu, Zn or Fe metal modified catalyst.
4. The method for preparing methyl acetate by carbonylation of dimethyl ether according to claim 1, wherein the reaction temperature of the carbonylation reaction is 140 to 190 ℃, and the reaction pressure is 1.0 to 10.0 MPa.
5. The method for preparing methyl acetate by carbonylation of dimethyl ether according to claim 1, wherein CO, DME and H are contained in the raw material gas of the carbonylation reaction2The volume ratio of (A) is 3-30: 0.5-5, and the airspeed is 1000-10000 h-1。
6. The method for preparing methyl acetate by carbonylation of dimethyl ether according to claim 1, wherein the volume ratio of CO to DME in step (1) is 30-100: 1, and the continuous reaction time is 10-30 h.
7. The process for preparing methyl acetate by carbonylation of dimethyl ether according to claim 1, wherein CO and H are added in the step (2)2The volume ratio of (A) to (B) is 1: 1-10, and the continuous reaction time is 10-30 h.
8. The process for preparing methyl acetate by carbonylation of dimethyl ether according to claim 1, wherein the step (3) comprises O2A gas mixed with an inert gas, the inert gas being N2Any one or a mixture of He and Ar, wherein O2The concentration is 1-500 ppm; o is2The concentration raising rate is (0.5-2) ppm/h, and the constant temperature time is 1-10 h.
9. The method for preparing methyl acetate by carbonylation of dimethyl ether according to claim 1, wherein the water content in the gas after the drying and water removal treatment in the step (3) is less than or equal to 10 ppm.
10. The method for preparing methyl acetate by carbonylation of dimethyl ether according to claim 1, wherein the volume ratio of CO to DME in the step (1) is 40-60: 1; CO and H in step (2)2The volume ratio of (A) to (B) is 1: 2-4; and (3) the water content in the gas after the drying and dewatering treatment is 0-5 ppm.
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