CN109200773B - Treatment method of tail gas of methyl ethyl ketone device - Google Patents
Treatment method of tail gas of methyl ethyl ketone device Download PDFInfo
- Publication number
- CN109200773B CN109200773B CN201710521938.1A CN201710521938A CN109200773B CN 109200773 B CN109200773 B CN 109200773B CN 201710521938 A CN201710521938 A CN 201710521938A CN 109200773 B CN109200773 B CN 109200773B
- Authority
- CN
- China
- Prior art keywords
- membrane
- gas
- methyl ethyl
- ethyl ketone
- tail gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D50/00—Combinations of methods or devices for separating particles from gases or vapours
- B01D50/20—Combinations of devices covered by groups B01D45/00 and B01D46/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/144—Purification; Separation; Use of additives using membranes, e.g. selective permeation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D2053/221—Devices
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for treating tail gas of a methyl ethyl ketone device comprises the steps of separating the tail gas through a membrane reactor, wherein a membrane in the membrane reactor is a silicon rubber/poly-maple composite membrane, the aperture of the membrane is 0.01-1.0 um, the inner diameter of the membrane is 0.1-1.5 mm, and the wall thickness of the membrane is 0.1-1.5 mm; the preparation is soaked in toluene, methyl isobutyl ketone and distilled water before use. The tail gas treatment method of the invention utilizes the membrane reactor with special treatment, changes the transmission characteristic of the membrane, can effectively separate effective components and impurities in the tail gas, and the content of butylene in the obtained permeation gas completely meets the requirement of directly recycling the permeation gas as a raw material.
Description
Technical Field
The invention relates to a method for treating tail gas of a methyl ethyl ketone device, in particular to a method for treating tail gas generated in a hydration process of producing methyl ethyl ketone by taking n-butene as a raw material.
Background
Methyl ethyl ketone is an important low-boiling point solvent, has excellent solubility and drying characteristics, can form an azeotrope with various solvents, has strong dissolving capacity for many substances such as resins, fiber derivatives, synthetic rubbers, greases and higher fatty acids, is a good solvent for high molecular compounds such as nitrocellulose, polyurethane, vinyl resins, acrylic resins, alkyd resins, phenolic resins, adhesives, inks, magnetic tapes, pharmaceutical production and lubricating oil dewaxing, and is widely applied to the fields of lubricating oil dewaxing, coatings, adhesives, inks, magnetic tapes, medicines, electronic components and the like. In addition, as an important organic chemical raw material and an intermediate, the organic chemical raw material can be used for producing high molecular ketone, cyclic compounds and the like, and also can be used for directly synthesizing methyl ethyl ketone peroxide and methyl ethyl ketone oxime, and preparing an antioxidant, a catalyst, a dye, an anti-skinning agent of a coating, an electronic element cleaning solution and the like.
The industrial production of methyl ethyl ketone in China starts in 1966, and a first set of methyl ethyl ketone device in China is built by a petrochemical second factory, and a technology for preparing secondary butyl alcohol aerated phase dehydrogenation by using an indirect hydration method of sulfuric acid is adopted. In 1988, the general petrochemical plant of Thai, Jiangsu introduced the technology of producing sec-butyl alcohol by hydration with a resin method from the company Deutsche Texco, West Germany, and in 1991, a set of 7300t/a methyl ethyl ketone device was built. Later, related research and design units in China continuously digest the direct hydration technology of the resin absorption method, and develop a methyl ethyl ketone complete set technology with independent intellectual property rights. A batch of methyl ethyl ketone devices are successively built in China, and the energy expansion is continuously improved. By 2014, the total design production capacity of the methyl ethyl ketone in China is about 60.2 ten thousand tons.
The main process route of the methyl ethyl ketone comprises the following steps: two-step process of hydration and dehydrogenation of butylene, liquid-phase oxidation of butane, catalytic hydrolysis of butadiene and mixing4Oxidation, direct oxidation of butene, electrolytic oxidation of butene, isobutylbenzene, isomerization of butylene oxide, isomerization of isobutylaldehyde, one-step oxidation of n-butene, etc. Among them, the main ones that have been industrialized are: butane liquid phase oxidation, butene hydration and dehydrogenation two-step method and sec-butyl alcohol oxidation method. The current production process of methyl ethyl ketone uses C4The method is a main production route of methyl ethyl ketone as a raw material, and has the advantages of earliest realization of industrialization, reliable and mature process and stable product quality.
A two-step method of butylene hydration and dehydrogenation is the most main method for producing sec-butyl alcohol at home and abroad at present. The method comprises the steps of taking resin as a catalyst, generating sec-butyl alcohol (SBA) from n-butene through proton catalysis, carrying out reaction under a three-phase condition, wherein the reaction temperature is 135-170 ℃, the reaction pressure is 6.0-8.0 MPa, the molar ratio of water to n-butene is about 1: 1-2: 1, and the resin is selected from strong-acid cation exchange resin with good heat resistance. The method has the advantages of simple process flow, easy product recovery and refining, less three wastes, small corrosion to equipment and high sec-butyl alcohol selectivity.
In the sec-butyl alcohol synthesis section, the conversion per pass of the direct water-based polymerization of n-butene to sec-butyl alcohol is generally lower than 6.0%, the tail gas contains a large amount of n-butene (the content of butene-1, cis-butene and trans-butene-2 is about 85%) and a small amount of impurities such as alcohol, ether, methyl ethyl ketone, water and the like, and if the impurities are directly recycled, the impurities can cause the poisoning of a butene concentration extractant. The tail gas is purified to remove impurities such as alcohol, ether, methyl ethyl ketone, water and the like, so that the tail gas can be recycled.
There are many schemes for purifying methyl ethyl ketone tail gas, such as: water washing, rectification, purification by MTBE unit, absorption-distillation purification process, etc. Among these methods, the water washing method cannot achieve the purification effect because ethers in the remaining butene are insoluble in water; in the rectification method, the water in the residual butene cannot be purified due to the azeotropic reaction with ethers, alcohols and methyl ethyl ketone. Therefore, the phase 9 of the 25 th volume of 2005 and the phase 1 of the 28 th volume of 2009 of the modern chemical industry report the adsorbent for removing sec-butyl alcohol by circulating butylene of a methyl ethyl ketone device, so that the adsorption capacity of the developed PUMS-01 adsorbent reaches 22%, and the adsorption temperature is normal temperature, the pressure is 0.5MPa, and the liquid space velocity is 0.2h－1Under the process conditions of (1), 0.5-2.5% of sec-butyl alcohol in the raw material can be removed to be below 100 mu g/g.
The application of a residual butene dehydration-rectification purification process in a 2500t/a methyl ethyl ketone device is reported in volume 33, No. 6 of 2012 of chemical industry and engineering technology, and the purification of tail gas by the dehydration-rectification purification process of the methyl ethyl ketone tail gas is introduced, and the result shows that after the treatment of the dehydration-rectification purification process, the water content mass fraction is reduced to 0.0006%, the sec-butyl alcohol, the sec-butyl ether and the methyl ethyl ketone in the residual butene are completely removed, the feeding requirement of the methyl ethyl ketone device is met, and the cyclic utilization can be realized.
The method generally has the defects of complex process and high production cost, in addition, the adsorbent needs to be regenerated to be usable after reaching a certain adsorption quantity, and a technical scheme for separating and treating tail gas of the methyl ethyl ketone device by adopting a membrane is not adopted in the prior art.
Disclosure of Invention
In order to solve the problems of complex treatment process, high cost and substandard tail gas treatment effect of the tail gas of the methyl ethyl ketone device in the prior art, the invention provides the tail gas treatment method of the methyl ethyl ketone device, the membrane component is treated by a specific means, the operation conditions are controlled to separate the tail gas, and the butylene component with the purity of more than 95 percent is obtained by separation and can be directly recycled.
In order to achieve the technical purpose, the invention adopts the following technical means:
the invention provides a method for treating tail gas of a methyl ethyl ketone device, wherein the tail gas of the methyl ethyl ketone device is tail gas in a hydration reaction stage in the process of producing methyl ethyl ketone by butylene through a two-step method of hydration and dehydrogenation, and the method for treating the tail gas of the methyl ethyl ketone device comprises the following steps: after the tail gas is dehydrated and dedusted, membrane separation is carried out by a membrane reactor, and the operation conditions of the membrane separation are as follows: the pressure is 0.1 MPa-1.5 MPa, the temperature is 50-120 ℃, the air inlet speed is 0.5 m/s-10.0 m/s, the permeation gas rich in the butylene and the residual gas rich in the alcohol, the ether and the methyl ethyl ketone are obtained, and the permeation gas rich in the butylene can return to a sec-butyl alcohol working section to be used as a raw material for continuous reaction;
wherein, the membrane in the membrane reactor is a silicon rubber/maple composite membrane, the aperture of the membrane is 0.01 um-1.0 um, the inner diameter is 0.1 mm-1.5 mm, and the wall thickness is 0.1 mm-1.5 mm;
the membrane reactor is treated before use by:
soaking toluene at 40-80 deg.c for 8-24 hr, soaking methyl isobutyl ketone at 40-60 deg.c for 4-12 hr, and soaking with distilled water with oxygen content not higher than 5mg/L in three stages: the first stage treatment conditions are that the pressure is 0.5MPa to 0.8MPa, the temperature is 60 ℃ to 75 ℃, and the soaking time is 8h to 24 h; the second stage treatment conditions are that the pressure is 0.9MPa to 1.5MPa, the temperature is 85 ℃ to 100 ℃, and the soaking time is 12h to 24 h; the third stage treatment conditions are that the pressure is 1.3MPa to 1.5MPa, the temperature is 120 ℃ to 150 ℃, and the soaking time is 12h to 48 h; and (4) simultaneously introducing inert gas or nitrogen into the three stages, and finally drying.
In the above processing method, it should be understood by those skilled in the art that the tail gas of the methyl ethyl ketone unit mainly contains impurities such as sec-butyl alcohol, sec-butyl ether, methyl ethyl ketone and water besides butene, and the content of each component in the tail gas differs according to the respective process differences, so that the processing method of the present invention is particularly suitable for the tail gas processing method with the following impurity content in order to make the present invention more fully understood by those skilled in the art: the content of the sec-butyl alcohol is 0.1-5.0%, preferably 1.0-3.0%, the content of the sec-butyl ether is 0.1-5.0%, preferably 0.15-3.0%, the content of the methyl ethyl ketone is 0.1-3.0%, preferably 0.5-2.0%, the content of the moisture is 0.5-10.0%, preferably 1.0-5.0%, and the balance is butylene. It should be noted that the tail gas of the above composition is treated by the method of the present invention, so as to obtain more ideal separation results, and the butene content in the separated gas meets the requirement of recycling as raw material, and the impurities therein are basically removed without affecting the process reaction, which is not the tail gas of the methyl ethyl ketone device outside the composition which is not suitable for being treated by the method.
In the treatment method, the dehydration and dust removal is to remove all solid particles, water mist and aerosol which are carried in the tail gas and have the diameter of more than 0.01 mu m, so that the content of micro-dust in the treated tail gas is less than or equal to 0.05mg/Nm3And the water content is less than or equal to 5 PPm. The treatment method is well known to those skilled in the art, such as inertial dust removal, wet dust removal, electrostatic dust removal, filtration dust removal, single-cylinder cyclone dust removal, multi-tube cyclone dust removal, centrifugal force separation, gravity settling, baffling separation, wire mesh separation, ultrafiltration separation, filler separation and the like, and the centrifugal force separation and filtration dust removal are preferred.
In the treatment method, the tail gas can be pressurized to the required pressure by a pneumatic booster pump or a gas booster before being introduced into the membrane separator; the temperature of the tail gas is reduced to the required temperature through a heat exchange mode, the heat exchange mode comprises various mixed type, heat accumulation type or dividing wall type heat exchangers, preferably the dividing wall type heat exchanger, wherein the dividing wall type heat exchanger can be a special type heat exchanger consisting of jacket type, pipe type, plate type or various special-shaped heat transfer surfaces; the flow modes of the cold and hot fluids in the heat exchanger include concurrent flow, countercurrent flow, alternating flow and mixed flow, and preferably countercurrent flow.
In the above treatment method, as a further preferable mode, the membrane separation is performed under the following conditions: the pressure is 0.5MPa to 1.0MPa, the temperature is 60 ℃ to 80 ℃, and the air inlet speed is 1.0m/s to 5.0m/s, wherein the air inlet speed is more preferably 1.0m/s to 2.0 m/s.
In the above treatment method, the silicone rubber/polyimide composite membrane preferably has a membrane pore diameter of 0.05 to 0.8um, more preferably 0.1 to 0.5 um; the inner diameter is 0.1mm to 1.0mm, more preferably 0.2mm to 0.8 mm; the thickness of the wall is 0.2mm to 1.0mm, and more preferably 0.2mm to 0.5 mm.
In the treatment method, the temperature for soaking the membrane reactor by the methylbenzene is 40-60 ℃ and the time is 10-20 h as further optimization; the temperature of the methyl isobutyl ketone for soaking the membrane reactor is 40-50 ℃, and the time is 4-8 h.
In the above treatment method, the oxygen content of the distilled water used for immersing the membrane module is preferably not more than 3mg/L, more preferably not more than 1mg/L (in the conditions of 20 ℃ and 100 kPa).
In the above treatment method, as a further preferable mode, the flow rates of the inert gas or the nitrogen gas introduced into the membrane reactor at three stages of the soaking in distilled water are respectively 20m3/h～25m3/h、10m3/h～15m3H and 5m3/h～8m3/h。
In the above treatment method, the soaking according to the present invention is based on the condition that the membrane module is completely submerged by the liquid.
In the treatment method, the membrane reactor comprises a shell and a membrane component, the membrane component is arranged in the shell, one end of the shell and the membrane component are provided with a methyl ethyl ketone tail gas inlet in parallel, the other end of the shell and the membrane component are provided with a residual gas seepage outlet in parallel, and the side surface of the shell is provided with a gas seepage outlet.
After the tail gas is treated, permeation gas rich in butylene and residual gas rich in alcohol, ether and methyl ethyl ketone are obtained, the permeation gas returns to a sec-butyl alcohol working section to be used as a raw material, one part of the residual gas can return to a membrane separator for further purification, and the other part of the residual gas can recover the alcohol, the ether and the methyl ethyl ketone.
Compared with the prior art, the tail gas treatment method for the methyl ethyl ketone device has the following advantages:
1. the invention removes the micromolecule polymer impurities in the membrane component by soaking the membrane reactor with toluene and methyl isobutyl ketone under specific conditions and treating with water in stages, so that the pore size distribution of the membrane component is more uniform, and the invention is more beneficial to removing alcohol, ether and methyl ethyl ketone in the permeating gas and enriching butylene.
2. Compared with other processes, the tail gas treatment method of the methyl ethyl ketone device has the advantages of low equipment investment cost, long service cycle, simple operation and low energy consumption; the membrane reactor after special treatment has good gas separation selectivity and high separation efficiency, effectively separates impurities in tail gas to ensure that the content of butylene reaches over 96 percent, completely meets the requirement of directly recycling as raw materials, and does not generate secondary pollution in the whole process.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a flow chart showing a specific process for treating tail gas of a methyl ethyl ketone unit used in the example;
FIG. 2 is a schematic diagram of a membrane reactor;
the system comprises a gas centrifuge 1, a gas booster I, a high-pressure storage tank 3, an activated carbon filter 4, a counter-flow heat exchanger 5, a precision filter 6, a membrane reactor 7, a gas booster II, a tail gas inlet 9, a permeate gas outlet 10, a membrane module 11, a shell 12, a permeate residual gas outlet 13, pipelines I and I, 15, pipelines II and 16 and a pipeline III.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
In the following embodiments, the process flow device shown in fig. 1 is used to treat methyl ethyl ketone tail gas, normal temperature tail gas from a process for preparing sec-butyl alcohol by hydrating butylene in the production process of methyl ethyl ketone is firstly passed through a gas centrifuge 1 to primarily remove solid particles and water carried in the tail gas, then is pressurized to 0.5 MPa-1.0 MPa by a gas booster i 2, enters a high pressure storage tank 3, is further dehydrated and dedusted by an activated carbon filter 4, is subjected to heat exchange by a tubular countercurrent heat exchanger 5 to make the temperature of the methyl ethyl ketone tail gas reach 50 ℃ -70 ℃, and is subjected to fine filter 6 to remove all solid particles with diameters larger than 0.01 μm to obtain the tail gas with the dust content of less than or equal to 0.01 μmmg/Nm3The membrane entering gas with water content less than or equal to 5PPm enters the membrane reactor 7 under the conditions of pressure of 0.5MPa to 1.0MPa, temperature of 60 ℃ to 80 ℃ and air inlet speed of 0.5m/s to 2.0m/s, and the purified permeation gas and the permeation residual gas concentrated with impurities are separated. Wherein the permeating gas is led out from a permeating gas outlet through a pipeline I14 and returned to a sec-butyl alcohol synthesis section, part of the permeating residual gas is returned to the activated carbon filter 4 through a pipeline II 15 through a gas booster II 8 and a pipeline III 16, and the other part of the permeating residual gas is subjected to recovery of alcohol, ether and methyl ethyl ketone.
FIG. 2 is a schematic diagram of a membrane reactor used in an embodiment of the invention. The membrane reactor is provided with a shell 12, a membrane module 11 is arranged in the shell, one end of the shell 12 is provided with a methyl ethyl ketone tail gas inlet 9 in parallel with the membrane module 11, the other end of the shell 12 is provided with a residual gas seepage outlet 13 in parallel with the membrane module 11, and the side surface of the shell is provided with a seepage gas outlet 10. The methyl ethyl ketone tail gas flows in the membrane component, impurity components as slow gas are discharged through the residual gas permeation outlet 13 by passing through the tube pass of the membrane component, and liquefied gas as fast gas is discharged through the membrane component through the gas permeation outlet 10. The membrane module is made of a silicon rubber/poly-maple composite membrane.
The film parameters used in the examples are shown in Table 1, and the volume composition of the tail gas from the methyl ethyl ketone unit is shown in Table 2.
TABLE 1
TABLE 2
Example 1
Taking tail gas of a methyl ethyl ketone device listed in Table 2 as a raw material, preliminarily removing solid particles and water carried in the tail gas through a gas centrifuge 1, pressurizing to 0.5MPa through a gas supercharger I2, and then feeding into a high-pressure storage tank 3; further dewatering and dedusting by an active carbon filter 4, and the content of the micro dust in the treated tail gas is 0.05mg/Nm3The water content is 2PPm, and then the water is processed by tube array inversionAfter heat exchange of the flow heat exchanger 5, the temperature of the methyl ethyl ketone tail gas reaches 50 ℃, the methyl ethyl ketone tail gas enters the membrane reactor 7 under the conditions that the pressure is 0.5MPa and the air inlet speed is 0.5m/s, and permeation gas rich in n-butene and residual gas containing alcohol, ether, methyl ethyl ketone and moisture are separated. The permeating gas is sent to a methyl ethyl ketone device to be used as a raw material for synthesizing sec-butyl alcohol; after the residual gas is adsorbed by different adsorbents, further removing alcohol, ether, methyl ethyl ketone and water in the residual gas, pressurizing the residual gas as reflux gas, and returning the residual gas to a membrane separator for continuous purification; and recovering alcohol, ether and methyl ethyl ketone from the other part of the residual gas, and returning the residual gas to the membrane reactor. The permeate composition results are shown in table 3.
Example 2
The process of example 1 was followed except that the gas was pressurized to 1.0MPa and then fed into the high-pressure tank 3; further dewatering and dedusting by an active carbon filter 4, and the content of the micro dust in the treated tail gas is 0.009mg/Nm3And the water content is 2PPm, the temperature of the methyl ethyl ketone tail gas reaches 60 ℃ after heat exchange is carried out by the countercurrent heat exchanger 5, the methyl ethyl ketone tail gas enters the membrane reactor 7 under the conditions of the pressure of 1.0MPa and the air inlet speed of 5m/s, and the permeating gas rich in n-butene and the permeating residual gas containing alcohol, ether, methyl ethyl ketone and water are separated. The permeating gas is sent to a methyl ethyl ketone device to be used as a raw material for synthesizing sec-butyl alcohol; after the residual gas is adsorbed by different adsorbents, further removing alcohol, ether, methyl ethyl ketone and water in the residual gas, pressurizing the residual gas as reflux gas, and returning the residual gas to a membrane separator for continuous purification; the other part of the residual gas is subjected to recovery of alcohol, ether and methyl ethyl ketone, and the residual gas returns to the membrane reactor, and the composition results of the residual gas are shown in Table 3.
Example 3
The process of example 1 was followed except that the gas was pressurized to 0.5MPa and then fed into the high-pressure tank 3; the content of the micro dust in the tail gas is 0.01mg/Nm through the active carbon filter 43And the membrane inlet gas with the water content of 1.0PPm is subjected to heat exchange by a countercurrent heat exchanger 5 to ensure that the temperature of the methyl ethyl ketone tail gas reaches 65 ℃, and the methyl ethyl ketone tail gas enters a membrane reactor 7 under the conditions of the pressure of 0.8MPa and the air inlet speed of 2.0m/s, so that the permeating gas rich in n-butene and the permeating residual gas containing alcohol, ether, methyl ethyl ketone and water are separated. The permeating gas is sent to a methyl ethyl ketone device to be used as a raw material for synthesizing sec-butyl alcohol; the residual gas is adsorbed by different adsorbents to further remove alcohol, ether, methyl ethyl ketone and water thereinThe return air is pressurized and then returns to the membrane separator for continuous purification; and recovering alcohol, ether and methyl ethyl ketone from the other part of the residual gas, and returning the residual gas to the membrane reactor. The permeate composition results are shown in table 3.
Example 4
The membrane module 11 is subjected to the following processes: soaking the membrane module 11 in toluene at 40 ℃ for 10h, then soaking in methyl isobutyl ketone at 50 ℃ for 8h, and treating the membrane module in three stages of distillation moisture with oxygen content of 1 mg/L: the first stage comprises soaking at 60 deg.C under 0.5MPa for 8 hr while introducing nitrogen at 20m flow rate3H; the second stage treatment condition is that the pressure is 0.9 MPa; soaking at 100 deg.C for 24 hr while introducing nitrogen gas at flow rate of 15m3H; the third stage treatment condition is 1.5 MPa; soaking at 120 deg.C for 12 hr while introducing nitrogen gas at flow rate of 5m3And h, drying after the treatment is finished to obtain the membrane component for purifying the methyl ethyl ketone tail gas.
The above treated module was used for off-gas treatment according to the method of example 1. The permeate composition results are shown in table 3.
Example 5
The membrane module 11 is subjected to the following processes: soaking the membrane module in toluene at 60 deg.c for 20 hr, and soaking in methyl isobutyl ketone at 60 deg.c for 4 hr. The membrane module is further treated in three stages of distilling moisture with the oxygen content of 2 mg/L: the first stage treatment condition is that the pressure is 0.8Mpa, the temperature is 75 ℃, the soaking is carried out for 24 hours, nitrogen is introduced while the soaking is carried out, and the flow rate is 25m3H; the second stage treatment condition is 1.0 MPa; soaking at 85 deg.C for 12h while introducing nitrogen gas at flow rate of 10m3H; the third stage treatment condition is 1.3 MPa; soaking at 150 deg.C for 48h while introducing nitrogen gas at flow rate of 8m3And h, drying after the treatment is finished to obtain the membrane component for purifying the methyl ethyl ketone tail gas.
The module after the above treatment was used for off-gas treatment according to the method of example 2. The permeate composition results are shown in table 3.
Example 6
The membrane module 11 is subjected to the following processes: the membrane module is soaked in toluene at the temperature of 80 ℃ for 12h, and then is soaked in methyl isobutyl ketone at the temperature of 50 ℃ for 4 h. The membrane module is further treated in three stages of distilling moisture with oxygen content of 1 mg/L: the first stage treatment condition is that the pressure is 0.6 MPa; soaking at 65 deg.C for 10h while introducing nitrogen gas at flow rate of 22m3H; the second stage treatment condition is 1.0 MPa; soaking at 90 deg.C for 16h while introducing nitrogen gas at flow rate of 12m3H; the third stage treatment condition is 1.5 MPa; soaking at 130 deg.C for 24 hr while introducing nitrogen gas at flow rate of 6m3And h, drying after the treatment is finished to obtain the membrane component for purifying the methyl ethyl ketone tail gas.
The above treated module was used for off-gas treatment according to the method of example 3. The permeate composition results are shown in table 3.
TABLE 3
As can be seen from tables 2 and 3, the content of effective components of butylene (butylene-1, maleic-2 and fumaric-2) in tail gas of the methyl ethyl ketone device is about 88%, the content of effective components of butylene (butylene-1, maleic-2 and fumaric-2) in tail gas can reach about 91% after the tail gas is refined by an untreated membrane module, the impurities of alcohol, ether, methyl ethyl ketone and moisture in the tail gas are effectively removed after the tail gas is refined by the treated membrane module, and the content of the effective components of butylene (butylene-1, maleic-2 and fumaric-2) in the tail gas is more than 96%, so that the tail gas can be completely used as a raw material for synthesizing a sec-butyl alcohol working section, and the purposes of purification, recovery and recycling are achieved.
Claims (10)
1. A processing method of tail gas of a methyl ethyl ketone device is provided, the tail gas of the methyl ethyl ketone device is tail gas of a hydration reaction stage in the process of producing methyl ethyl ketone by butylene through a two-step method of hydration and dehydrogenation, and the processing method comprises the following steps: after the tail gas is dehydrated and dedusted, membrane separation is carried out by a membrane reactor, and the operation conditions of the membrane separation are as follows: the pressure is 0.1 MPa-1.5 MPa, the temperature is 50-120 ℃, the air inlet speed is 0.5 m/s-10.0 m/s, the permeation gas rich in the butylene and the residual gas rich in the alcohol, the ether and the methyl ethyl ketone are obtained, and the permeation gas rich in the butylene can return to a sec-butyl alcohol working section to be used as a raw material for continuous reaction;
wherein, the membrane in the membrane reactor is a silicon rubber/polysulfone composite membrane, the aperture of the membrane is 0.05-0.8 μm, the inner diameter is 0.1-1.5 mm, and the wall thickness is 0.1-1.5 mm;
the membrane reactor is treated before use by:
soaking toluene at 40-80 deg.c for 8-24 hr, soaking methyl isobutyl ketone at 40-60 deg.c for 4-12 hr, and soaking with distilled water with oxygen content not higher than 5mg/L in three stages: the first stage treatment conditions are that the pressure is 0.5 MPa-0.8 MP a, the temperature is 60-75 ℃, and the soaking time is 8-24 h; the second stage treatment conditions are that the pressure is 0.9 MPa-1.5 MP a, the temperature is 85-100 ℃, and the soaking time is 12-24 h; the third stage treatment conditions are that the pressure is 1.3 MPa-1.5 MP a, the temperature is 120-150 ℃, and the soaking time is 12-48 h; and (4) simultaneously introducing inert gas or nitrogen into the three stages, and finally drying.
2. The process according to claim 1, characterized in that the operating conditions of the membrane separation are: the pressure is 0.5MPa to 1.0MPa, the temperature is 60 ℃ to 80 ℃, and the air inlet speed is 1.0m/s to 5.0 m/s.
3. The process of claim 2, wherein the membrane separation has an inlet gas velocity of 1.0m/s to 2.0 m/s.
4. The method according to claim 1, wherein the silicone rubber/polysulfone composite membrane has an inner diameter of 0.1mm to 1.0mm and a wall thickness of 0.2mm to 1.0 mm.
5. The method according to claim 4, wherein the silicone rubber/polysulfone composite membrane has a membrane pore diameter of 0.1 to 0.5 μm, an inner diameter of 0.2 to 0.8mm, and a wall thickness of 0.2 to 0.5 mm.
6. The process of claim 1 wherein the toluene immersion treatment of the membrane reactor is carried out at a temperature of 40 ℃ to 60 ℃ for a period of 10 hours to 20 hours.
7. The process of claim 1 wherein the methyl isobutyl ketone is soaked in the membrane reactor at a temperature of 40 ℃ to 50 ℃ for 4h to 8 h.
8. The process of claim 1 wherein the flow rates of inert gas or nitrogen gas to the membrane reactor during the three stages of the soaking in distilled water are 20m each3/h～25m3/h、10m3/h～15m3H and 5m3/h～8m3/h。
9. The treatment method according to claim 1, wherein the dehydration and dust removal are carried out so that the content of the fine dust in the treated tail gas is less than or equal to 0.05mg/Nm3And the water content is less than or equal to 5 ppm.
10. The process according to claim 1, characterized in that the composition of the off-gas is: according to weight, the content of sec-butyl alcohol is 0.1-5.0%, the content of sec-butyl ether is 0.1-5.0%, the content of methyl ethyl ketone is 0.1-3.0%, the content of water is 0.5-10.0%, and the balance is butylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710521938.1A CN109200773B (en) | 2017-06-30 | 2017-06-30 | Treatment method of tail gas of methyl ethyl ketone device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710521938.1A CN109200773B (en) | 2017-06-30 | 2017-06-30 | Treatment method of tail gas of methyl ethyl ketone device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109200773A CN109200773A (en) | 2019-01-15 |
| CN109200773B true CN109200773B (en) | 2021-06-04 |
Family
ID=64977043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710521938.1A Active CN109200773B (en) | 2017-06-30 | 2017-06-30 | Treatment method of tail gas of methyl ethyl ketone device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109200773B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1497018A2 (en) * | 2002-01-25 | 2005-01-19 | Colorado School Of Mines | Polymer blends and methods of separation using the same |
| CN106674003A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Method for preparing cyclopentanol by hydrating cyclopentene |
| CN106669375A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Process for treating tail gases of methyl ethyl ketone unit |
| CN106669376A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Method for using butane oxidation tail gas |
-
2017
- 2017-06-30 CN CN201710521938.1A patent/CN109200773B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1497018A2 (en) * | 2002-01-25 | 2005-01-19 | Colorado School Of Mines | Polymer blends and methods of separation using the same |
| CN106674003A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Method for preparing cyclopentanol by hydrating cyclopentene |
| CN106669375A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Process for treating tail gases of methyl ethyl ketone unit |
| CN106669376A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Method for using butane oxidation tail gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109200773A (en) | 2019-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106669375B (en) | Process for treating tail gas of methyl ethyl ketone device | |
| CN104098441B (en) | Commercial syngas mesohigh carbonylation produces dimethyl oxalate and the technique of Hydrogenation ethylene glycol and apparatus system | |
| US4545965A (en) | Process of selective separation of hydrogen sulfide from gaseous mixtures containing also carbon dioxide | |
| WO2015184677A1 (en) | Process and device system for producing dimethyl oxalate by high-pressure carbonylation of industrial synthesis gas and producing ethylene glycol by hydrogenation | |
| CN106669376B (en) | A kind of utilization method of butane oxidation tail gas | |
| CN106672911A (en) | Oxidation-extraction technology for production of hydrogen peroxide by anthraquinone process | |
| CN108997081A (en) | A kind of reaction and rectification device and method of cyclohexene hydration cyclohexanol | |
| CN114506820A (en) | Method for directly producing electronic grade hydrogen peroxide from hydrogen and oxygen | |
| CN109200773B (en) | Treatment method of tail gas of methyl ethyl ketone device | |
| CN109200771B (en) | Method for treating tail gas in methyl ethyl ketone production process | |
| CN111377801B (en) | Method and system for refining low carbon alcohol | |
| CN109200770B (en) | Treatment method of tail gas from butane oxidation to maleic anhydride | |
| CN111909120B (en) | Energy-saving separation process of water-containing ternary azeotropic system | |
| CN213680472U (en) | Tetrahydrofuran dehydration refining plant | |
| CN109200772B (en) | Method for treating tail gas in process of preparing maleic anhydride from butane | |
| CN109205571B (en) | Method for separating and purifying hydrogen peroxide | |
| CN109206294A (en) | A kind of processing method producing tail gas in MEK process | |
| CN109200769B (en) | Method for treating tail gas in process of preparing maleic anhydride by butane oxidation | |
| CN109200617B (en) | Method for treating hydrogen peroxide oxidized tail gas | |
| CN109205568B (en) | Method for purifying hydrogen peroxide | |
| CN109384654B (en) | Method for producing ethylene glycol mono-tert-butyl ether | |
| CN109205569B (en) | Method for purifying hydrogen peroxide produced by anthraquinone process | |
| CN107400103B (en) | Preparation process of olefin epoxidation oxidation liquid, oxidation liquid and application | |
| CN110606798A (en) | Method for preparing benzyl alcohol by using microchannel reactor without alkali | |
| CN113968789B (en) | Purification method and purification system of isophorone diamine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230918 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
|
| TR01 | Transfer of patent right |