CN109200769B - Method for treating tail gas in process of preparing maleic anhydride by butane oxidation - Google Patents

Method for treating tail gas in process of preparing maleic anhydride by butane oxidation Download PDF

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CN109200769B
CN109200769B CN201710521677.3A CN201710521677A CN109200769B CN 109200769 B CN109200769 B CN 109200769B CN 201710521677 A CN201710521677 A CN 201710521677A CN 109200769 B CN109200769 B CN 109200769B
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membrane
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tail gas
butane
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CN109200769A (en
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霍稳周
吕清林
刘野
李花伊
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • 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
    • B01D50/10—Combinations of devices covered by groups B01D45/00, B01D46/00 and B01D47/00
    • 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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • 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
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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Abstract

The tail gas treatment method in the process of preparing maleic anhydride by butane oxidation comprises the steps of separating the tail gas by a membrane reactor, wherein a membrane in the membrane reactor is a cellulose acetate membrane, the aperture of the membrane is 0.1-0.5 um, the inner diameter of the membrane is 0.2-1.0 mm, and the wall thickness of the membrane is 0.1-1.0 mm; before use, the product is soaked in low carbon alcohol and treated with inert gas or nitrogen in three stages. According to the tail gas treatment method, the special treatment membrane reactor is utilized, so that small molecular polymer impurities in the membrane component are removed, the pore size distribution of the membrane component is more uniform, effective components and impurities in the tail gas can be effectively separated, and the enrichment of butane components in the residual gas is facilitated; the invention also has the advantages of low equipment investment cost, long service cycle, simple operation and low energy consumption.

Description

Method for treating tail gas in process of preparing maleic anhydride by butane oxidation
Technical Field
The invention relates to a method for treating tail gas generated in the process of preparing maleic anhydride by butane oxidation.
Background
Maleic anhydride (maleic anhydride, MA), also known as maleic anhydride, is an extremely important organic chemical raw material, and the consumption is second only to that of phthalic anhydride and acetic anhydride. Maleic anhydride has wide application, and is mainly used for producing series fine chemicals such as Unsaturated Polyester Resin (UPR), 1, 4-Butanediol (BDO), coating resin, bismaleimide, Tetrahydrofuran (THF), gamma-butyrolactone, maleic acid, tetrahydroanhydride and the like, and raw materials of textile printing and dyeing auxiliaries, lubricating oil additives, medicines, food additives and the like. Among the most important uses of maleic anhydride are the production of UPR and BDO, accounting for about 41.7% and 17.4% of the total consumption, respectively. The annual output of the maleic anhydride reaches about 800kt in China, and is increased by 5 times compared with 2000. The newly increased capacity is nearly 400kt/a by the end of 2014.
The production process route of maleic anhydride can be divided into a phthalic anhydride by-product method, a benzene oxidation method and C according to raw materials44 olefin oxidation methods and n-butane oxidation methods. The yield of the maleic anhydride by-product of the phthalic anhydride device is very limited, and only accounts for 5 percent of the yield of the phthalic anhydride by-product, and the maleic anhydride produced by taking benzene as a raw material through catalytic oxidation accounts for most of the yield of the maleic anhydride before the 60 th of the 20 th century. But the benzene catalytic oxidation process causes serious pollution to the environment, and the utilization rate and the price of the benzene are lowThe technology for producing maleic anhydride by using cheap and low-pollution raw materials is becoming a hot point of attention.
In the early 60 s of the 20 th century, low-cost C began to be utilized4The research on the new process for producing the maleic anhydride by using the fraction (mainly containing n-butene) as the raw material, but the development of the technology is delayed because the dehydrogenation process belongs to an endothermic reaction and a large number of byproducts are generated. In 1974, Monsanto and Texas oil companies in the United states succeeded in producing maleic anhydride from n-butane on the basis of the original benzene production plant, and subsequently, Hakang (Halcon) and scientific design and technology (SD) companies in the United states developed a novel catalyst and production technology for producing maleic anhydride by oxidation of n-butane, so that a novel technology for producing maleic anhydride by oxidation of n-butane was developed more rapidly.
The reaction rate constant for the oxidation of n-butane to maleic anhydride was K = 11.44X 105exp (-7180/T), and studies showed that the reaction rate was changed in the presence of a catalyst (VO)2P2O7One V atom in the (020) plane of the phase forms a bond with the ligand cavity and the other V atom forms a bond with the O atom providing allyl activity, since V2O2 and P2OX combine to form (VO)2P2O7When, the structure lacks an O atom, the result is (VO)2P2O7(020) The structure of the crystal face is deformed to force the V-O position to reverse or adjust the bond strength, and a high-activity V-V ion pair is formed through coordination chemical reaction. The bond distance V-V is 0.333nm, corresponding exactly to C in n-butane1And C3Bond distance between atom and H atom, thus illustrating (VO) in the catalyst2P2O7Against the action of n-butane and V2O5-P2OXThe interaction between them.
In the production process of preparing maleic anhydride by butane oxidation, the conversion rate of n-butane is about 82 percent, the tail gas contains 18 percent of unreacted n-butane, and the unreacted n-butane is separated from the tail gas from the viewpoint of recycling and reducing the consumption of raw materials and is recycled to a reaction system. However, the tail gas also contains components such as carbon monoxide, acrylic acid, acetic acid, solvent and the like, which belong to toxic, corrosive, flammable and explosive media. If tail gas does not have fine processing, get into the air-blower entry, recycle contains media such as water, acid in the tail gas, will cause the corruption to equipment such as the leaf of air-blower, seriously influences the operation safety of device.
In the production of maleic anhydride by butane oxidation, the tail gas separation and normal butane recovery method comprises an absorption method, a condensation method, an adsorption method and the like: 1) absorption method: the absorption method is a method for treating the exhaust gas by utilizing the characteristic that the exhaust gas is dissolved in a special solvent (or a solution added with a chemical agent); 2) condensation method: for high-content tail gas, the tail gas can be passed through a condenser, the available gas can be reduced to be below the boiling point, and the tail gas can be condensed into liquid for recycling; 3) an adsorption method: adsorption is a process for removing impurities from a tail gas by using certain porous solids (adsorbents) having the ability to selectively adsorb certain components from a gas-phase mixture. Currently, the most common adsorbents used for treating impurities in tail gas are activated carbon and activated carbon fiber, and the used device is a valve switching type two-bed (or multi-bed) adsorber.
Chemical industry and engineering technology, 2006, volume 23, No. 4, reports a tail gas treatment technology for producing maleic anhydride through n-butane oxidation, tail gas for producing maleic anhydride through butane oxidation is treated by a thermal combustion type oxidizer method, the main body of the tail gas treatment technology is an incinerator, the incinerator comprises a combustor, a mixing section, a combustion section and an exhaust section, and a waste heat boiler is arranged to recover heat to generate steam. The method is a treatment method for tail gas generated in the preparation of maleic anhydride by butane oxidation, and does not achieve the aim of recycling.
The petrochemical technology and application reported in No. 32, No. 1 of 2014 that the tail gas of the maleic anhydride production process by the n-butane oxidation method is recycled, and the principle of the tail gas recycling process is to separate impurities such as solvent, acrylic acid, acetic acid, water and the like carried in the tail gas of a reaction absorption tower through the working procedures such as cooling, separation, washing and the like so as to recover unreacted n-butane. The method has complex process and high production cost, and can generate a large amount of washing waste liquid to pollute the environment.
In conclusion, the method in the prior art generally has the defects of complex process and high production cost, the butane purification rate is low, and a technical scheme for separating and treating the tail gas generated in the preparation of maleic anhydride by butane oxidation by using 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 in the prior art in the tail gas produced by preparing maleic anhydride through butane oxidation, the invention aims to provide the method for treating the tail gas produced by preparing the maleic anhydride through butane oxidation, a membrane component is treated by a specific means, the operation conditions are controlled to separate the tail gas, and the separated tail gas is separated to obtain a butane component with higher purity 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 in a process of preparing maleic anhydride by butane oxidation, which 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 0.5MPa to 1.5MPa, the temperature is 50 ℃ to 100 ℃, and the air inlet speed is 0.5m/s to 3.0m/s, so as to obtain the permeation gas rich in carbon monoxide, propionic acid, acetic acid, solvent and water vapor and the residual gas rich in butane gas and nitrogen;
wherein, the membrane in the membrane reactor is a cellulose acetate membrane, the aperture of the membrane is 0.1 um-0.5 um, the inner diameter is 0.2 mm-1.0 mm, and the wall thickness is 0.1 mm-1.0 mm;
the membrane reactor is treated before use by:
low carbon alcohol is first soaked at 50-200 deg.c for 4-24 hr and then inert gas or nitrogen is introduced in three stages at the pressure of 0.5-1.0 MPa, temperature of 50-80 deg.c and flow rate of 1m3/h-5m3H; the conditions of introducing inert gas or nitrogen in the second stage are that the pressure is 0.8MPa-1.0MPa, the temperature is 60-80 ℃, and the flow speed is 3m3/h-5m3H; the third stage is fed with inert gas or nitrogen under the conditions of pressure of 1.0MPa-1.5MPa, temperature of 90-100 deg.C and flow rate of 6m3/h-8m3/h。
In the above treatment method, it should be understood by those skilled in the art that the tail gas from the oxidation of butane to maleic anhydride contains unreacted butenes, which can be recycled for reproduction, but also contains impurities such as water, carbon monoxide, nitrogen, oxygen, carbon dioxide, acetic acid, propionic acid, maleic anhydride, etc., and the content of each component in the tail gas varies depending on the respective process differences, so that the treatment method of the present invention is particularly suitable for the treatment method of the tail gas with the following impurity contents, in order to make those skilled in the art more fully understand the present invention: by weight, the water content is 1.5-5.0%, the carbon monoxide content is 0.1-5.0%, the nitrogen content is 60.0-75.0%, the oxygen content is 5.0-20.0%, the carbon dioxide content is 0.5-5.5%, the acetic acid content is 0.001-0.5%, the propionic acid content is 0.001-0.10%, the maleic anhydride content is 0.001-0.1%, and the balance is butane. Among them, more preferred are: by weight, the water content is 1.5-3.0%, the carbon monoxide content is 0.5-3.0%, the nitrogen content is 65.0-70.0%, the oxygen content is 10.0-15.0%, the carbon dioxide content is 0.5-3.5%, the acetic acid content is 0.001-0.30%, the propionic acid content is 0.001-0.02%, the maleic anhydride content is 0.001-0.05%, and the balance is butane. It should be noted that the tail gas with the above composition is treated by the method of the present invention, so as to obtain more ideal separation results, and the butane content in the separated gas meets the requirement of the recycling production as raw material, and the impurities therein are basically removed without affecting the process reaction, which is not the tail gas with the composition outside the present composition is not suitable for the treatment 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 0.02 mu m, so that the content of micro-dust in the treated tail gas is less than or equal to 0.02mg/Nm3And the water content is less than or equal to 3 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 50 ℃ to 90 ℃, and the temperature is preferably 50 ℃ to 80 ℃; the air intake speed is 0.5m/s to 2.0m/s, wherein the air intake speed is more preferably 0.5m/s to 1.5 m/s.
In the above treatment method, as a further preferable mode, the lower alcohol is selected from C1-C7Preferably C, at least one of normal or isomeric alcohols1-C4More preferably C1-C3At least one of normal alcohols or isomeric alcohols.
In the above treatment method, as a further preference, the soaking condition using a lower alcohol is preferably a soaking condition at a temperature of 50 ℃ to 150 ℃ for 12 hours to 24 hours.
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, a tail gas inlet is arranged at one end of the shell in parallel with the membrane component, a residual gas seepage outlet is arranged at the other end of the shell in parallel with the membrane component, and a seepage gas outlet is arranged on the side surface of the shell.
After the tail gas is treated, permeation gas rich in carbon monoxide, propionic acid, acetic acid, solvent and water vapor and residual permeation gas rich in butane gas and nitrogen are obtained, the residual permeation gas is returned to the butane oxidation stage to be used as a raw material, and the permeation gas can further recover each component.
Compared with the prior art, the tail gas treatment method for the device for preparing maleic anhydride by butane oxidation has the following advantages:
1. the invention removes the micromolecule polymer impurities in the membrane component by soaking the membrane reactor with low carbon alcohol under specific conditions and treating with inert gas or nitrogen by stages, so that the pore size distribution of the membrane component is more uniform, and the enrichment of butane component in the residual gas is more facilitated.
2. Compared with other processes, the method for treating the tail gas generated in the preparation of maleic anhydride by butane oxidation has the advantages of low equipment investment cost, long service cycle, simplicity in operation and low energy consumption; the membrane reactor after special treatment has good gas separation selectivity and high separation efficiency, effectively removes impurities of acetic acid, propionic acid, maleic anhydride and water in tail gas, increases the content of an effective component butane in the tail gas from 1.1 to more than 1.60 percent, completely meets the requirement of directly recycling the butane as a raw material, 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 of a specific process for treating tail gas from the production of maleic anhydride by oxidation of butane, which is 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 examples, the process flow apparatus shown in FIG. 1 is used to treat the tail gas from the oxidation of butane to maleic anhydride, the normal temperature tail gas from the oxidation process of butane is first passed through a gas centrifuge 1 to primarily remove solid particles and water carried in the tail gas, then pressurized to 0.5MPa-1.0MPa by a gas booster I2, and then fed into a high pressure storage tank 3, further dewatered and dedusted by an activated carbon filter 4, and then heat exchanged by a tubular countercurrent heat exchanger 5 to make the temperature of the tail gas reach 50-80 ℃, and then removed by a precision filter 6 to remove all the tail gas with a diameter larger than 0.01 μmThe content of dust particles obtained after the solid particles of m is less than or equal to 0.01mg/Nm3The membrane entering gas with water content less than or equal to 2PPm enters the membrane reactor 7 under the conditions of pressure of 0.5MPa to 1.0MPa, temperature of 50 ℃ to 80 ℃ and air inlet speed of 0.5m/s to 3.0m/s, and the purified residual gas and the permeating gas concentrated with impurities are separated out. Wherein the residual gas is led out from the residual gas outlet through a pipeline II 15 and returned to the butane oxidation device, part of the permeation gas is returned to the activated carbon filter 4 through a pipeline I14 through a gas booster II 8 and a pipeline III 16, and the other part of the permeation gas is recovered by acrylic acid, acetic acid and solvent.
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, a tail gas inlet 9 is arranged at one end of the shell 12 in parallel with the membrane module 11, a residual gas seepage outlet 13 is arranged at the other end of the shell 12 in parallel with the membrane module 11, and a seepage gas outlet 10 is arranged on the side surface of the shell. The tail gas flows in the membrane component, the butane component as slow gas is discharged through the residual gas permeation outlet 13 along the tube pass of the membrane component, and the impurity gas as fast gas is discharged through the membrane component through the permeation gas outlet 10. The membrane component is made of cellulose acetate membrane, the membrane aperture is 0.1um-0.3um, the inner diameter is 0.4mm-0.8mm, and the wall thickness is 0.1mm-0.3 mm.
The membrane parameters used in the examples are shown in Table 1, and the composition of the butane oxidation unit off-gas used is shown in Table 2.
TABLE 1
Figure 115673DEST_PATH_IMAGE001
TABLE 2
Figure 32814DEST_PATH_IMAGE002
The percentages in the following examples are by weight unless otherwise specified.
Example 1
Taking tail gas of a butane oxidation device listed in Table 2 as a raw material, preliminarily removing solid particles and water carried in the tail gas by a gas centrifuge 1, and introducingAfter the pressure of the gas passing supercharger I2 is increased to 0.5MPa, the gas enters 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 0.005mg/Nm3And the water content is 1PPm, the tail gas temperature reaches 60 ℃ after heat exchange is carried out by a tubular countercurrent heat exchanger 5, the tail gas enters a membrane reactor 7 under the conditions of the pressure of 0.8MPa and the air inlet speed of 1.0m/s, and the residual gas rich in butane and the permeating gas containing acetic acid, propionic acid, maleic anhydride and moisture are separated. Sending the residual gas into a butane oxidation device to be used as a raw material for synthesizing maleic anhydride; the permeation gas is further removed of butane after being adsorbed by different adsorbents and is used as return gas to be pressurized and then returns to the membrane separator 7 for continuous purification; and the other part of the permeate gas is used for recovering acetic acid, propionic acid and maleic anhydride. The retentate gas composition results are shown in Table 3.
Example 2
The process of example 1 was followed except that the gas was pressurized to 0.6MPa 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 0.01mg/Nm3And the water content is 2.5PPm, the temperature of the tail gas reaches 80 ℃ after heat exchange by a countercurrent heat exchanger 5, the tail gas enters a membrane reactor 7 under the conditions of the pressure of 1.0MPa and the air inlet speed of 1.5m/s, and the residual gas rich in butane and the permeating gas containing acetic acid, propionic acid, maleic anhydride and moisture are separated. Sending the residual gas into a butane oxidation device to be used as a raw material for synthesizing maleic anhydride; the permeation gas is further removed of butane after being adsorbed by different adsorbents and is used as return gas to be pressurized and then returns to the membrane separator 7 for continuous purification; and the other part of the permeate gas is used for recovering acetic acid, propionic acid and maleic anhydride. The retentate gas composition results are shown in Table 3.
Example 3
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; the content of the micro dust in the tail gas is 0.02mg/Nm through an active carbon filter 43And the membrane inlet gas with the water content of 3PPm enters a membrane reactor 7 under the conditions that the temperature of tail gas reaches 80 ℃ after heat exchange is carried out by a countercurrent heat exchanger 5 and the pressure is 0.8MPa and the air inlet speed is 3.0m/s, so that residual gas rich in butane and permeate gas containing acetic acid, propionic acid, maleic anhydride and moisture are separated. Sending the residual gas into a butane oxidation device to be used as a raw material for synthesizing maleic anhydride; permeating gas channelAfter being adsorbed by different adsorbents, further removing butane in the adsorbents, taking the butane as return gas, pressurizing the return gas and returning the return gas to the membrane separator 7 for continuous purification; and the other part of the permeate gas is used for recovering acetic acid, propionic acid and maleic anhydride. The retentate gas composition results are shown in Table 3.
Example 4
The membrane module 11 is subjected to the following processes: soaking the membrane component 11 in isopropanol at 50 deg.C for 12h, introducing nitrogen gas at three stages, wherein the nitrogen gas is introduced at 80 deg.C under 0.5MPa at 5m flow rate3H; the second stage is fed with nitrogen under the conditions of 0.8MPa of pressure, 60 ℃ of temperature and 3m of flow speed3H; the nitrogen is introduced into the third stage under the conditions of 1.5MPa of pressure, 100 ℃ of temperature and 8m of flow speed3And h, purifying butane oxidation tail gas after treatment.
The membrane module after the above treatment was used for off-gas treatment according to the method of example 1. The retentate gas composition results are shown in Table 3.
Example 5
The procedure of example 4 was followed except that isopropanol was changed to ethanol and the composition of the retentate gas is shown in Table 3.
Example 6
The procedure of example 4 was followed except that isopropanol was changed to n-butanol, and the composition of retentate gas is shown in Table 3.
Example 7
The procedure of example 4 was followed except that isopropanol was changed to octanol and the composition of the retentate gas is shown in Table 3.
Example 8
The membrane module 11 is subjected to the following processes: soaking the membrane module in ethanol at 80 deg.C for 12h, introducing nitrogen gas in three stages, wherein the nitrogen gas is introduced at 80 deg.C under 1.0MPa at 5m flow rate3H; the second stage is fed with nitrogen under the conditions of 0.8MPa of pressure, 60 ℃ of temperature and 3m of flow speed3H; the nitrogen is introduced into the reactor at 100 deg.C under 1.5MPa and 6m3And h, purifying butane oxidation tail gas after treatment.
The membrane module after the above treatment was used for off-gas treatment according to the method of example 1. The retentate gas composition results are shown in Table 3.
Example 9
The procedure of example 8 was followed except that ethanol was changed to sec-butanol and the composition of the retentate gas is shown in Table 3.
Example 10
The procedure of example 8 was followed except that ethanol was changed to methanol and the composition of the retentate gas was as shown in Table 3.
Example 11
The membrane module 11 is subjected to the following processes: soaking the membrane module in methanol at 50 deg.C for 24h, introducing nitrogen gas in three stages, wherein the nitrogen gas is introduced at 80 deg.C under 1.0MPa at 5m flow rate3H; the second stage is fed with nitrogen under the conditions of pressure of 0.8MPa, temperature of 80 deg.C and flow rate of 3m3H; the nitrogen is introduced into the third stage under the conditions of 1.5MPa of pressure, 100 ℃ of temperature and 8m of flow speed3And h, purifying butane oxidation tail gas after treatment.
The membrane module after the above treatment was used for off-gas treatment according to the method of example 1. The retentate gas composition results are shown in Table 3.
Example 12
The procedure of example 11 was followed except that methanol was changed to ethanol and the composition of the retentate gas was as shown in Table 3.
Example 13
The procedure of example 11 was followed except that methanol was changed to isopropanol and the composition of the retentate gas was as shown in Table 3.
Example 14
The procedure of example 11 was followed except that methanol was changed to butanol and the composition of the retentate gas was as shown in Table 3.
As can be seen from Table 3, after the tail gas of the butane oxidation device is refined by the membrane separator which is not pretreated, the content of effective components butane in the tail gas is about 1.1%, and the tail gas still contains a small amount of impurities such as acetic acid, propionic acid, maleic anhydride and the like, and after the tail gas is refined by the membrane separator which is pretreated, the impurities such as acetic acid, propionic acid, maleic anhydride and water in the tail gas are effectively removed, the content of the effective components butane in the tail gas is more than 1.60%, and the tail gas can be completely used as a raw material for a section for synthesizing maleic anhydride, so that the requirement of recycling is met.
TABLE 3
Figure 314016DEST_PATH_IMAGE004

Claims (8)

1. The method for treating tail gas in the process of preparing maleic anhydride by butane oxidation 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 0.5MPa to 1.5MPa, the temperature is 50 ℃ to 100 ℃, and the air inlet speed is 0.5m/s to 3.0m/s, so as to obtain the permeation gas rich in carbon monoxide, propionic acid, acetic acid, solvent and water vapor and the residual gas rich in butane gas and nitrogen;
wherein the membrane in the membrane reactor is a cellulose acetate membrane, the aperture of the membrane is 0.1-0.5 μm, the inner diameter is 0.2-1.0 mm, and the wall thickness is 0.1-1.0 mm;
the membrane reactor is treated before use by:
low carbon alcohol is first soaked at 50-200 deg.c for 4-24 hr and then inert gas or nitrogen is introduced in three stages at the pressure of 0.5-1.0 MPa, temperature of 50-80 deg.c and flow rate of 1m3/h-5m3H; the conditions of introducing inert gas or nitrogen in the second stage are that the pressure is 0.8MPa-1.0MPa, the temperature is 60-80 ℃, and the flow speed is 3m3/h-5m3H; the third stage is fed with inert gas or nitrogen under the conditions of pressure of 1.0MPa-1.5MPa, temperature of 90-100 deg.C and flow rate of 6m3/h-8m3/h。
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 50 ℃ to 90 ℃, and the air inlet speed is 0.5m/s to 2.0 m/s.
3. The process according to claim 1, characterized in that the lower alcohol is selected from C1-C7At least one of normal alcohols or isomeric alcohols.
4. The process according to claim 3, characterized in that the lower alcohol is selected from C1-C4At least one of normal alcohols or isomeric alcohols.
5. The treatment method according to claim 3 or 4, wherein the soaking with the lower alcohol is carried out at a temperature of 50 ℃ to 150 ℃ for 12 hours to 24 hours.
6. The treatment method according to claim 1, wherein the dehydration and dust removal are carried out so that the content of the micro dust in the treated tail gas is less than or equal to 0.02mg/Nm3And the water content is less than or equal to 3 ppm.
7. The process according to claim 1, characterized in that the composition of the off-gas is: by weight, the water content is 1.5-5.0%, the carbon monoxide content is 0.1-5.0%, the nitrogen content is 60.0-75.0%, the oxygen content is 5.0-20.0%, the carbon dioxide content is 0.5-5.5%, the acetic acid content is 0.001-0.5%, the propionic acid content is 0.001-0.10%, the maleic anhydride content is 0.001-0.1%, and the balance is butane.
8. The process according to claim 7, characterized in that the composition of the off-gas is: by weight, the water content is 1.5-3.0%, the carbon monoxide content is 0.5-3.0%, the nitrogen content is 65.0-70.0%, the oxygen content is 10.0-15.0%, the carbon dioxide content is 0.5-3.5%, the acetic acid content is 0.001-0.30%, the propionic acid content is 0.001-0.02%, the maleic anhydride content is 0.001-0.05%, and the balance is butane.
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JPH0747222A (en) * 1993-08-04 1995-02-21 Nitto Denko Corp Method for treating exhaust gas containing organic vapor
CN106673962A (en) * 2015-11-09 2017-05-17 中国石油化工股份有限公司 Preparation method of isopropanol
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
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0747222A (en) * 1993-08-04 1995-02-21 Nitto Denko Corp Method for treating exhaust gas containing organic vapor
CN106673962A (en) * 2015-11-09 2017-05-17 中国石油化工股份有限公司 Preparation method of isopropanol
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
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

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