WO2016058400A1 - 一种含挥发性有机物尾气净化工艺 - Google Patents

一种含挥发性有机物尾气净化工艺 Download PDF

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Publication number
WO2016058400A1
WO2016058400A1 PCT/CN2015/081356 CN2015081356W WO2016058400A1 WO 2016058400 A1 WO2016058400 A1 WO 2016058400A1 CN 2015081356 W CN2015081356 W CN 2015081356W WO 2016058400 A1 WO2016058400 A1 WO 2016058400A1
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Prior art keywords
solvent
tower
absorption
recovery
volatile organic
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PCT/CN2015/081356
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English (en)
French (fr)
Inventor
张兵
李建明
阮杰
张春璐
安喜报
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天津奥展兴达化工技术有限公司
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Priority claimed from CN201410550131.7A external-priority patent/CN104357096B/zh
Priority claimed from CN201510016096.5A external-priority patent/CN104524929A/zh
Application filed by 天津奥展兴达化工技术有限公司 filed Critical 天津奥展兴达化工技术有限公司
Publication of WO2016058400A1 publication Critical patent/WO2016058400A1/zh

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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
    • B01D53/14—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 absorption
    • 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
    • B01D53/14—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 absorption
    • B01D53/18—Absorbing units; Liquid distributors therefor

Definitions

  • the invention belongs to the technical field of chemical industry and relates to one or more kinds of organic exhaust gas including acetone, methanol, ethanol, benzene, toluene, xylene, butanol and butyl ester in the fields of coal chemical industry, oil refining, petrochemical industry, fine chemical industry and pharmaceutical industry. Purification and recycling, especially related to a highly efficient and energy-saving purification process of volatile organic compounds.
  • Industrial waste gas is an important source of atmospheric pollutants.
  • the discharge of a large amount of industrial waste gas into the atmosphere will inevitably degrade the quality of the atmospheric environment and cause serious harm to human health.
  • the most difficult to deal with in industrial waste gas is organic waste gas.
  • organic waste gas After entering the human body through the respiratory tract and skin, organic waste gas can cause temporary and permanent damage to human respiratory and blood, liver and other systems and organs, especially benzopyrene polycyclic.
  • Aromatic hydrocarbons can cause direct carcinogenesis in human body and have attracted the attention of human beings.
  • various organic waste gases are produced, mainly including various hydrocarbons, alcohols, aldehydes, acids, ketones and amines. These organic waste gases cause air pollution, endanger human health, and cause waste. Therefore, the treatment and purification of organic waste gas is imperative.
  • the emission control of volatile organic compounds is an important project in environmental protection.
  • end control there are three common methods.
  • the first is the recycling process.
  • the main method is condensation, adsorption-pressure conversion. , adsorption-hot air regeneration, adsorption-steam regeneration, adsorption-chemical regeneration;
  • second adsorption-based treatment process, including adsorption-recycling regeneration, adsorption-disposal (critical waste);
  • the third method is destruction
  • the main scheme the main processes used are: TO direct combustion, RTO regenerative combustion, RCO regenerative catalytic combustion, SQU resonance quantum synergy, JETI jet ion, ACP atmospheric glow plasma.
  • the problem to be solved by the invention is to provide a solvent absorption and regeneration process that can be used to remove volatile organic compounds in the exhaust gas efficiently, and to recycle the absorbent by an energy-saving process.
  • the technical solution adopted by the present invention is to provide a process for purifying a volatile organic-containing exhaust gas: the tail gas to be treated is introduced into the segmented absorption tower from the bottom of the tower, and the exhaust gas is removed by solvent absorption to remove volatile organic compounds; The exhaust gas continues to rise and is removed by the water to remove the volatile solvent and/or the solvent entrained in the exhaust gas to obtain a purified exhaust gas.
  • the purification process further includes a solvent and water recycling step, and the solvent and water recovery and reuse steps include:
  • the recovered solvent and the recovered water discharged after the absorption step are mixed, and then the regenerated solvent and the regenerated water are obtained by rectification and standing stratification;
  • the recovered solvent and the recovered water discharged after the absorption step are subjected to rectification to obtain a regenerated solvent and reclaimed water.
  • the regenerated solvent and the reclaimed water are separately recycled into the segmented absorption tower for reuse.
  • the purification process further comprises a step of re-absorption of volatile organic compounds, and the volatile organic compounds not condensed into a liquid state are added to the multi-stage absorption tower for reabsorption.
  • the solvent comprises one or more of N-methylpyrrolidone, N-ethylpyrrolidone, N-formylmorpholine, dimethyl sulfoxide, sulfolane, propylene carbonate, ionic liquid or ⁇ -pyrrolidone.
  • the solvent is a mixed solvent of N-methylpyrrolidone and N-formylmorpholine
  • the mass ratio of the mixture of N-methylpyrrolidone and N-formylmorpholine is 1:99 to 99:1.
  • the ionic liquid refers to a molten salt which exhibits a liquid state at or near room temperature, and is composed of a specific organic cation and an inorganic anion or an organic anion.
  • the ionic liquid may be a quaternary ammonium salt, a quaternary phosphonium ion, or an imidazolium salt.
  • the solvent absorption step is a multi-stage absorption mode.
  • the plurality of segments can be two segments, three segments or more.
  • the multi-stage absorption method can be used for targeted segmentation of volatile organic compounds of different nature in the exhaust gas, and further can be used for the solvent list after absorption. Recycling alone reduces the difficulty of recycling energy and subsequent separation.
  • the purified gas is produced at the top of the staged absorption tower, the mixture of volatile organic compounds and solvent is produced on the side of the column and/or the side of the column, and the mixture of water and solvent is produced on the side line of the column.
  • the operating environment in the segmented absorption tower is normal temperature and normal pressure, and the liquid-gas ratio (V/V) in the column operating condition. ) is 1: (800-3000), the purified gas with volatile organic content ⁇ 0.8mg/m 3 is produced at the top of the tower, the mixture of volatile organic compounds and solvent is produced in the tower, and the mixture of water and solvent is produced on the side line of the tower. .
  • the solvent absorption section may be 2-5 segments. For example, it is 2, 3, 4, and 5.
  • the purification process can be used for gas purification, and the solvent absorption step is two-stage absorption.
  • the gas enters the segmented absorption tower from the bottom of the column, and the gas is removed by the first solvent to remove naphthalene, naphthalene homologs and other highs.
  • the gas after the first absorption is continued to enter the second stage of the absorption tower, and then the solvent is absorbed to remove benzene and its homologues, phenol and polyphenol; After the second stage of absorption, the gas continues to rise and is absorbed by the water to remove the volatilized and/or entrained solvent in the gas, and finally the purified gas is obtained.
  • the purified gas is obtained.
  • each of the absorbed solvents is separately recovered.
  • the first recovered solvent after the first stage absorption in the segmented absorption tower enters a first recovery column (for example, a reduced pressure dividing wall distillation column), and the first solvent is recovered.
  • the operating pressure of the column is 0.01-0.09MPA
  • the temperature of the column is 180-230 ° C
  • the temperature at the top of the column is 40-90 ° C
  • the production temperature of the side line is 150-210 ° C
  • the top of the column is produced with benzene, phenol and low boiling point (such as boiling point).
  • Impurities and water below 100 ° C, naphthalene and high boiling point (for example, boiling point higher than 250 ° C) impurities are collected at the bottom of the tower, and a solvent having a purity of ⁇ 99.5% is produced in the middle of the column.
  • the segmented absorption tower enters a second recovery column (for example, a reduced pressure dividing wall distillation column) through the second recovered solvent in the second stage, and the second recovery tower
  • the operating pressure is 0.01-0.05MPA
  • the temperature of the column is 150-210°C
  • the temperature at the top of the column is 40-90°C
  • the reflux ratio is 0.1-5.0.
  • the top of the column is extracted with impurities such as benzene and homologues, phenol and polyphenols.
  • the kettle produced a solvent with a purity of ⁇ 99.5%.
  • the water after absorption of the segmented absorption tower enters a third recovery column (for example, a vacuum distillation column), and the operating pressure of the third recovery column is 0.01- 0.09MPA, the temperature of the column is 150-210 ° C, the temperature at the top of the column is 40-90 ° C, the reflux ratio is 0.1-5.0, the water at the top of the column is ⁇ 99.5%, and the solvent at the bottom of the column is ⁇ 99.5%.
  • a third recovery column for example, a vacuum distillation column
  • the operating pressure of the third recovery column is 0.01- 0.09MPA
  • the temperature of the column is 150-210 ° C
  • the temperature at the top of the column is 40-90 ° C
  • the reflux ratio is 0.1-5.0
  • the water at the top of the column is ⁇ 99.5%
  • the solvent at the bottom of the column is ⁇ 99.5%.
  • the present invention also provides a volatile organic-containing exhaust gas purification treatment apparatus comprising a segmented absorption tower, the segmented absorption tower comprising a water absorption section located above the tower and a solvent absorption section located below the water absorption section .
  • the purification apparatus further includes a storage tank and a recovery tower, and the recovery water outlet and the recovery solvent outlet of the sectional absorption tower are connected to the storage tank through a transmission pipeline, and the storage tank is connected by the transmission pipeline
  • the recovery tower is provided with a phase separation tank at the top outlet of the recovery tower, and the transmission pipeline is correspondingly provided with a pump and a heat exchanger.
  • the purification device further includes a storage tank and a recovery tower, and the recovery solvent outlet of the sectional absorption tower is sequentially connected to the first storage tank and the first recovery tower through a transmission pipeline, and is processed by the first recovery tower.
  • the recovery solvent outlet of the sectional absorption tower is sequentially connected to the first storage tank and the first recovery tower through a transmission pipeline, and is processed by the first recovery tower.
  • Obtaining a volatile organic substance and a regenerating solvent wherein the recovered water outlet of the segmented absorption tower is sequentially connected to the second storage tank and the second recovery tower through a transfer pipeline, and the recycled water and the regenerated solvent are obtained after being processed by the second recovery tower, Corresponding pumps and heat exchangers are provided on the transfer line.
  • the regeneration solvent and the reclaimed water are respectively recycled into the segmented absorption tower through a transmission pipe for recycling.
  • the purification apparatus further includes a gas-liquid separator and a compressor, the gas-liquid separator and a phase separation tank or a recovery tower containing a volatile organic substance are connected through a pipeline, the compressor and the segmented absorption tower and the gas-liquid respectively
  • the gas ports of the separator are connected by a transfer line.
  • the gas-liquid separator is used for separating volatile organic compounds which are condensed into a liquid state and which are not condensed into a liquid state.
  • the compressor increases the volatile organic compounds which are not condensed into a liquid state, and then transports them to a multi-stage absorption tower through a transmission pipe to be absorbed.
  • the gas-liquid separator may be a gas-liquid separator conventional in the art, or may be a heat exchanger as long as it can realize the liquid The separation of the body and the gas is sufficient.
  • the solvent absorption section is multi-stage
  • the water absorption section adopts a high efficiency low resistance tray
  • the recovery column is a vacuum distillation column.
  • the recovery solvent outlet may be one or more, for example, 1-5, specifically 1, 2, 3, 4, 5; when the recovery solvent outlet is one, it is located The tower tank of the segmented absorption tower; when the recovery solvent outlet is plural, it is located below the corresponding solvent absorption section.
  • the recovery solvent outlet is plural, a plurality of storage tanks and a plurality of recovery towers may be correspondingly included.
  • a heat exchanger may be externally connected between each adjacent two-stage solvent absorption section.
  • the segmented absorption tower may comprise a filler, which may be a granular, honeycomb, spherical, porous filler of metal, plastic or ceramic, such as corrugated board, wire mesh, orifice plate, spherical lightweight ceramic General fillers such as grain, quartz sand, Raschig ring, Pall ring, triple Y ring, conjugate ring, 84 inner arc ring, flat ring, saddle ring, step ring and so on.
  • a filler which may be a granular, honeycomb, spherical, porous filler of metal, plastic or ceramic, such as corrugated board, wire mesh, orifice plate, spherical lightweight ceramic General fillers such as grain, quartz sand, Raschig ring, Pall ring, triple Y ring, conjugate ring, 84 inner arc ring, flat ring, saddle ring, step ring and so on.
  • the invention has the advantages and positive effects: Compared with the prior art, the invention has the advantages of providing an efficient and energy-saving process for purifying and recovering volatile organic compounds.
  • the invention can recycle and reuse volatile organic compounds in the exhaust gas instead of burning or decomposing, and achieve the discharge standard of the gas; remove the generated heat in time during the absorption process, improve the absorption effect, and improve the heat reuse; solvent recovery
  • the energy consumption of the tower is much lower than that of catalytic combustion, regenerative combustion, activated carbon desorption and other processes.
  • the absorption solvent can be recycled, and it is chemically stable, non-toxic, non-corrosive and easy to recycle. The pollution caused by the discharge of the solvent into the air is reduced.
  • the absorbed solvent is recovered by the recycling process of the present invention and can be recycled, and the raw material consumption is reduced in industrial production; the condensed liquid is not condensed at the outlet end of the recovery tower.
  • the reabsorption of organic matter further reduces the air pollution caused by volatile organic compounds.
  • FIG. 1 is a schematic structural view of a process equipment created by the present invention
  • FIG. 2 is a schematic structural view of another process equipment created by the present invention.
  • FIG 3 is a schematic view of the mechanism of a process apparatus created by the present invention.
  • T101, T111 and T121 are absorption towers
  • T102, T112 ⁇ T113 and T122 ⁇ T124 are recovery towers
  • E101 ⁇ E105, E111 ⁇ E117 and E121 ⁇ E130 are all The heat exchanger
  • P101 ⁇ P102, P111 ⁇ P114 and P121 ⁇ P125 are all pumps
  • V101 ⁇ V104, V111 ⁇ V114 and V121 ⁇ V123 are all storage tanks.
  • Volatile organic compounds in the context of the present invention represent compounds having a boiling point of from 50 to 250 ° C, saturated vapor pressures exceeding 133.32 Pa at room temperature, and a class of organic substances present in the form of vapors in air at ambient temperature, including alkanes and aromatic hydrocarbons. And alkenes, halocarbons, esters, aldehydes, ketones and the like, for example, benzene series, organic chlorides, freon series, organic ketones, amines, alcohols, ethers, esters, acids and petroleum hydrocarbon compounds.
  • the tail gas discharge of a pharmaceutical company contains butyl acetate (immiscible with water). According to the needs of the subsequent work section, the butyl acetate in the tail gas should be removed to below 10 mg/m 3 , and the quality of n-butyl acetate in the raw material tail gas. The score is ⁇ 1%;
  • the inhalation temperature of the gas to be treated is 25 ° C, and the content of n-butyl acetate in the liquid of the absorption tower is ⁇ 1%;
  • the raw material exhaust gas enters the absorption tower T101 from the raw material inlet of the bottom of the absorption tower, and the operating conditions of the absorption tower T101 are normal temperature and normal pressure operation, and the solvent for purifying the exhaust gas passes through the upper end of the absorption tower packing 2
  • the supplementary solvent pipeline enters the absorption tower T101, and the water enters from the inlet pipe located at the upper end of the packing 1 of the absorption tower T101, and is in reverse contact with the raw material exhaust gas in the absorption tower T101, and the metal mesh corrugated packing is used in the tower, and the liquid-gas ratio of the working condition is (V: V) 1: 800-1000 (wherein the absorption tower is a three-stage packing, the packing 2 and the packing 3 in the column are both butyl acetate-depleted segments, and the filler 1 is a solvent-free section);
  • the purified gas is taken out through the purified gas outlet at the upper end of the absorption tower T101, and the butyl acetate content in the purified gas is 7 mg/m 3 ;
  • the recovered solvent is taken out from the recovery solvent outlet at the lower part of the absorption tower T101, and the recovered water is taken out from the side line of the recovery water outlet in the middle of the absorption tower T101, and the recovered solvent and the recovered water are mixed into the storage tank V101 through the pipeline and then passed through the pipeline.
  • the distillation column T102 is subjected to vacuum distillation.
  • the operation temperature of the recovery tower T102 is 155 ° C, the top of the column is 42 ° C, the operating pressure is 0.01 MPA (A), the reflux ratio is 1, and the solvent and water are recovered from the middle of the column.
  • the number of theoretical plates of the recovery tower T102 is 15 (the 8th feed), and the wire mesh is corrugated high.
  • the filler is mixed with butyl acetate and water at the top of the tower.
  • the mixture enters the phase separation tank V102 and is allowed to stand for separation. After stratification, the water is returned to the absorption tower T101 for recycling.
  • the butyl acetate is collected and the mass fraction of the tower is mass fraction. >99.5% of solvent, the solvent is exchanged with the feed of the recovery tower T102 through the heat exchanger E102, and is returned to the absorption tower T101 for recycling after heat exchange.
  • the process and equipment are suitable for a system in which the organic matter and the water contained in the raw material exhaust gas are not miscible, and the recycled water and the recovery solvent are mixed, the treatment efficiency is high, and the equipment investment is effectively reduced.
  • the solvent is dissolved in the solvent of the absorption tower, causing a portion of the non-condensable gas at the outlet of the recovery tower and/or the phase separation tank, and the gas is partially entrapped with liquefied butyl acetate.
  • the liquid separator and the compressor connect the gas-liquid separator with the recovery tower and/or the phase separation tank through a pipeline, wherein the gas-liquid separator can also be a heat exchanger (the gas-liquid separator and the recovery shown in FIG. 1)
  • the tower is connected, the gas-liquid separator is a heat exchanger, and the non-condensable gas is taken out from the upper end of the heat exchanger.
  • the compressor is connected to the gas ports of the segmented absorption tower and the gas-liquid separator respectively through a transmission pipeline.
  • the gas-liquid separator is used to condense the separation into a liquid and non-condensed volatile organic matter.
  • the compressor increases the volatile organic compounds that are not condensed into a liquid, and then transports them through a transmission pipe to a multi-stage absorption tower for absorption.
  • the gas source for treatment is the same as in Example 1.
  • the absorption solvent is N-methylpyrrolidone and N-formylmorpholine, and the mixture is mixed at a mass ratio of 1:1 to prepare a mixed solvent to purify the tail gas, and the gas to be treated has a suction temperature of 28 ° C.
  • the content of butyl acetate in the liquid of the absorption tower is ⁇ 1%;
  • Toluene and xylene are contained in the exhaust gas of a chemical enterprise. According to the emission requirements, the toluene and xylene in the tail gas should be removed to 10 mg/m 3 , and the mass fraction of toluene and xylene in the raw material tail gas is ⁇ 1%;
  • the inhalation temperature of the gas to be treated is 25 ° C, and the toluene and xylene content in the liquid of the absorption tower is ⁇ 1%;
  • the raw material exhaust gas enters the absorption tower T101 from the raw material inlet 1 at the bottom of the tower, and sucks
  • the condition of the tower T101 is normal temperature and normal pressure operation
  • the solvent for purifying the tail gas enters the absorption tower T101 through the supplementary solvent conduit 2 located at the upper end of the absorption tower packing 6, and the water enters from the inlet pipe 3 at the upper end of the packing 5 of the absorption tower T101.
  • the raw material exhaust gas is reversely contacted, and the wire mesh corrugated packing is used in the tower, and the working condition liquid-gas ratio is (V:V) 1:1200-1500 (in which the packing 6 and the packing 7 in the absorption tower are both Detoluene, xylene section, the filler is the desolvation section 5);
  • the purified gas is collected through the purified gas outlet 4 at the upper end of the absorption tower T101, and the toluene and xylene content in the purified gas is 8 mg/m 3 ;
  • the recovered solvent is recovered from the recovered solvent outlet 7 at the lower portion of the absorption tower T101, and the recovered water is recovered from the recovered water outlet 8 in the middle of the absorption tower T101, and the recovered solvent and the recovered water are passed through the pipeline to the recovery tower T102 for vacuum distillation.
  • the distillation column T102 tower is operated at a temperature of 156 ° C, the top of the column is 40 ° C, the operating pressure is 0.01 MPA (A), the reflux ratio is 1.5, and the recovered solvent is fed from the middle of the column.
  • the number of theoretical plates is 15 (the eighth feed)
  • the wire mesh corrugated high-efficiency filler is used, the top of the tower is toluene, xylene and water.
  • the water is returned to the absorption tower for recycling, toluene xylene is collected, and the column kettle is >99.5% solvent and the T102 feed is passed.
  • the heat exchanger performs heat exchange and returns to the absorption tower for recycling after heat exchange.
  • the treatment gas source is the same as in the third embodiment, the absorption solvent is N-methylpyrrolidone and N-formylmorpholine, and the mixture is mixed at a mass ratio of 3:1 to prepare a mixed solvent to purify the tail gas, and the gas to be treated has a suction temperature of 28 ° C.
  • the content of toluene and xylene in the liquid of the absorption tower is ⁇ 1%;
  • Exhaust gas from a chemical company contains methanol and acetone (miscible with water), and the absorption solvent is N-methylpyrrolidone and N-formylmorpholine.
  • the mixture is mixed at a mass ratio of 5:1 to prepare a mixed solvent to purify the tail gas.
  • the gas to be treated has a suction temperature of 32 ° C, and the methanol and acetone content in the absorption tower liquid is ⁇ 1%;
  • the raw material exhaust gas enters the absorption tower T111 from the raw material inlet of the bottom of the absorption tower, and the operating conditions of the absorption tower T111 are normal temperature and normal pressure operation, and the solvent for purifying the exhaust gas passes through the upper end of the absorption tower packing 5.
  • the supplementary solvent pipe enters the absorption tower T111, and the water enters from the inlet pipe at the upper end of the packing 4 of the absorption tower T111, in the absorption tower T111 is in reverse contact with the raw material exhaust gas, and the wire mesh corrugated packing is used in the tower.
  • the working condition liquid-gas ratio is (V:V) 1:800-1000 (in which the absorption tower is a two-stage packing, the middle and lower packing in the tower) 5 is to remove the methanol and acetone segments, and the middle and upper filler 4 in the column is a solvent removal section);
  • the equipment shown in Fig. 2 is used for recycling and reuse, and the recovered solvent is taken out from the recovery solvent outlet at the lower part of the absorption tower, and is recycled to the recovery tower T112 through a pipeline, and the regenerated solvent is regenerated.
  • the bottom of the recovery tower T112 is recovered and reused through the pipeline from the supplementary solvent inlet to the absorption tower T111.
  • the recovered water is taken from the side line of the absorption tower T111 through the pipeline into the recovery tower T113 for vacuum distillation, and the reclaimed water is produced from the top of the T113.
  • the water pipe enters the absorption tower T113 for recycling and reuse, and the regenerated solvent is collected from the bottom of the T113 through the pipeline from the supplemental solvent inlet to the absorption tower T113 for recycling (at the same time, in order to meet the equipment requirements, the recovered water, the recovered solvent, the reclaimed water and the regenerated solvent are also needed.
  • a corresponding storage tank, pump and heat exchanger are added to the pipeline).
  • the recovered methanol, acetone and water in the above process are mutually soluble, so it is necessary to use a plurality of recovery towers for solvent recovery and reuse.
  • the solvent in the segmented absorption tower T111 dissolves the air, causing a portion of the non-condensable gas at the outlet of the recovery tower T112/T 113, and the gas contains a portion of the unliquefied volatile organic compounds, thus setting a gas-liquid separator and a compressor, the gas-liquid separator is connected to the recovery tower T112 and/or T113 (shown in FIG. 2 to be connected to T112 and T113) through a pipeline, the compressor and the segmented absorption tower T111 and the gas-liquid respectively The gas ports of the separator are connected by a transfer line. The gas-liquid separator is used to condense the separation into a liquid and non-condensed volatile organic matter.
  • the compressor increases the volatile organic compounds that are not condensed into a liquid, and then transports them through a transmission pipe to a multi-stage absorption tower for absorption.
  • a gas-liquid separator and a compressor By providing a gas-liquid separator and a compressor, the volatile organic substances in the collected liquid which may be entrained in the gas are transported to the absorption tower for further recovery treatment, thereby reducing environmental pollution.
  • the coking coal gas of a coking plant contains impurities such as aromatic hydrocarbons. According to the needs of the subsequent sections, the aromatics in the gas should be removed to 3 mg/m 3 .
  • the mass fraction of the main components in the raw gas is as follows:
  • the raw material gas enters the absorption tower T121 from the raw material inlet 16 at the bottom of the tower, and the conditions of the absorption tower T121 are normal temperature and normal pressure operation, and the solvent for purifying the gas is dispersed by the supplementary solvent conduit 12, respectively From the upper end of the first section of the absorption tower (ie, the deparaffinization section 15) and the second section (ie, the dearomatization section 14), the absorption tower T121 is entered, and the water enters from the upper end of the third section (ie, the desolvation section 13), in the absorption tower T121.
  • the wire mesh corrugated packing is used in the tower, and the ratio of liquid to gas in the working condition is 1:600-700;
  • the purified gas is collected through the purified gas outlet 17 at the upper end of the absorption tower T121, and the aromatic hydrocarbon content in the purified gas is 1.6 mg/m 3 , wherein benzene 15 PPM, toluene, xylene, naphthalene, phenol and polyphenol are ⁇ 5 PPM;
  • the first recovered solvent is recovered from the first recovery solvent outlet 20 located at the bottom of the absorption tower T121 and is recycled to the first solvent recovery tower (for the dividing wall distillation column) T122 through a pipeline, and the column reactor operation of the dividing wall distillation column T122
  • the temperature is 181 ° C
  • the top of the tower is 40 ° C
  • the middle part of the tower is 158 ° C
  • the operating pressure is 0.01 MPA (A)
  • the first recovered solvent is fed from the middle of the column
  • the number of theoretical plates of the dividing wall distillation column T122 is 30 (the 9th feed)
  • the wire mesh corrugated high-efficiency filler is used, a small amount of benzene, phenol and low-boiling impurities and water are collected at the top of the tower, the column is a small amount of naphthalene and high-boiling impurities, and the solvent in the middle of the tower is 99.5% of the solvent and the partition wall distillation.
  • the second recovered solvent is recovered from the second recovery solvent outlet 19 located at the lower portion of the second section of the absorption tower T121, and is passed through the pipeline to the second solvent recovery tower (for the dividing wall distillation column) T123 for regeneration, and the distillation column T123 is operated by the column.
  • the temperature is 158 ° C
  • the top of the tower is 42 ° C
  • the operating pressure is 0.015 MPA (A)
  • the reflux ratio is 1
  • the second recovered solvent is fed from the middle of the column
  • the theoretical number of plates is 10 (the fifth feed)
  • the wire mesh is used.
  • the top of the column is benzene and homologue, phenol and polyphenol, 99.5% solvent in the column reactor and the feed solvent of the rectification column T123 (ie the second recovery solvent) are exchanged through the heat exchanger E124;
  • the pure water enters the absorption tower T121 through the supplementary water pipe 11 located at the upper portion of the third section of the absorption tower T121, and the recovered water after 4-5 times is taken out from the recovered water outlet 18 located at the lower portion of the third section of the absorption tower T121.
  • the distillation tower T124 tower kettle operating temperature is 165 ° C
  • the top of the tower is 43 ° C
  • the operating pressure is 0.015 MPA (A)
  • the reflux ratio is 0.4
  • the water is fed from the middle of the tower
  • the theoretical number of plates 15 (the eighth block feed) is made of wire mesh corrugated high-efficiency filler.
  • the tower is a solvent with a purity of 99.5%.
  • the top of the column is 99.55% pure water and the distillation tower T124 feed water is exchanged.
  • the absorption of the granule is compared with the absorption by the targeted segmentation, the amount of the solvent is small, and the low-boiling impurities of the impurities in the solvent are separated from the high-boiling impurities, thereby reducing the energy consumption for recovery and improving Economic applicability.
  • the solvent in the segmented absorption tower T121 dissolves the air, causing a portion of the non-condensable gas at the outlet of the recovery tower T122, T123 or T124, and the gas contains a portion of the unliquefied volatile organic matter.
  • the gas-liquid separator and the compressor are arranged, and the gas-liquid separator is connected to the recovery tower through a pipeline, and the compressor is respectively connected to the gas passage of the segmented absorption tower T121 and the gas-liquid separator through a transmission pipeline.
  • the gas-liquid separator is used to condense the separation into a liquid and non-condensed volatile organic matter.
  • the compressor increases the volatile organic compounds that are not condensed into a liquid, and then transports them through a transmission pipe to a multi-stage absorption tower for absorption.
  • a gas-liquid separator and a compressor By providing a gas-liquid separator and a compressor, the volatile organic substances in the collected liquid which may be entrained in the gas are transported to the absorption tower for further recovery treatment, thereby reducing environmental pollution.
  • the gas source for treatment is the same as in Example 6.
  • the absorption solvent is ⁇ -pyrrolidone and N-formylmorpholine, and the mixture is mixed at a mass ratio of 2:1 to prepare a mixed solvent to purify the coking gas, and the gas to be treated has a suction temperature of 28 ° C.
  • the aromatics content in the absorption tower liquid is ⁇ 0.2%;
  • the first solvent recovery tower T122 the temperature of the tower is 201 ° C, the temperature of the top of the tower is 58 ° C, the temperature of the measuring line is 190 ° C, the operating pressure is 0.05 MPA (A), and other operating conditions are the same as in the sixth embodiment;
  • the gas source for treatment is the same as in Example 6.
  • the absorption solvent is ⁇ -pyrrolidone and N-methylpyrrolidone, and the mixture is mixed at a mass ratio of 1:90 to prepare a mixed solvent for purifying the coking gas.
  • the gas to be treated is inhaled at a temperature of 28 ° C and absorbed.
  • the aromatics content in the liquid of the tower is ⁇ 0.2%;
  • the first solvent recovery tower T122 the temperature of the tower is 210 ° C, the temperature of the top of the tower is 71 ° C, the temperature of the line is 198 ° C, the operating pressure is 0.07 MPA (A), and other operating conditions are the same as in the embodiment 6;
  • the gas source for treatment is the same as in Example 6.
  • the absorption solvent is ⁇ -pyrrolidone, N-methylpyrrolidone and N-formylmorpholine, and the mixture is mixed at a mass ratio of 1:1:1 to prepare a mixed solvent for purifying the coking gas.
  • the treatment gas suction temperature is 28 ° C, and the aromatic hydrocarbon content in the absorption tower liquid is ⁇ 0.2%;
  • Example 10 Comparison test of acetic acid-containing tail gas absorption
  • the tail gas treatment process of the first embodiment of the invention is used to purify the tail gas containing the acetate, and the tail gas enters the absorption tower T101 from the raw material inlet of the bottom of the absorption tower, and the absorption tower T101 operates.
  • the conditions are normal temperature and normal pressure operation, and the solvent for purifying the tail gas enters the absorption tower T101 through the supplementary solvent pipeline located at the upper end of the absorption tower packing 2, and the water enters from the inlet pipe located at the upper end of the packing 1 of the absorption tower T101, in the absorption tower T101.
  • the wire mesh corrugated packing is used in the tower, and the liquid-gas ratio is 1:800-1000 in the working condition; the purified gas is taken out through the purified gas outlet at the upper end of the absorption tower T101;
  • the exhaust gas enters the absorption tower T101 from the raw material inlet of the bottom of the absorption tower, and the operating conditions of the absorption tower T101 are normal temperature and normal pressure operation, and the solvent for purifying the exhaust gas enters the absorption tower T101 through the supplementary solvent pipeline located at the upper end of the absorption tower packing 2,
  • the raw material exhaust gas is reversely contacted, and the metal mesh corrugated packing is used in the tower, and the working condition liquid-gas ratio is 1:800-1000; the purified gas is collected through the purified gas outlet at the upper end of the absorption tower T101;
  • the purified gas treated by 2) or 3) is taken out at a flow rate of 0-500 mL/min through a gas sampler, and adsorbed by a solvent-type activated carbon adsorption tube, and then detected by a gas chromatograph (Northern SP-3420A).
  • the chromatographic conditions were as follows: oven temperature 60 ° C, temperature rise to 100 ° C at 4 ° C / min, hold for 2 min, vaporization chamber temperature 180 ° C, detector temperature 180 ° C; detection standard: GBZT 160.63-2007 workplace air toxic substances determination Saturated aliphatic ester compounds.
  • the removal rate can reach 99.99%. It can be seen that after the tail gas is subjected to the water absorption step, the solvent entrained in the exhaust gas is absorbed, on the one hand, the pollution caused by the solvent being discharged into the air is reduced, and on the other hand, the absorbed solvent is recovered by the recycling process of the invention, and can be recycled. In industrial production, the consumption of raw materials is reduced.
  • the gas after treatment (treated by water) using the exhaust gas purifying device of the present invention has an ester substance removal rate of more than 99.8% and a high purification efficiency.
  • Example 11 Comparison test of tail gas absorption of high boiling point solvents including esters, alcohols, ketones and the like
  • the chromatographic detection conditions are: oven temperature 80 ° C, hold for 2 min, heat up to 100 ° C at 5 ° C / min, then increase to 10 ° C / min to 220 ° C, hold 10 min, vaporization chamber temperature 250 ° C, detector temperature 250 °C; test standard: GBZT 160.48-2007 workplace air toxic substances determination of alcohol compounds, GBZT 160.42-2007 workplace air toxic substances determination of aromatic hydrocarbon compounds, GBZT 160.63-2007 workplace air toxic substances determination of saturated aliphatic esters The compound; the remaining operating conditions were the same as in Example 10.
  • Table 3 Comparison of natural gas tail gas containing tetrahydrothiophene by water absorption/non-water absorption comparison test:
  • the PCT of the present application is disclosed in Chinese.
  • some differences may be caused due to different ways of processing the characters in different languages, but these differences should not be the reason for affecting the scope of the present invention.
  • all differences in translation caused by specific or non-specific, singular or plural are within the scope of protection of the present invention.

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Abstract

一种含挥发性有机物尾气的净化工艺及设备，将待处理尾气从塔底进入分段式吸收塔（T101、T111、T121）内，尾气经溶剂吸收脱除挥发性有机物；尾气继续上升经水吸收脱除挥发的和/或尾气中夹带的溶剂，得到净化尾气；该设备包括分段式吸收塔（T101、T111、T121），该吸收塔（T101、T111、T121）包括位于塔内上方的水吸收段和位于水吸收段下方的溶剂吸收段。

Description

一种含挥发性有机物尾气净化工艺 技术领域
本发明属于化工技术领域，涉及煤化工、炼油、石油化工、精细化工、制药等领域中含丙酮、甲醇、乙醇、苯、甲苯、二甲苯、丁醇、丁酯等一种或者多种有机尾气的净化回收利用，尤其是涉及一种高效节能的挥发性有机物尾气的净化回收工艺。
背景技术
大气污染是我国目前最突出的环境问题之一，工业废气是大气污染物的重要来源。大量工业废气排入大气，必然使大气环境质量下降，给人体健康带来严重危害。工业废气中最难处理的就是有机废气，有机废气通过呼吸道和皮肤进入人体后，能给人的呼吸、血液、肝脏等系统和器官造成暂时性和永久性病变，尤其是苯并芘类多环芳烃能使人体直接致癌，已经引起人类的高度重视。工业生产中会产生各种有机物废气，主要包括各种烃类、醇类、醛类、酸类、酮类和胺类等，这些有机废气会造成大气污染，危害人体健康，而且还会造成浪费，所以有机废气的处理与净化势在必行。
挥发性有机物(volatile organic compound)的排放控制是环境保护的一项重要工程，在末端控制方面，目前比较常见的做法有三种，一是回收工艺，主要采用的手段是冷凝、吸附-变压再生、吸附-热风再生、吸附-蒸汽再生、吸附-化学再生；二是以吸附为主的处理工艺，采用的方案包括吸附-回炉再生、吸附-丢弃(危废)；第三种方法是破坏为主的方案，主要采用的工艺是，TO直接燃烧、RTO蓄热燃烧、RCO蓄热催化燃烧、SQU共振量子协同、JETI射流离子、ACP大气压辉光等离子体等。
常见方法的主要优缺点汇总如下：
Figure PCTCN2015081356-appb-000001
Figure PCTCN2015081356-appb-000002
因此，需要一种更加高效节能的处理方式用来处理工业废气，脱除废气中的挥发性有机物，并尽量回收利用，进而提高人们生活环境的质量，为人们的身体健康提供保障。
发明内容
本发明创造要解决的问题是提供一种经过筛选的溶剂吸收和再生工艺，可以高效的脱除尾气中挥发性有机物，同时采用节能工艺将吸收剂再生循环利用。
为解决上述技术问题，本发明采用的技术方案是：提供一种含挥发性有机物尾气净化工艺：将待处理尾气从塔底进入分段式吸收塔内，尾气经溶剂吸收脱除挥发性有机物；尾气继续上升经水吸收脱除挥发的和/或尾气中夹带的溶剂，得到净化尾气。
优选的，所述净化工艺中还包括溶剂与水的回收再利用步骤，所述溶剂与水的回收再利用步骤包括：
将经吸收步骤后排出的回收溶剂和回收水经混合后通过精馏和静置分层的方式得到再生溶剂和再生水；
或者，将经吸收步骤后排出的回收溶剂和回收水通过精馏的方式得到再生溶剂和再生水。
优选的，所述再生溶剂和再生水分别进入所述分段式吸收塔中循环再利用。
优选的，所述净化工艺中还包括挥发性有机物尾气的再吸收步骤，将未凝结成液态的挥发性有机物加入多段式吸收塔中再吸收。
优选的，所述溶剂包括N-甲基吡咯烷酮、N-乙基吡咯烷酮、N-甲酰吗啉、二甲基亚砜、环丁砜、碳酸丙烯酯、离子液或α-吡咯烷酮中的一种或多种。更优选的，当溶剂为N-甲基吡咯烷酮和N-甲酰吗啉的混合溶剂时，N-甲基吡咯烷酮和N-甲酰吗啉的混合质量比为1:99～99:1。所述离子液是指在室温或接近室温下呈现液态的融盐，由特定的有机阳离子和无机阴离子/或有机阴离子构成，例如离子液可为季铵盐离子、季磷盐离子、咪唑盐离子、吡啶盐离子、卤素离子、四氟硼酸根离子、六氟磷酸根离子等。
优选的，所述溶剂吸收步骤为多段式的吸收方式。所述多段可为两段、三段或更多。采用多段式吸收方式，可对尾气中不同性质的挥发性有机物进行针对性分段吸收，进一步可对吸收后的溶剂单 独回收处理，降低回收能耗、后续分离的难度。
优选的，在分段式吸收塔的塔顶采出净化气，塔釜和/或塔侧线采出挥发性有机物和溶剂的混合液，塔侧线采出水和溶剂的混合液。
在一个具体的实施方式中，当溶剂吸收步骤为单段式吸收时，优选的，所述的分段式吸收塔内的操作环境为常温常压，塔内工况液气比(V/V)为1:(800-3000)，塔顶采出挥发性有机物含量≤0.8mg/m3的净化气，塔釜采出挥发性有机物和溶剂的混合液，塔侧线采出水和溶剂的混合液。
在一个具体的实施方式中，当溶剂吸收步骤为多段式吸收时，相应溶剂吸收段的下方采出挥发性有机物和溶剂的混合液，具体的，所述溶剂吸收段可为2-5段，例如为2，3，4，5段。
优选的，所述净化工艺可用于煤气净化，溶剂吸收步骤为两段式吸收，首先煤气从塔底进入分段式吸收塔，煤气经第一段溶剂吸收脱除萘、萘同系物及其它高沸点(例如沸点高于250℃)的重杂质；然后经过第一段吸收后的煤气继续进入吸收塔第二段，再经溶剂吸收脱除苯及其同系物、苯酚及多元酚；最后经过第二段吸收后的煤气继续上升经水吸收脱除挥发的和/或煤气中夹带的溶剂，最终得到净化煤气。第一段溶剂吸收段脱除重杂质后，避免重杂质与第二段溶剂吸收段混合后不好分离，降低了第二段溶剂吸收段分离的难度和能耗。
更优选的，对每段吸收后的溶剂单独回收处理。
在一个具体的实施方式中，所述的分段式吸收塔中经第一段吸收后的第一回收溶剂进入第一回收塔(例如，减压间壁精馏塔)，所述第一溶剂回收塔操作压力为0.01-0.09MPA，塔釜温度为180-230℃，塔顶温度为40-90℃，侧线采出温度为150-210℃，塔顶采出苯、苯酚及低沸点(例如沸点低于100℃)杂质和水，塔底采出萘及高沸点(例如沸点高于250℃)杂质，塔中部采出纯度≥99.5％的溶剂。
在一个具体的实施方式中，所述的分段式吸收塔经中第二段吸收后的第二回收溶剂进入第二回收塔(例如，减压间壁精馏塔)，所述第二回收塔的操作压力0.01-0.05MPA，塔釜温度为150-210℃，塔顶温度为40-90℃，回流比为0.1-5.0，塔顶采出苯及同系物、苯酚及多元酚等杂质，塔釜采出纯度≥99.5％的溶剂。
在一个具体的实施方式中，所述的分段式吸收塔经水吸收后的回收水进入第三回收塔(例如：减压精馏塔)，所述第三回收塔的操作压力为0.01-0.09MPA，塔釜温度为150-210℃，塔顶温度为40-90℃，回流比为0.1-5.0，塔顶采出纯度≥99.5％的水，塔釜采出纯度≥99.5％的溶剂。
本领域技术人员知晓，当溶剂吸收段的数量继续增加时，可以相应的增加回收塔的数量；本领域技术人员也可以理解，对每段吸收后的溶剂单独回收处理的优点是：在处理含不同性质的挥发性有机物的尾气时，能够减少回收能耗、降低后续分离的难度。本领域技术人员同样可以知晓，即使溶剂吸收段为多段，也可将吸收后的溶剂通过一个回收溶剂出口采出，进入一个回收塔进行处理。
此外，本发明还提供一种含挥发性有机物尾气净化处理设备，包括分段式吸收塔，所述分段式吸收塔包括位于塔内上方的水吸收段和位于水吸收段下方的溶剂吸收段。
优选的，所述净化设备还包括储料罐和回收塔，所述分段式吸收塔的回收水出口和回收溶剂出口通过传输管道连接储料罐，所述储料罐通过传输管道连接所述回收塔，所述回收塔的塔顶输出口处设有分相罐，所述传输管道上相应的设有泵和换热器。
优选的，所述净化设备还包括储料罐和回收塔，所述分段式吸收塔的回收溶剂出口通过传输管道依次连接第一储料罐和第一回收塔，经第一回收塔处理后得到挥发性有机物和再生溶剂，所述分段式吸收塔的回收水出口通过传输管道依次连接第二储料罐和第二回收塔，经第二回收塔处理后得到再生水和再生溶剂，所述传输管道上相应的设有泵和换热器。
优选的，所述再生溶剂和再生水通过传输管道分别进入所述分段式吸收塔中循环再利用。
所述净化设备还包括气液分离器和压缩机，所述气液分离器与分相罐或含挥发性有机物的回收塔通过管路相连，所述压缩机分别与分段式吸收塔和气液分离器的气体端口通过传输管道相连。所述气液分离器用于分离凝结成液态和未凝结成液态的挥发性有机物，所述压缩机将未凝结成液态的挥发性有机物增加后通过传输管道输送至多段式吸收塔中再吸收。在具体的实施方式中，气液分离器可为本领域常规的气液分离器，也可为换热器，只要其能够实现将液 体和气体的分离即可。
优选的，所述溶剂吸收段为多段式；
和/或，所述水吸收段采用高效低阻力塔盘；
和/或，所述回收塔为减压精馏塔。
优选的，当溶剂吸收段为多段式时，回收溶剂出口可为一个或多个，例如1-5，具体可为1，2，3，4，5；当回收溶剂出口为一个时，其位于分段式吸收塔的塔釜处；当回收溶剂出口为多个时，其位于相应溶剂吸收段的下方。本领域技术人员可以知晓，当回收溶剂出口为多个时，也可相应的包括多个储料罐和多个回收塔。
优选的，当溶剂吸收段为多段式时，每相邻两段溶剂吸收段之间可外接一换热器。
优选的，所述分段式吸收塔可包括填料，所述填料可以是金属、塑料或陶瓷的粒状、蜂窝状、球形、多孔填料，例如波纹板、金属丝网、孔板、球形轻质陶粒、石英砂、拉西环、鲍尔环、三Y环、共轭环、八四内弧环、扁环、矩鞍环、阶梯环等通用填料。
本发明创造具有的优点和积极效果是：与现有技术相比，本发明创造的优点在于提供一种高效节能含挥发性有机物尾气净化、回收工艺。本发明能将尾气中的挥发性有机物回收再利用，而不是燃烧或者分解，并且使气体达到排放标准；吸收过程中及时取走生成的热量，提高吸收效果，并提高热量的再利用；溶剂回收塔的能耗要远低于催化燃烧、蓄热燃烧、活性炭脱附等工艺的能耗，吸收溶剂可循环使用，且化学性质稳定、无毒、无腐蚀性、易回收；通过水吸收一方面减少了溶剂排放到空气中造成的污染，另一方面，吸收的溶剂经本发明回收工艺回收，可以循环利用，在工业生产中，减少原料消耗；对回收塔出口端的未凝结成液态的挥发性有机物再吸收，进一步降低了挥发性有机物对空气造成的污染。
附图说明
图1是本发明创造的一种工艺设备的结构示意图；
图2是本发明创造的另一种工艺设备的结构示意图；
图3是本发明创造的还一种工艺设备的机构示意图。
图中：T101、T111和T121为吸收塔，T102、T112～T113和T122～T124均为回收塔，E101～E105、E111～E117和E121～E130均为 换热器，P101～P102、P111～P114和P121～P125均为泵，V101～V104、V111～V114和V121～V123均为储料罐。
具体实施方式
本发明上下文中挥发性有机物(VOCs)表示沸点在50-250℃的化合物，室温下饱和蒸气压超过133.32Pa，在常温下以蒸气形式存在于空气中的一类有机物，包括烷类、芳烃类、烯类、卤烃类、酯类、醛类、酮类等，例如：苯系物、有机氯化物、氟里昂系列、有机酮、胺、醇、醚、酯、酸和石油烃化合物等。
本发明上下文中“储料罐”和“回收塔”前的“第一”、“第二”、“第三”仅用于区分“储料罐”和“回收塔”的数量，并不用于限定或区分“储料罐”和“回收塔”的结构。
下面结合附图及具体实施方式对本发明作进一步说明。
实施例1：
1)某制药企业尾气排放中含有醋酸丁酯(与水不互溶)，根据后续工段的需要，需将尾气中的醋酸丁酯脱除至10mg/m3以下，原料尾气中醋酸正丁酯质量分数为＜1％；
2)采用N-甲基吡咯烷酮为溶剂，净化该尾气，待处理气体的吸入温度为25℃，入吸收塔液体中醋酸正丁酯含量＜1％；
3)如图1所示，原料尾气从吸收塔底部的原料进气口进入吸收塔T101中，吸收塔T101操作条件为常温、常压操作，净化尾气用的溶剂通过位于吸收塔填料2上端的补充溶剂管道进入吸收塔T101中，水从位于吸收塔T101填料1上端的进水管道进入，在吸收塔T101中与原料尾气逆向接触，塔内采用金属丝网波纹填料，工况液气比为(V:V)1:800-1000(其中吸收塔为三段式填料，塔内填料2与填料3均为脱醋酸丁酯段，填料1为脱溶剂段)；
4)净化后的气体通过吸收塔T101上端的净化气出口采出，净化气中醋酸丁酯含量为7mg/m3；
5)回收溶剂从吸收塔T101下部的回收溶剂出口采出，回收水从吸收塔T101中部的回收水出口侧线采出，回收溶剂和回收水一起通过管道进入储料罐V101混合后再通过管道进入到回收塔T102进行减压精馏，回收塔T102的塔釜操作温度为155℃，塔顶为42℃，操作压力0.01MPA(A)，回流比为1，回收溶剂和水从塔中部进料，回收塔T102的理论板数为15(第8块进料)，采用金属丝网波纹高 效填料，塔顶采出醋酸丁酯和水的混合物，该混合物进入分相罐V102静置分层，分层后水返回至吸收塔T101循环使用，醋酸丁酯进行收集，塔釜为质量分数＞99.5％的溶剂，该溶剂与回收塔T102的进料通过换热器E102进行换热，换热后返回至吸收塔T101循环使用。该工艺与设备适用于原料尾气中所含有机物与水不互溶的体系，将回收水与回收溶剂混合处理，处理效率高，有效降低设备投资。
在一个具体的实施方式中，吸收塔的溶剂中会溶解空气，导致回收塔和/或分相罐出口处有部分不凝气体，气体中夹带有部分未液化的醋酸丁酯，因此，设置气液分离器和压缩机，将气液分离器与回收塔和/或分相罐通过管路相连，其中，气液分离器也可为换热器(图1所示为气液分离器与回收塔相连，气液分离器为换热器，不凝气体从换热器末端上部接出)，压缩机分别与分段式吸收塔和气液分离器的气体端口通过传输管道相连。气液分离器用于将分离凝结成液态和未凝结成液态的挥发性有机物，压缩机将未凝结成液态的挥发性有机物增加后通过传输管道输送至多段式吸收塔中再吸收。通过设置气液分离器和压缩机，将收集液中有可能夹带在气体中的挥发性有机物输送至吸收塔中进一步回收处理，降低了对环境的污染。
实施例2：
1)处理气源同实施例1，吸收溶剂为N-甲基吡咯烷酮与N-甲酰吗啉，按质量比1:1进行混合，制备混合溶剂净化该尾气，待处理气体吸入温度28℃，入吸收塔液体中醋酸丁酯含量＜1％；
2)净化后出吸收塔的净化气体中醋酸丁酯含量降低到5mg/m3以下；
3)回收塔T102，塔釜温度171℃，塔顶温度45℃，回流比4，操作压力0.03MPA(A)，其他操作条件与实施例1相同。
实施例3：
1)某化工企业尾气排放中含有甲苯、二甲苯，根据排放要求，需将尾气中的甲苯、二甲苯脱除至10mg/m3，原料尾气中甲苯、二甲苯质量分数为＜1％；
2)采用N-甲基吡咯烷酮为溶剂，净化该尾气，待处理气体的吸入温度为25℃，入吸收塔液体中甲苯、二甲苯含量＜1％；
3)原料尾气从塔底部的原料进气口1进入吸收塔T101中，吸 收塔T101条件为常温、常压操作，净化尾气用的溶剂通过位于吸收塔填料6上端的补充溶剂管道2进入吸收塔T101中，水从位于吸收塔T101的填料5上端的进水管道3进入，在吸收塔T101中与原料尾气逆向接触，塔内采用金属丝网波纹填料，工况液气比为(V:V)1:1200-1500(其中吸收塔内的填料6与填料7均为脱甲苯、二甲苯段，填料为脱溶剂段5)；
4)净化后的气体通过吸收塔T101上端的净化气出口4采出，净化气中甲苯、二甲苯含量为8mg/m3；
5)回收溶剂从吸收塔T101下部的回收溶剂出口7采出，回收水从吸收塔T101中部的回收水出口8采出，回收溶剂和回收水一起通过管道进入到回收塔T102进行减压精馏，精馏塔T102塔釜操作温度为156℃，塔顶40℃，操作压力0.01MPA(A)，回流比为1.5，回收溶剂从塔中部进料，理论板数15(第8块进料)，采用金属丝网波纹高效填料，塔顶为甲苯、二甲苯和水，分层后水返回至吸收塔循环使用，甲苯二甲苯进行收集，塔釜为＞99.5％的溶剂与T102的进料通过换热器进行换热，换热后返回至吸收塔循环使用。
实施例4：
1)处理气源同实施例3，吸收溶剂为N-甲基吡咯烷酮与N-甲酰吗啉，按质量比3:1进行混合，制备混合溶剂净化该尾气，待处理气体吸入温度28℃，入吸收塔液体中甲苯、二甲苯含量＜1％；
2)净化后出吸收塔的净化气体中甲苯、二甲苯含量降低到8mg/m3以下；
3)回收塔T102，塔釜温度183℃，塔顶温度58℃，回流比2，操作压力0.04MPA(A)，其他操作条件与实施例1相同。
实施例5：
1)某化工企业尾气排放中含有甲醇、丙酮(与水互溶)，吸收溶剂为N-甲基吡咯烷酮与N-甲酰吗啉，按质量比5:1进行混合，制备混合溶剂净化该尾气，待处理气体吸入温度32℃，入吸收塔液体中甲醇、丙酮含量＜1％；
2)如图2所示，原料尾气从吸收塔底部的原料进气口进入吸收塔T111中，吸收塔T111操作条件为常温、常压操作，净化尾气用的溶剂通过位于吸收塔填料5上端的补充溶剂管道进入吸收塔T111中，水从位于吸收塔T111的填料4上端的进水管道进入，在吸收塔 T111中与原料尾气逆向接触，塔内采用金属丝网波纹填料，工况液气比为(V:V)1:800-1000(其中吸收塔为两段式填料，塔内的中下部的填料5为脱除甲醇、丙酮段，塔内的中上部填料4为脱溶剂段)；
3)净化后出吸收塔的净化气体中甲醇、丙酮含量降低到8mg/m3以下；
4)由于回收的甲醇、丙酮与水互溶，故采用图2所示设备回收再利用，回收溶剂从吸收塔下部的回收溶剂出口采出，经管道进入回收塔T112减压精馏，再生溶剂从回收塔T112底部采出经管道由补充溶剂入口进入吸收塔T111回收再利用，回收水从吸收塔T111侧线采出经管道进回收塔T113减压精馏，由T113顶部采出再生水经管道由进水管道进入吸收塔T113回收再利用，由T113底部采出再生溶剂经管道由补充溶剂入口进入吸收塔T113回收再利用(同时，为了满足设备需要还需要在回收水、回收溶剂、再生水和再生溶剂的管道上加设相应的储料罐、泵和换热器)。
上述工艺中的回收的甲醇、丙酮与水互溶，因此需要采用多个回收塔进行溶剂回收再利用。
在一个具体的实施方式中，分段式吸收塔T111中的溶剂会溶解空气，导致回收塔T112/T 113出口处有部分不凝气体，气体中夹带有部分未液化挥发性有机物，因此，设置气液分离器和压缩机，将气液分离器与回收塔T112和/或T113(图2所示为与T112和T113连接)通过管路相连，压缩机分别与分段式吸收塔T111和气液分离器的气体端口通过传输管道相连。气液分离器用于将分离凝结成液态和未凝结成液态的挥发性有机物，压缩机将未凝结成液态的挥发性有机物增加后通过传输管道输送至多段式吸收塔中再吸收。通过设置气液分离器和压缩机，将收集液中有可能夹带在气体中的挥发性有机物输送至吸收塔中进一步回收处理，降低了对环境的污染。
实施例6：
1)某焦化厂焦化煤气含有芳烃等杂质，根据后续工段的需要，需将煤气中的芳烃脱除至3mg/m3，原料煤气中主要组分质量分数如下：
H2:12％，N2:14％，O2:3％，CO:15％，CO2:10％，CH4:35％，苯:3％，甲苯:2％，二甲苯:1％，萘:1％，苯酚及多元酚1％；
2)采用N-甲基吡咯烷酮和N-甲酰吗啉按质量比1:1进行混合， 制备混合溶剂作为吸收剂净化该焦化煤气，待处理气体的吸入温度为25℃，入吸收塔液体中芳烃含量＜0.2％；
3)如图3所示，原料煤气从塔底部的原料进气口16进入吸收塔T121中，吸收塔T121条件为常温、常压操作，净化煤气用的溶剂通过补充溶剂管道12分散后，分别从吸收塔第一段(即脱萘段15)和第二段(即脱芳烃段14)上端进入吸收塔T121中，水从第三段(即脱溶剂段13)上端进入，在吸收塔T121中与原料煤气逆向接触，塔内采用金属丝网波纹填料，工况液气比为1:600-700；
4)净化后的气体通过吸收塔T121上端的净化气出口17采出，净化气中芳烃含量1.6mg/m3，其中苯15PPM，甲苯、二甲苯、萘、苯酚及多元酚均＜5PPM；
5)第一回收溶剂从位于吸收塔T121底部的第一回收溶剂出口20采出通过管道进入到第一溶剂回收塔(为间壁精馏塔)T122再生，该间壁精馏塔T122的塔釜操作温度为181℃，塔顶40℃，塔中部158℃，操作压力0.01MPA(A)，第一回收溶剂从塔中部进料，间壁精馏塔T122理论板数为30(第9块进料)，采用金属丝网波纹高效填料，塔顶采出少量苯、苯酚及低沸点杂质和水，塔釜为少量萘及高沸点杂质，塔中部测线采出纯度为99.5％的溶剂与间壁精馏塔T122的进料溶剂(即第一回收溶剂)通过换热器E121进行换热；
6)第二回收溶剂从位于吸收塔T121第二段下部的第二回收溶剂出口19采出通过管道进入到第二溶剂回收塔(为间壁精馏塔)T123再生，精馏塔T123塔釜操作温度为158℃，塔顶42℃，操作压力0.015MPA(A)，回流比为1，第二回收溶剂从塔中部进料，理论板数10(第5块进料)，采用金属丝网波纹高效填料，塔顶为苯及同系物，苯酚及多元酚，塔釜为99.5％的溶剂与精馏塔T123的进料溶剂(即第二回收溶剂)通过换热器E124进行换热；
7)纯水通过位于吸收塔T121第三段上部的补充水管道11进入吸收塔T121，使用4-5次后的回收水从位于吸收塔T121第三段下部的回收水出口18采出通过管道进入到水回收塔(为普通精馏塔)T124再生，精馏塔T124塔釜操作温度为165℃，塔顶43℃，操作压力0.015MPA(A)，回流比0.4，水从塔中部进料，理论板数15(第8块进料)，采用金属丝网波纹高效填料，塔釜为纯度为99.5％的溶剂，塔顶为纯度为99.55％的水与精馏塔T124进料水通过换热器E127进行 换热；
8)三个再生回收塔回收的溶剂进行混合、冷却，再通过补充溶剂管道2送至吸收塔T121中循环使用。
另外，如附图3所示管道中还根据实际需要设有不同的泵(编号依次为P121～P125)、换热器(编号依次为E121～E130)和储罐(编号依次为V121～V123)。
以上实施例中，针对含复杂杂质的尾气，通过针对性分段吸收相比一次进行冲剂吸收，溶剂用量小，吸收后溶剂中杂质低沸点杂质与高沸点杂质分开，从而降低回收能耗，提高了经济适用性。
在一个具体的实施方式中，分段式吸收塔T121中的溶剂会溶解空气，导致回收塔T122、T123或T124出口处有部分不凝气体，气体中夹带有部分未液化挥发性有机物，因此，设置气液分离器和压缩机，将气液分离器与回收塔通过管路相连，压缩机分别与分段式吸收塔T121和气液分离器的气体端口通过传输管道相连。气液分离器用于将分离凝结成液态和未凝结成液态的挥发性有机物，压缩机将未凝结成液态的挥发性有机物增加后通过传输管道输送至多段式吸收塔中再吸收。通过设置气液分离器和压缩机，将收集液中有可能夹带在气体中的挥发性有机物输送至吸收塔中进一步回收处理，降低了对环境的污染。
实施例7：
1)处理气源同实施例6，吸收溶剂为α-吡咯烷酮与N-甲酰吗啉，按质量比2:1进行混合，制备混合溶剂净化该焦化煤气，待处理气体吸入温度28℃，入吸收塔液体中芳烃含量＜0.2％；
2)净化后出吸收塔的净化气体中芳烃及酚类含量降低到1.7mg/m3以下，其主要组成与实施例6相同；
3)第一溶剂回收塔T122，塔釜温度201℃，塔顶温度58℃，测线采出温度190℃，操作压力0.05MPA(A)，其他操作条件与实施例6相同；
4)第二溶剂回收塔T123，塔釜温度172℃，塔顶温度56℃，操作压力0.02MPA(A)，回流比0.2，其他操作条件与实施例6相同；
5)水回收塔T124，塔釜温度186℃，塔顶温度49℃，操作压力0.02MPA(A)，回流比1，其他操作条件与实施例6相同。
实施例8：
1)处理气源同实施例6，吸收溶剂为α-吡咯烷酮与N-甲基吡咯烷酮，按质量比1:90进行混合，制备混合溶剂净化该焦化煤气，待处理气体吸入温度28℃，入吸收塔液体中芳烃含量＜0.2％；
2)净化后出吸收塔的净化气体中芳烃及酚类含量降低到1.5mg/m3，其主要组成与实施例6相同；
3)第一溶剂回收塔T122，塔釜温度210℃，塔顶温度71℃，测线采出温度198℃，操作压力0.07MPA(A)，其他操作条件与实施例6相同；
4)第二溶剂回收塔T123，塔釜温度190℃，塔顶温度66℃，操作压力0.05MPA(A)，回流比3.5，其他操作条件与实施例6相同；
5)水回收塔T124，塔釜温度192℃，塔顶温度65℃，操作压力0.06MPA(A)，回流比4，其他操作条件与实施例6相同。
实施例9：
1)处理气源同实施例6，吸收溶剂为α-吡咯烷酮、N-甲基吡咯烷酮、N-甲酰吗啉，按质量比1:1:1进行混合，制备混合溶剂净化该焦化煤气，待处理气体吸入温度28℃，入吸收塔液体中芳烃含量＜0.2％；
2)净化后出吸收塔的净化气体中芳烃及酚类含量降低到1.5mg/m3，其主要组成与实施例6相同；
3)第一溶剂回收塔T122，塔釜温度228℃，塔顶温度89℃，测线采出温度208℃，操作压力0.09MPA(A)，其他操作条件与实施例6相同；
4)第二溶剂回收塔T123，塔釜温度208℃，塔顶温度82℃，操作压力0.05MPA(A)，回流比5，其他操作条件与实施例6相同；
5)水回收塔T124，塔釜温度209℃，塔顶温度88℃，操作压力0.09MPA(A)，回流比2.5，其他操作条件与实施例6相同。
实施例10：含乙酸酯类尾气吸收对比试验
1)在气体中加入含量分别为3875mg/m3的乙酸乙酯、乙酸丙酯和乙酸丁酯模拟尾气，尾气处理流量1.2m3/h，采用N-甲基吡咯烷酮为溶剂，溶剂的流量30-40mL/min；
2)尾气经水吸收：
采用本发明实施例1尾气处理工艺净化含有乙酸酯的尾气，尾气从吸收塔底部的原料进气口进入吸收塔T101中，吸收塔T101操 作条件为常温、常压操作，净化尾气用的溶剂通过位于吸收塔填料2上端的补充溶剂管道进入吸收塔T101中，水从位于吸收塔T101填料1上端的进水管道进入，在吸收塔T101中与原料尾气逆向接触，塔内采用金属丝网波纹填料，工况液气比为1:800-1000；净化后的气体通过吸收塔T101上端的净化气出口采出；
3)尾气不经水吸收(无脱溶剂段)：
尾气从吸收塔底部的原料进气口进入吸收塔T101中，吸收塔T101操作条件为常温、常压操作，净化尾气用的溶剂通过位于吸收塔填料2上端的补充溶剂管道进入吸收塔T101中，在吸收塔T101中与原料尾气逆向接触，塔内采用金属丝网波纹填料，工况液气比为1:800-1000；净化后的气体通过吸收塔T101上端的净化气出口采出；
4)经2)或3)处理的净化气经气体采样器以0-500mL/min流速采出，经溶剂型活性炭吸附管吸附后，采用气相色谱仪(北分SP-3420A)进行检测。色谱检测条件为：柱箱温度60℃，以4℃/min升温至100℃，保持2min，汽化室温度180℃，检测器温度180℃；检测标准为：GBZT 160.63-2007工作场所空气有毒物质测定饱和脂肪族酯类化合物。
检测结果参见下表1：
表1：含乙酸酯类尾气经水吸收/不经水吸收对比试验
Figure PCTCN2015081356-appb-000003
Figure PCTCN2015081356-appb-000004
由上表1的检测结果可知，尾气不经水吸收，尾气中夹带的溶剂含量高达2208mg/m3，而尾气经水吸收后，尾气中夹带的溶剂含量分别为35.7mg/m3、28.6mg/m3和24.8mg/m3，去除率可达99.99％。由此可见，尾气经水吸收步骤后，尾气中夹带的溶剂被吸收，一方面减少了溶剂排放到空气中造成的污染，另一方面，吸收的溶剂经本发明回收工艺回收，可以循环利用，在工业生产中，减少原料消耗。此外，由表1检测结果可知，采用本发明尾气净化装置处理后(经水处理)的气体，酯类物质去除率大于99.8％，净化效率高。
实施例11：含酯类、醇类、酮类等高沸点溶剂尾气吸收对比试验
1)在气体中加入含量分别为3875mg/m3的丙二醇甲醚醋酸酯、二甲苯、正丁醇、150#溶剂油(均四甲苯)、DBE(高沸点溶剂混合二元酸酯，为丁二酸二甲酯、戊二酸二甲酯、己二酸二甲酯的混合物)、异氟尔酮和乙二醇甲丁醚模拟涂料尾气，尾气处理流量1.2m3/h，采用氮甲酰吗啉为溶剂，溶剂的流量25-30mL/min；
2)操作条件与实施例10相同；
3)操作条件与实施例10相同；
4)色谱检测条件为：柱箱温度80℃，保持2min，以5℃/min升温至100℃，再以10℃/min升温至220℃，保持10min，汽化室温度250℃，检测器温度250℃；检测标准为：GBZT 160.48-2007工作场所空气有毒物质测定醇类化合物，GBZT 160.42-2007工作场所空气有毒物质测定芳香烃类化合物，GBZT 160.63-2007工作场所空气有毒物质测定饱和脂肪族酯类化合物；其余操作条件与实施例10相同。
检测结果参见下表2：
表2：涂料尾气经水吸收/不经水吸收对比试验:
Figure PCTCN2015081356-appb-000005
Figure PCTCN2015081356-appb-000006
由上表2的检测结果可知，尾气不经水吸收，尾气中夹带的溶剂含量高达507.7mg/m3，而尾气经水吸收后，尾气中未检测出溶剂，去除率大于99.99％。由此可见，尾气经水吸收步骤后，尾气中夹带的溶剂几乎完全被吸收。此外，由表2检测结果可知，采用本发明尾气净化装置处理后(经水处理)的气体，尾气中绝大部分可挥发性物质的去除率大于99％，净化效率高。
实施例12：天然气除臭对比试验
1)在天然气中加入含量为1000mg/m3的四氢噻吩，尾气处理流量0.6m3/h，采用氮甲酰吗啉为溶剂，溶剂的流量30-40mL/min；
2)操作条件与实施例10相同；
3)操作条件与实施例10相同；
4)经2)或3)处理的净化气用气体采样袋收集，采用岛津气质联用色谱仪进行检测；检测标准为：标准为ISO 19739-2004《用气相色谱法测定天然气中含硫化合物》。
检测结果参见下表3：
表3：含四氢噻吩的天然气尾气经水吸收/不经水吸收对比试验:
Figure PCTCN2015081356-appb-000007
由上表3的检测结果可知，尾气不经水吸收，尾气中夹带的溶剂含量高达2490mg/m3，而尾气经水吸收后，尾气中未检测出溶剂，去除率大于99.99％。由此可见，尾气经水吸收步骤后，尾气中夹带的溶剂几乎完全被吸收。
本申请PCT利用中文进行公开，在后续进入国家阶段进行翻译时，由于不同语言对文字的处理方式不同，会造成一些差异，但这些差异不应成为影响本发明范围的原因。比如在进行中文翻译英文时，一切因特指或不特指，单数或复数等造成的翻译差异，都属于本发明的保护范围。
尽管上面结合附图对本发明进行了描述，但是本发明并不局限于上述的具体实施方式，上述的具体实施方式仅仅是示意性的，而不是限制性的，本领域的普通技术人员在本发明的启示下，在不脱离本发明宗旨的情况下，所作的任何修改、等同替换、改进等，这些均属于本发明的保护之内。

Claims (13)

  1. 一种含挥发性有机物尾气净化工艺，其特征在于：将待处理尾气从塔底进入分段式吸收塔内，尾气经溶剂吸收脱除挥发性有机物；尾气继续上升经水吸收脱除挥发的和/或尾气中夹带的溶剂，得到净化尾气。
  2. 根据权利要求1所述的含挥发性有机物尾气净化工艺，其特征在于：所述净化工艺中还包括溶剂与水的回收再利用步骤，所述溶剂与水的回收再利用步骤包括：
    将经吸收步骤后排出的回收溶剂和回收水经混合后通过精馏和静置分层的方式得到再生溶剂和再生水；
    或者，将经吸收步骤后排出的回收溶剂和回收水通过精馏的方式得到再生溶剂和再生水。
  3. 如权利要求2所述的含挥发性有机物尾气净化工艺，其特征在于：所述净化工艺中还包括挥发性有机物尾气的再吸收步骤，将未凝结成液态的挥发性有机物加入多段式吸收塔中再吸收。
  4. 根据权利要求1-3任一项所述的含挥发性有机物尾气净化工艺，其特征在于：所述溶剂包括N-甲基吡咯烷酮、N-乙基吡咯烷酮、N-甲酰吗啉、二甲基亚砜、环丁砜、碳酸丙烯酯、离子液或α-吡咯烷酮中的一种或多种。
  5. 根据权利要求1-4任一项所述的含挥发性有机物尾气净化工艺，其特征在于：所述溶剂吸收步骤为多段式的吸收方式，优选的，为2-5段，更优选的，为2段。
  6. 根据权利要求1-5任一项所述的含挥发性有机物尾气净化工艺，其特征在于：在分段式吸收塔塔顶采出净化气，塔釜和/或塔侧线采出挥发性有机物和溶剂的混合液，塔侧线采出水和溶剂的混合液。
  7. 一种含挥发性有机物尾气净化设备，其特征在于：包括分段式吸收塔，所述分段式吸收塔包括位于塔内上方的水吸收段和位于水吸收段下方的溶剂吸收段。
  8. 根据权利要求7所述的含挥发性有机物尾气净化设备，其特征在于：所述净化设备还包括储料罐和回收塔，所述分段式吸收塔的回收水出口和回收溶剂出口通过传输管道连接储料罐，所述储料罐 通过传输管道连接所述回收塔，所述回收塔的塔顶输出口处设有分相罐，所述传输管道上相应的设有泵和换热器。
  9. 根据权利要求7所述的含挥发性有机物尾气净化设备，其特征在于：所述净化设备还包括储料罐和回收塔，所述分段式吸收塔的回收溶剂出口通过传输管道依次连接第一储料罐和第一回收塔，经第一回收塔处理后得到挥发性有机物和再生溶剂，所述分段式吸收塔的回收水出口通过传输管道依次连接第二储料罐和第二回收塔，经第二回收塔处理后得到再生水和再生溶剂，所述传输管道上相应的设有泵和换热器。
  10. 根据权利要求8或9所述的含挥发性有机物尾气净化设备，其特征在于：所述再生溶剂和再生水通过传输管道分别进入所述分段式吸收塔中循环再利用。
  11. 根据权利要求8或9所述的含挥发性有机物尾气净化设备，其特征在于：所述净化设备还包括气液分离器和压缩机，所述气液分离器与分相罐和/或回收塔通过管路相连，所述压缩机分别与分段式吸收塔和气液分离器的气体端口通过传输管道相连。
  12. 根据权利要求7-11任一项所述的含挥发性有机物尾气净化设备，其特征在于：
    所述溶剂吸收段为多段式，优选的，为2-5段，更优选的，为2段；
    和/或，所述水吸收段采用高效低阻力塔盘；
    和/或，所述回收塔为减压精馏塔。
  13. 根据权利要求12所述的含挥发性有机物尾气净化设备，其特征在于：每相邻两段溶剂吸收段之间外接一换热器。
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