CN102698558A - Device and method for adsorbing, recycling and treating organic waste gases efficiently - Google Patents
Device and method for adsorbing, recycling and treating organic waste gases efficiently Download PDFInfo
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- CN102698558A CN102698558A CN2012101022386A CN201210102238A CN102698558A CN 102698558 A CN102698558 A CN 102698558A CN 2012101022386 A CN2012101022386 A CN 2012101022386A CN 201210102238 A CN201210102238 A CN 201210102238A CN 102698558 A CN102698558 A CN 102698558A
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Abstract
The invention relates to a method for purifying, recycling and treating organic waste gases and provides a device for adsorbing, recycling and treating organic waste gases efficiently, which comprises an organic-waste-gas conveying pipe, a steam conveying pipe, a water absorption tower, an adsorption and desorption tower, an organic-solvent separating and recycling system, a switching valve, a condenser, an organic-solvent recycling tank and a steam generator, wherein two or more adsorption tanks are juxtaposedly arranged on the adsorption and desorption tower. Because the adsorption and desorption tower with two or more adsorption tanks arranged juxtaposedly are connected in series with the rear part of the water absorption tower, and the novel MIL-101 metal organic framework material are used as the adsorbent to replace the traditional adsorbents such as the granular activated carbon or activated carbon used for purifying and recycling organic waste gases in the synthetic leather industries and the like, the problems that the efficiency of removing the organic waste gases by using the single water absorption tower is low and the discharge of the organic waste gases does not reach the standard are solved, and the efficiency of adsorbing and recycling the organic waste gases is improved.
Description
Technical field
The present invention relates to the efficient absorption recovery and treatment method of organic exhaust gas, particularly relate to the efficient absorption recycling and processing device and the method for volatile organic waste gas in a kind of synthetic leather production process.
Background technology
In the synthetic leather production process, need to use a large amount of volatile organic solvents (like dimethyl formamide (DMF), toluene, xylenes, butanone); The synthetic leather goods that contain a large amount of organic solvents are through high-temperature process the time; These organic solvents all are discharged in the atmosphere as waste gas; Environment is caused severe contamination, also cause huge waste to enterprise.Therefore, take economical and practical waste gas pollution control and treatment technology, develop suitable technological process, make the waste gas qualified discharge of numerous synthetic leather enterprise, and reclaim organic solvent, the raising performance of enterprises has important practical significance.
The development of synthetic leather waste gas pollution control and treatment technology is constantly to change along with the change of synthetic leather technology.General absorption techniques and the adsorption desorption technology of adopting of existing synthetic leather waste gas pollution control and treatment technology.In absorption techniques; The absorption tower is adopted water to absorb as absorbent and is reclaimed the organic solvent in the waste gas, and this method can be removed the DMF in the waste gas preferably, and clearance is about 90%; But the clearance to toluene, xylenes and butanone is very low, far can not reach emission request.Some enterprise adopts the series multistage absorption tower; Circulation absorbs; Although improved the clearance of DMF, because the poorly water-soluble of toluene, xylenes, their clearance does not obviously improve; This does not only reach emission request, causes the exhaust-gas treatment cost to increase substantially owing to having increased absorption equipment simultaneously.For the adsorption desorption technology, its core technology is selected high performance adsorbent exactly for use.It is adsorbent that present industrial adsorption desorption generally adopts granular activated carbon or NACF isoreactivity carbon-based material when handling synthetic leather waste gas.The specific area of granular activated carbon is generally 600~1600m
2/ g, pore-size distribution is wide, and being processed gas will spread from outside to inside, longer through distance, and so adsorption-desorption is all slower, and absorption is saturated easily, so the rate of recovery lower (about 80%), and service life is not long, and operating cost is high.The NACF pore is less, and specific area is big, and it is to lean on intermolecular attractive interaction to adsorb; Chemical reaction does not take place each other, is physical adsorption process, and the direct opening of aperture is outside; Gas diffusion length is shorter, and adsorption-desorption is all very fast, and the rate of recovery is high; Can reach more than 90%, but NACF costing an arm and a leg, is more than ten times of active carbon.In addition, because absorbent charcoal based adsorbent has certain water imbibition, when absorption has the synthetic leather waste gas of certain humidity; The adsorption capacity of absorbent charcoal based sorbing material can sharply descend, and also is because absorptive characteristics make adsorbent in the steam regenerative process; Need carry out long dry run, so not only time-consuming but also cost is high, therefore; A lot of enterprises generally do not carry out desorption and Regeneration Treatment after absorbent charcoal based adsorbents adsorb is saturated, and direct burn processing.In addition, there is inflammable security hidden trouble in absorbent charcoal based sorbing material in practical applications.
In recent years; A kind ofly be connected with transition metal and new material-metal-organic framework materials (MOFs of the mesh skeleton that forms by the organic ligand that contains oxygen or nitrogen; Metal organic frameworks); Owing to have very flourishing pore structure and incomparable huge specific area, and pore structure is regular, the pore size design is adjustable, surface chemistry group modified advantage that conventional adsorbent such as adjustable do not possess, has good application prospects at chemical adsorbing separation, catalytic reaction, environmental protection and energy field.In the MOFs material, with the novel MOFs material-MIL-101 (Cr of chromium ion as metal ligand
3F (H
2O)
2O [(O
2C)-C
6H
4-(CO
2)]
3NH
2O, n ≈ 25) owing to have largest specific surface area (5900 ± 300m
2/ g) and pore volume (≈ 2.0cm
3/ g) and high hydrothermal stability; Become the gas absorption material of excellent performance, particularly to the adsorption capacity of organic compounds such as stupid, toluene, xylenes, acetaldehyde, chlorohydrocarbon far above sorbing materials such as active carbon, molecular sieve, silicon gel, SBA-15.
Summary of the invention
What the present invention will solve is that present absorption techniques is low to the clearance of organic solvents such as toluene, xylenes, butanone in the synthetic leather organic exhaust gas, can not qualified discharge and the problem of recycling.Be employed in water absorption tower that the synthetic leather organic exhaust gas the handles adsorption desorption tower that is connected in series at the back; Adopting the MIL-101 novel absorption material is adsorbent; Replace present absorbent charcoal based adsorbent, adsorbing separation reclaims the volatile organic solvents such as toluene, xylenes, butanone and DMF from the moisture organic exhaust gas that discharge on the water absorption tower.Overcoming existing single water absorption tower, to handle DMF, particularly toluene in the synthetic leather organic exhaust gas, xylenes, butanone clearance low, defective that can not qualified discharge.
A kind of device of efficient absorption recycling organic exhaust gas; Comprise that organic waste gas pipeline road, steam conveying pipe, water absorption tower, parallel connection are provided with the adsorption desorption tower of two or more adsorption tanks, transfer valve, condenser, organic solvent separation and recovery system, organic solvent recycling can and steam generator; It is characterized in that: in the organic waste gas treatment device; The water absorption tower adsorption desorption tower that is connected in series at the back is provided with the metal-organic framework materials adsorbent in the adsorption tanks of adsorption desorption tower.
Described metal-organic framework materials is the MIL-101 material, and chemical property is stable, and acid and alkali-resistance is water-fast, high temperature high voltage resistant.
Described MIL-101 has high specific surface, and pore passage structure is regular, hole dimension homogeneous, even aperture distribution.
Typically, the specific area of said MIL-101 is 4500~6200m
2/ g, pore volume are 1.5~2.5cm
3/ g, the aperture is 0.6-3.5nm, has excellent absorption property.
A kind of method of efficient absorption recycling organic exhaust gas may further comprise the steps:
1) organic exhaust gas is admitted to the water absorption tower through the organic exhaust gas conveyance conduit, after contained organic solvent absorbs processing through water in the waste gas, discharges the entering adsorption desorption by cat head and handles;
2) organic exhaust gas of water absorption tower discharge gets into the adsorption desorption tower through conveyance conduit, and contained organic exhaust gas is adsorbed a jar interior MIL-101 adsorbents adsorb in the waste gas, and the waste gas after the adsorption treatment is discharged from adsorption tanks;
3) after the MIL-101 adsorbents adsorb in the adsorption tanks is saturated, through transfer valve the organic exhaust gas conveyance conduit is switched to next adsorption tanks, organic exhaust gas is admitted to next adsorption tanks adsorption treatment;
4) water vapour is admitted to the saturated adsorption tanks of absorption through steam conveying pipe and carries out the desorption desorb, and the stripping gas that contains the organic solvent of water vapour and desorption is discharged into condenser from adsorption tanks and carries out condensation, the organic solvent of condensation entering solvent recovery jar;
5) make said two or more adsorption tanks carry out adsorption treatment and desorption desorption cycle in turn through transfer valve.
A kind of apparatus and method of efficient absorption recycling organic exhaust gas; Its characteristic also is; Said water vapour is not directly to discharge as waste water, but is heated as steam through steam generator after condenser condenses; Be admitted to the saturated adsorption tanks of absorption through the steam transfer passage again and carry out the desorption desorb, thereby realize recycling of desorb water steam.
The present invention's adsorption desorption tower that is connected in series at the back on the water absorption tower of synthetic leather organic waste gas treatment equipment; And adopting the MIL-101 new material is that adsorbent is to replace existing absorbent charcoal based adsorbent; Overcome the defective of traditional single water absorption tower technology, improved the efficient of organic exhaust gas absorption recycling.
Description of drawings
Accompanying drawing 1 is the process chart of embodiment 1.
Among the figure: 1, water absorption tower, 2, adsorption tanks 2,3, adsorption tanks 3,4, condenser, 5, steam generator, 6, the organic solvent recycling can, 7, the organic solvent separation and recovery system, V1, transfer valve 1, V2, transfer valve 2.
The specific embodiment
Embodiment one:
Present embodiment provides a kind of device and processing method of efficient absorption recycling organic exhaust gas.
Certain synthetic leather workshop discharge tail gas, its main component is DMF, toluene, xylenes, butanone and air etc., the tail gas air quantity is 25000m
3/ h, DMF concentration is 2500mg/m
3, toluene concentration is 1200mg/m
3, xylene concentration is 1000mg/m
3, butanone concentration is 600mg/m
3
Accompanying drawing 1 is the process chart of embodiment 1.A kind of device of efficient absorption recycling organic exhaust gas comprises that organic waste gas pipeline road, steam conveying pipe, water absorption tower, parallel connection are provided with the adsorption desorption tower of two or more adsorption tanks, transfer valve, condenser, organic solvent separation and recovery system, organic solvent recycling can and steam generator.
Adsorption tanks 2 are provided with the MIL-101 adsorbent with adsorption tanks 3.
The employed adsorbent of present embodiment is MIL-101, and chemical formula is Cr
3F (H
2O)
2O [(O
2C)-C
6H
4-(CO
2)]
3NH
2O, n=23~26 wherein, chemical property is stable, and acid and alkali-resistance is water-fast, high temperature high voltage resistant.MIL-101 has the following advantages as adsorbent: there is not the inflammable potential safety hazard of acticarbon in 1, good flame resistance; 2, be easy to processing, can be as required with any dosage form production, like bulk, particle, powder, bar-shaped etc.; 3, have wide range of applications, both can also can under vacuum or other physical parameter conditions, use at normal pressure; 4, production cost is low.
Described MIL-101 has high specific surface, and pore passage structure is regular, hole dimension homogeneous, even aperture distribution.
Typically, specific area 4500~6200m of said MIL-101
2/ g, pore volume are 1.5~2.5cm3/g, and the aperture is 0.6~3.5nm, have excellent absorption property.
A kind of method of efficient absorption recycling organic exhaust gas may further comprise the steps:
1) organic exhaust gas is admitted to water absorption tower 1 through the organic exhaust gas conveyance conduit, and contained organic solvent absorbs through water and handles in the waste gas; Water absorbs organic exhaust gas 1 discharge from the water absorption tower after handling; The waste water that absorbs organic exhaust gas is transported to the Separation and Recovery that organic solvent separation and recovery system 7 carries out organic solvent through pipeline;
2) water absorption tower 1 organic exhaust gas of discharging is sent into the adsorption tanks 2 of adsorption desorption tower through conveyance conduit, and contained organic solvent is adsorbed the MIL-101 adsorbents adsorb in jars 2 in the organic exhaust gas, and the waste gas after the adsorption treatment is discharged from adsorption tanks 2;
3) after the MIL-101 adsorbents adsorb in the adsorption tanks 2 is saturated, through transfer valve V1, V2 the organic exhaust gas conveyance conduit is switched to adsorption tanks 3, organic exhaust gas is admitted to adsorption tanks 3 adsorption treatment;
4) water vapour is admitted to the saturated adsorption tanks 2 of absorption through steam conveying pipe and carries out the desorption desorb, and the stripping gas that contains the organic solvent of water vapour and desorption is discharged into condenser 4 from adsorption tanks 2 and carries out condensation, the organic solvent of condensation entering organic solvent recycling can 6;
5) make adsorption tanks 2, adsorption tanks 3 carry out adsorption treatment and desorption desorption cycle in turn through transfer valve V1, V2.
A kind of method of efficient absorption recycling organic exhaust gas; Its characteristic also is; Said water vapour is not directly to discharge as waste water, but is heated as steam through steam generator 5 after condenser 4 condensations; Be admitted to the saturated adsorption tanks of absorption through the steam transfer passage again and carry out the desorption desorb, thereby realize recycling of desorb water steam.
Use absorption tower series connection adsorption desorption tower technology of the present invention in order to study; And adopt the MIL-101 material to carry out the efficient of organic waste-gas purification recycling process as adsorbent; Under different operating modes, the organic exhaust gas handling property that absorbs the series adsorption retracting device is tested, to obtain preferred technological parameter.
Table 1 is that to adopt MIL-101 be the absorption tower series connection adsorption desorption tower technology of adsorbent and the voc_s removal performance test test result contrast of single absorption tower technology in the present invention; Wherein absorption tower series connection adsorption desorption tower technology employing MIL-101 is an adsorbent; The relative humidity of the organic exhaust gas that discharge on the absorption tower is 10%; Clearance is in the time of 25 ℃, the result of device operation test in the time of 20 minutes.Table 2 is activated carbon fiber adsorbing substance The performance test results under different relative humidity conditions that absorption tower series connection adsorption desorption tower technology adopts MIL-101 adsorbent and process hydrophobic treatments respectively.
Result of the test shows that as shown in table 1, the organic exhaust gas handling property of absorption tower series connection adsorption desorption tower technology of the present invention is technology apparently higher than single absorption tower.Single absorption tower technology has only 83.6% to the clearance of DMF, and the clearance of butanone is 53.8%, and the clearance of toluene and xylenes all is lower than 10%.And absorption tower series connection adsorption desorption tower technology of the present invention, the organic solvent clearance in the waste gas all is higher than 99%, has extraordinary organic exhaust gas treatment effect.
Table 1 absorption tower series connection adsorption desorption tower technology and single absorption tower engineering test result
Table 2MIL-101 adsorbent and the result of the test of activated carbon fiber adsorbing substance under different relative humidity conditions
Under 20% low relative humidity condition, use MIL-101 to compare as adsorbent with NACF as adsorbent, the clearance of organic exhaust gas is more or less the same, but the adsorption saturation time of MIL-101 adsorbent but is 4 times of NACF.Along with the increase of ambient humidity, the adsorption saturation time of activated carbon fiber adsorbing substance and the clearance of organic solvent significantly descended particularly under high humidity, has been difficult to have satisfied emission request that industrial waste gas is handled.Though and the adsorption saturation time of MIL-101 adsorbent and clearance also have decline, the amplitude that reduces is less, and the clearance of various organic solvents all is higher than 98%, obviously is superior to existing hydrophobic activated carbon fiber adsorbing material.Show provided by the invention with MIL-101 be the absorption tower series connection adsorption desorption tower technology of adsorbent for the synthetic leather organic exhaust gas, particularly the organic exhaust gas under the high humility operating condition has very outstanding processing and reclaims ability.
Claims (6)
1. one kind efficiently adsorbs the device that recycles organic exhaust gas; Comprise that organic waste gas pipeline road, steam conveying pipe, water absorption tower, parallel connection are provided with the adsorption desorption tower of two or more adsorption tanks, transfer valve, condenser, organic solvent separation and recovery system, organic solvent recycling can and steam generator; It is characterized in that: in the organic waste gas treatment device; The water absorption tower adsorption desorption tower that is connected in series at the back is provided with the metal-organic framework materials adsorbent in the adsorption tanks of adsorption desorption tower.
2. the device of efficient absorption recycling organic exhaust gas according to claim 1 is characterized in that, the water absorption tower is connected in series at the back and has the adsorption desorption tower that two or more adsorption tanks parallel connections are provided with.
3. the device of efficient absorption recycling organic exhaust gas according to claim 1 is characterized in that described metal-organic framework materials adsorbent is MIL-101, and molecular formula is Cr
3F (H
2O)
2O [(O
2C)-C
6H
4-(CO
2)]
3NH
2O, wherein n=23~26.
4. the device of efficient absorption recycling organic exhaust gas according to claim 3 is characterized in that the specific area of said MIL-101 is 4500~6200m
2/ g, pore volume are 1.5~2.5cm
3/ g, the aperture is 0.6~3.5nm.
5. the method for efficient absorption recycling organic exhaust gas according to claim 1 is characterized in that, may further comprise the steps:
1) organic exhaust gas is admitted to the water adsorption tower through the organic exhaust gas conveyance conduit, after contained organic solvent absorbs processing through water in the organic exhaust gas, gets into adsorption desorption and handles;
2) organic exhaust gas of absorption tower discharge gets into the adsorption desorption tower through conveyance conduit, and contained organic solvent is adsorbed a jar interior MIL-101 adsorbents adsorb in the organic exhaust gas, and the waste gas after the adsorption treatment is discharged from adsorption tanks;
3) after the MIL-101 adsorbents adsorb in the adsorption tanks is saturated, through transfer valve the organic exhaust gas conveyance conduit is switched to next adsorption tanks, organic exhaust gas is admitted to next adsorption tanks adsorption treatment;
4) water vapour is admitted to the saturated adsorption tanks of absorption through steam conveying pipe and carries out the desorption desorb, and the stripping gas that contains the organic solvent of water vapour and desorption is discharged into condenser from adsorption tanks and carries out condensation, the organic solvent of condensation entering solvent recovery jar;
5) make said two or more adsorption tanks carry out adsorption treatment and desorption desorption cycle in turn through transfer valve.
6. the method for efficient absorption recycling organic exhaust gas according to claim 5; Its characteristic also is; Said water vapour is heated as steam through steam generator after condenser condenses, be admitted to the saturated adsorption tanks of absorption through steam conveying pipe again and carry out the desorption desorb.
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CN103170315A (en) * | 2013-02-28 | 2013-06-26 | 北京化工大学常州先进材料研究院 | Hydrophobic cellular metal organic skeleton for waste gas treatment and preparation method thereof |
CN103463928A (en) * | 2013-09-11 | 2013-12-25 | 中节能天辰(北京)环保科技有限公司 | Method and device for adsorbing and recovering organic waste gas |
CN103537173A (en) * | 2013-11-07 | 2014-01-29 | 中国海洋石油总公司 | Pilot-scale experiment device of gas-liquid mass transfer tower with switchable series-parallel connection |
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CN105536429B (en) * | 2015-12-11 | 2018-05-11 | 凯天环保科技股份有限公司 | Exhaust gas absorbing treatment device and processing method |
CN107790103A (en) * | 2016-08-29 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of composite adsorbing material and preparation method thereof |
CN107790103B (en) * | 2016-08-29 | 2020-04-14 | 中国石油化工股份有限公司 | Composite adsorption material and preparation method thereof |
CN107670629A (en) * | 2017-11-09 | 2018-02-09 | 大丰鑫源达化工有限公司 | A kind of device that salt is analysed using tail gas acid gas |
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CN110194721B (en) * | 2019-06-06 | 2022-05-24 | 浙江工业大学 | Hydroxyphenylglycine centrifugal mother liquor treatment device and method |
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Application publication date: 20121003 |