CN101108296A - Process method of purifying and recycling mixed organic waste gas - Google Patents
Process method of purifying and recycling mixed organic waste gas Download PDFInfo
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- CN101108296A CN101108296A CNA2007100452013A CN200710045201A CN101108296A CN 101108296 A CN101108296 A CN 101108296A CN A2007100452013 A CNA2007100452013 A CN A2007100452013A CN 200710045201 A CN200710045201 A CN 200710045201A CN 101108296 A CN101108296 A CN 101108296A
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Abstract
The invention belongs to chemical industry and waste gas process field, in particular providing a process method which mixes organic waste gas purifying and resource recovery. The specific procedure is that: make the mixed waste gas pass through a filter to be filtered, and then enters into a single-seat multilevel absorption tower and contacts with a packing layer and a liquid distribution device; when the series of the single-seat tower is 3, the second-grade liquid distribution device adopts a kind of absorbent which is a mixing liquid comprising the mixing liquid which is pumped in after cooled by a heat interchanger at the bottom of the adsorption tower and the mixing liquid which generates in the middle groove of the third-grade; the third-grade liquid distribution device adopts a kind of absorbent which is a mixing liquid comprising fresh absorbent, the regenerating liquid recycled by a mixing liquid separation device and the collecting liquid collected by a collecting hopper of third-grade; when the series of the single-seat tower is N and is larger than 3, all grades of absorbent from the second grade to the N minus 2 is a mixing liquid comprising a mixing liquid generated in the middle groove of the next grade and a collecting liquid collected by the collecting hopper on the same grade, the absorbent of the N minus grade is the colleting liquid collected by the collecting hopper of the N minus 1 grade, the absorbent of the N grade is a mixing liquid comprising of pumped fresh absorbent and the regenerating liquid recycled by the mixing liquid separation device. The fresh absorbent is an environment-protected organic solvent with high boiling point, strong lipophilicity and low volatility. The invention can recycle a plurality of organic infectant in waste gas, the technics procedure is simple, practical, and the operation cost is low.
Description
Technical field
The invention belongs to chemical industry and exhaust-gas treatment field, a kind of mixing organic waste-gas purification and recycling processing method specifically are provided.
Background technology
At present, to mixing organic exhaust gas, as containing organic pollution waste gas such as dimethyl formamide (DMF), toluene and butanone in the synthetic leather industry, waste gas purification mainly concentrates on end treatment, and mature technique mainly contains: catalytic combustion technology, charcoal absorption technology and water and DMF solvent absorption cleaning technology.Wherein, catalytic combustion technology can be handled DMF, toluene, the butanone in the waste gas simultaneously, but the operating cost height belongs to elimination type technology, can't realize that the organic matter resource reclaims.Though the charcoal absorption technology is the above-mentioned three kinds of pollutants of absorption from waste gas simultaneously, because DMF boiling point height, perfect active carbon regenerating technology still remains to be developed.Though some experts and scholars improve above-mentioned technology in recent years, as improve charcoal absorption, improve and directly burn, improve catalytic combustion etc., but these technology still are based on the waste gas purification of end treatment, can't carry out resource to the useful component in the waste gas and recycle, cause the significant wastage of resource.Conventional absorption techniques, as making absorbent with water, only can effectively reclaim DMF, but can't the recycle-water dissolubility low or insoluble toluene, butanone etc., for example the patent No. is the absorption technique that 200510061856.0 " dimethyl formamide effluent gases recovering and processing method for dry method synthetic leather " mentioned.The absorption process technology of DMF in the recovery waste gas of Italy exploitation can reach 90% to the overall recovery of DMF, but can't satisfy the requirement that toluene and butanone in China's leather technology waste gas are administered the environmental emission standard of discharging.Application number be 200410053246.1 " recovery method of toluene, butanone and dimethyl formamide in the wet-method synthetic leather process gas " though in the technology mentioned can reclaim DMF, toluene, butanone in the waste gas simultaneously, but still have following problems: (1) organic efficiency is low.The rate of recovery of this technology toluene and acetone is respectively 83.5% and 49.2%, and toluene and butanone obviously exceed standard in the gas after the processing, can't reach the environment protection emission requirement; (2) investment is big, the operating cost height.This process using double tower two-stage absorption plant, the one-time investment of technology is big, and the pressure drop of this process tower equipment operation simultaneously is big, the system energy consumption height, and DMF concentration surpasses 10000mg/Nm in the one-level absorption plant outlet waste gas
3, cause the absorption load of sponge oil unit high, the consumption of absorbent is big, reclaims DMF purified solution expense height.(3) there is serious potential safety hazard in system's operation.When absorption plant at summer operation, first grade absorption tower outlet waste gas is at high O
2, high DMF concentration, high EGT (summer can up to 60 ℃, near the flash-point of DMF) environment under, treatment process exists serious fire or hidden peril of explosion.(4) flow process complexity, the operation requirement is high, difficulty is big, is not suitable for environment-friendly engineering practical application and popularization.
Summary of the invention
The object of the present invention is to provide a kind of mixing organic waste-gas purification and recycling processing method, be intended to realize that waste gas is in environment improvement up to standard, realize the recovery and reuse of efficient resource, and realize the system resource configuration rationally, the target of economic benefit and environmental benefit doulbe-sides' victory.
Mixing organic waste-gas purification and recycling processing method that the present invention proposes, mixing organic exhaust gas adopts the multistage absorption tower of single seat to handle, press the air inlet order of waste gas, this treating column first order adopts spraying technique, only contain spraying layer 17, all the other every grade employing packed tower absorption techniques all is made up of packing layer 15 and liquid distribution device 14 for every grade, be provided with liquid collecting bucket 16 between the packing layer 15 of next stage and the liquid distribution device 14 of upper level, concrete steps are as follows:
(1) mix waste gas of collecting is filtered through filter 2, remove degranulation or fibrous substance;
(2) mix waste gas after the filtration enters the multistage absorption tower of single seat, and in tower, the mix waste gas after the filtration directly contacts with absorbent in first order spraying layer 17 earlier, the circulation fluid that the absorbent of the first order adopts the bottom, absorption tower to pump into after heat exchanger 5 coolings;
(3) mist after step (2) is handled enters second level packing layer 15, and in packing layer 15, contact with filler, enter second level liquid distribution device 14 then and directly contact, enter third level packing layer 15, liquid distribution device 14 more successively with absorbent; And the like, mix waste gas enters packing layer 15, the liquid distribution device 14 of next stage;
(4) when single tower progression is 3 grades, the mixing material that the mixed liquor that the absorbent that second level liquid distribution device 14 adopts produces for the medial launder 6 of the mixed liquor that pumped into after heat exchanger 5 coolings by the bottom, absorption tower and the third level is formed, the mixing material of the regenerated liquid that the absorbent that third level liquid distribution device 14 adopts is a fresh absorbent, mixed liquor separator 7 reclaims and the collection liquid three composition of this grade liquid collecting bucket 16; When single tower progression is N, and N was greater than 3 o'clock, the mixing material that the mixed liquor that the absorbents at different levels of the second level to the N-2 level all produce for the medial launder 6 by next stage and the collection liquid of this grade liquid collecting bucket 16 are formed, the absorbent of N-1 level is the collection liquid of N-1 level liquid collecting bucket 16, and the absorbent of N level is the mixing material that the regenerated liquid of fresh absorbent, 7 recovery of mixed liquor separator is formed; Wherein, fresh absorbent employing boiling point is 180 ℃～400 ℃ strong oil-wet, a low volatility environment-friendly type organic solvent;
(5) gas after step (4) is handled enters demist layer 13, is discharged by absorption tower 4 cats head, and the mixed liquor at the bottom of the absorption Tata is after heat exchanger 5 coolings, a part enters mixed liquor separator 7 as getting rid of liquid outward, as absorbent, wherein, get rid of liquid measure outward is 0.1m to remainder through blowback stream
3/ h～5m
3/ h, reflux ratio is artificial or adjustment automatically according to the gas concentration of absorption tower exhaust outlet;
(6) in the step (5) behind mixed liquor separator 7, separate the solvent that contains low pollutant levels obtain and pump into afterbody liquid distribution device 14 as regenerated liquid, separate the contaminant component that obtains and reclaim.
Among the present invention, the fresh absorbent that pumps in the multistage absorption tower can adopt higher boiling, strong oil-wet, low volatility environment-friendly type organic matter, or the organic combination of environment-friendly type or the mixing of several higher boiling, strong oil-wet, low volatility.As in dibutyl phthalate, repefral, myristyl bromine or the diallyl phthalate etc. any or several.So-called higher boiling is meant boiling point between 180 ℃～400 ℃, and so-called environment-friendly type is meant that the volatility of absorbent is low, handles in the waste gas process to be difficult for evaporateing in the atmosphere, and environment is caused secondary pollution.So-called fresh absorbent is meant the absorbent that does not carry out absorption reaction with waste gas.
Among the present invention, mix waste gas before filtration, the air-flow immixture that can adopt collection chamber 1 or waste gas header road all with pollutant levels and flow.
Among the present invention, filter 2 can adopt conventional woven wire or unique rolling porous type material filter.
Among the present invention, spray in the multistage absorption tower can adopt single hop spray or multistage spray, the spray mode can be to arrange against airflow direction or with airflow direction, nozzle can be solid nozzle that also can be conventional, the nozzle quantity of arranging is more than or equal to 1, and is even, reasonable as long as the position of nozzle sprays absorbent.
Among the present invention, liquid distribution device 14 is routine techniques, can select dissimilar technologies or device according to Practical Calculation.
Among the present invention, the place that packing layers at different levels fully contact as this grade absorbent and pollutant, it also is the main place of pollutant absorption cleaning in the waste gas, used filler can be the diffusing heap or the structured packing of metal or non-metal type, and common have general chemical fillers such as corrugated plating, woven wire, orifice plate, metal Raschig ring, Pall ring.
Among the present invention, get rid of liquid outward and be and outside the branch road of circulating-pump outlet by band flowmeter and by-pass valve control carries out, get rid of or directly from picking out to the appointed place at the bottom of the tower.
Among the present invention, mix waste gas enters demist layer 13 and removes remaining absorption liquid after multistage liquid distribution device 14 and packing layer 15 absorb.The effect of absorption tower demisting layer is the absorption liquid of carrying secretly in the waste gas behind minimizing and the elimination absorption cleaning, and demist layer 13 adopts wire mesh packings.
Among the present invention, consider the motive force of absorption process, advance the order of tower according to waste gas, total melting concn of organic pollution reduces successively in the absorption liquid of each absorber portion or the absorbent, to improve overall absorption efficient.The absorption liquid measure of each absorber portion can be adjusted according to different processing objects, but absorbent is the bottom mixed liquor of mixed liquor at the bottom of the tower, packing layers at different levels, gets rid of regeneration type absorbent that liquid separation system regeneration obtains outward, several liquid such as fresh absorbent of pumping into are on a small quantity allocated or use separately.
Among the present invention, medial launder is 1～10.
Among the present invention, the kind of organic pollution is more than or equal to 1, as one or more combination such as DMF, toluene, butanone in the waste gas that relates to.
Among the present invention, mix waste gas absorbs through single absorption tower multi-stage spray and filler, and liquid distribution device 14 can be arranged in order with packing layer 15 or alternately arrange.Wherein, liquid distribution device 14 is all 1～10 grade with packing layer 15 progression.
Among the present invention, the column bottom temperature on absorption tower is 35 ℃～70 ℃, and tower top temperature is 25 ℃～80 ℃.
Among the present invention, the absorbent that adopt on the absorption tower is the environment-friendly highly efficient absorbent, and this absorbent strong oil-wet all has good assimilation effect to organic pollutions such as DMF, toluene and butanone, and assimilation effect obviously is better than traditional water absorption techniques.Because this environment-friendly type absorbent volatility is poor, in absorbing processing procedure, be difficult for entering waste gas, need not as application number is that the employing secondary water absorption tower mentioned in 200510061856.0 " dimethyl formamide effluent gases recovering and processing method for dry method synthetic leather " absorbs a large amount of absorbents in the waste gas, only needs to adopt mono-tower multi-stage to absorb the qualified discharge that can guarantee waste gas.Simultaneously, the flash-point height of this environment-friendly type absorbent, it is higher, wideer to be suitable for the technological temperature of handling, the potential safety hazard when not having " dimethyl formamide effluent gases recovering and processing method for dry method synthetic leather " actual motion.In addition, the boiling point difference of this absorbent and DMF, toluene, butanone is bigger, the motive force of component lock out operation is big, easier the carrying out of recovery technology that the separation recycling of the follow-up contaminant component of blend absorbent also proposes than " dimethyl formamide effluent gases recovering and processing method for dry method synthetic leather ".
Simultaneously, the present invention compares with other traditional handicrafts, and its advantage is:
(1) the present invention can reclaim multiple organic pollution in the waste gas simultaneously, and to containing boiling point greater than the pollutant waste gas more than 110 ℃, the absorption efficiency height of pollutant can be controlled exit gas concentration such as toluene, butanone etc. simultaneously less than 20mg/m especially
3, DMF is less than 30mg/m
3
(2) the inventive method process route is simple, practical, and operating cost is low, and operating cost only is 1/5 of a condensation method recovery technology, 1/3 of absorption method recovery technology.
(3) the present invention combines filler absorption and spray absorption techniques advantage, tower is handled the air speed height, disposal ability is strong, be 3～4 times of conventional absorption techniques, pressure drop only is traditional same tower height, same 1/2～1/3 of the load of handling, solved the problem that the absorption tower load is little in the conventional absorption technique, pressure drop is big, administering for the technology waste gas of atm number provides technical guarantee, and cost of investment is saved.
(4) to handle object extensive in the present invention, and the organic EGT wide ranges of callable mixing, organic pollutant category are many.As industry surface-treated waste gas such as synthetic leather industry, auto manufacturing, printing industry, textile industry, sprayings.
Description of drawings
Fig. 1 is the process flow diagram of the embodiment of the invention 1.
Fig. 2 is the process flow diagram of the embodiment of the invention 2.
Number in the figure: 1 is collection chamber, and 2 is filter, and 3 is air-introduced machine, 4 is multistage absorption tower, and 5 is heat exchanger, and 6 is intermediate storage tank, 7 is the mixed liquor separator, and 8 is water pump, and 9 is valve, 10 is exhaust blower, and 11 is the absorption tower exhaust outlet, and 12 is the absorption tower housing, 13 are the demist layer, and 14 is liquid distribution device, and 15 is packing layer, 16 is liquid collecting bucket, and 17 is spraying layer, and 18 are the absorption liquid outlet.
The specific embodiment
Below by accompanying drawing this invention of further explaining.
The fresh absorbent that pumps on mix waste gas absorption tower adopts dibutyl phthalate, and absorption tower 4 is three grades of absorption towers.Press the air inlet order of waste gas, this treating column is except that the first order only has spraying layer 17, all form for all the other every grade by packing layer 15 and liquid distribution device 14, be provided with liquid collecting bucket 16 between the packing layer 15 of next stage and the liquid distribution device 14 of upper level, secondary medial launder 6 connects at the bottom of the tower absorption liquid respectively through medial launder 6, the second level liquid distribution device 14 of the cooled liquid of heat exchanger, the third level; The medial launder 6 of the third level connects liquid collecting bucket 16, mixed liquid separating apparatus 7, the third level liquid distribution device 14 that fresh absorbent pumps into pipeline, the third level respectively.Waste gas after collecting, send into collection chamber 1 all with concentration and flow, then by entering efficient three grades of absorption towers behind the filter 2 interception large granular impurities, gas contacts with the high speed in reversed direction of absorbent, contacts absorption with packing layer 15, discharges behind the steam that the layer of process demist at last 13 is removed in the gas.The concentration of toluene and butanone etc. is less than 5mg/m in the outlet waste gas
3, DMF concentration is less than 20mg/m
3, temperature is about 45 ℃.Absorption liquid is discharged by outlet 18 at the bottom of the tower, and after heat exchanger 5 was cooled to about 40 ℃, major part was used for circulation and absorbs, and small part enters mixed liquor separator 7 and separates recovery as getting rid of liquid outward, and getting rid of liquid measure outward is 0.2m
3/ h.
The absorbent difference of this absorption tower liquid distribution devices 14 at different levels.Along with waste gas absorbs successively from the bottom up, the absorbent of spraying layer 17 is the circulation fluid that absorption liquid is stamped by pump after the heat exchanger cooling at the bottom of the tower; The absorbent of second level liquid distribution device 14 be at the bottom of the tower absorption liquid through the mixed liquor of cooled liquid of heat exchanger and third level medial launder liquid; The absorbent of third level liquid distribution device 14 is the mixed liquor of these three kinds of liquid of collection liquid of liquid collecting bucket 16 under the regenerated liquid, third level packing layer of the dibutyl phthalate that reclaims of fresh absorbent, mixed liquor separator 7.In the operating process, the intermittently a small amount of third level medial launder that adds of the fresh absorbent that pumps into, the regenerated liquid of dibutyl phthalate, the continuous service of third level spray equipment mainly relies on collection liquid constantly recycling of liquid collecting bucket 16 under the third level packing layer, and the continuous service of second level spray equipment, spraying layer 17 mainly depends on the constantly recycling of at the bottom of the tower of heat exchanger cooling absorption liquid, thereby not only improved the absorption efficiency of total tower, and saved the consumption of dibutyl phthalate fresh absorbent and regenerated liquid, also guaranteed outer concentration of having got rid of liquid.
The fresh absorbent on mix waste gas absorption tower adopts repefral, and the absorption tower is the level Four absorption tower.Press the air inlet order of waste gas, this treating column is except that the first order only has spraying layer 17, all form for all the other every grade by packing layer 15 and liquid distribution device 14, be provided with liquid collecting bucket 16 between the packing layer 15 of next stage and the liquid distribution device 14 of upper level, partial medial launder 6 connects at the bottom of the tower absorption liquid respectively through medial launder 6, partial liquid collecting bucket 16, the partial spray equipment 14 of the cooled liquid of heat exchanger, the third level; The medial launder 6 of the third level connects the liquid distribution device 14 of the liquid collecting bucket 16 of the third level, mixed liquid separating apparatus 7, partial medial launder 6, the third level respectively.Waste gas after collecting, send into collection chamber 1 all with concentration and flow, then by entering efficient level Four absorption tower behind the filter 2 interception large granular impurities, gas contacts with the high speed in reversed direction of absorbent, contacts absorption with packing layer 15, discharges behind the steam that the layer of process demist at last 13 is removed in the gas.The concentration of toluene and butanone etc. is less than 4mg/m in the outlet waste gas
3, DMF concentration is less than 17mg/m
3, temperature is about 47 ℃.Absorption liquid is discharged by outlet 18 at the bottom of the tower, and after heat exchanger 5 was cooled to about 40 ℃, part absorbed by being used for circulation, and part enters mixed liquor separator 7 and separates recovery as getting rid of liquid outward, and getting rid of liquid measure outward is 4m
3/ h.。
The absorbent difference of these absorption tower liquid distribution devices at different levels.Along with waste gas absorbs successively from the bottom up, the absorbent of spraying layer 17 is the circulation fluid that absorption liquid is stamped by pump after the heat exchanger cooling at the bottom of the tower; The absorbent of second level liquid distribution device is the collection liquid of liquid collecting bucket 16 under the packing layer of the second level and the mixed liquor of third level medial launder 6 liquid; The absorbent of third level liquid distribution device is the collection liquid of liquid collecting bucket 16 under the third level packing layer; The absorbent of fourth stage liquid distribution device is the mixed liquor of the absorbent regeneration that obtains of fresh absorbent and mixed liquor separator 7.In the operating process, the regenerated liquid of fresh absorbent, repefral continues to enter fourth stage liquid distribution device, and first order liquid distribution device continuous service mainly depends on the constantly recycling of at the bottom of the tower of heat exchanger cooling absorption liquid, thereby improved the absorption efficiency of total tower, reduced the concentration of outlet pollutant.
Claims (10)
1. one kind is mixed organic waste-gas purification and recycling processing method, it is characterized in that mixing organic exhaust gas adopts the multistage absorption tower of single seat to handle, press the air inlet order of waste gas, this treating column first order adopts spraying technique, only contain outside the spraying layer (17), all the other every grade employing packed tower absorption techniques all is made up of packing layer (15) and liquid distribution device (14) for every grade, be provided with liquid collecting bucket (16) between the liquid distribution device (14) of packing layer of next stage (15) and upper level, concrete steps are as follows:
(1) mix waste gas of collecting is filtered through filter (2), remove degranulation or fibrous substance;
(2) mix waste gas after the filtration enters the multistage absorption tower of single seat, and in tower, the mix waste gas after the filtration directly contacts with absorbent in first order spraying layer 17 earlier, the circulation fluid that the absorbent of the first order adopts the bottom, absorption tower to pump into after heat exchanger (5) cooling;
(3) mist after step (2) is handled enters second level packing layer (15), and in packing layer, contact with filler, enter second level liquid distribution device (14) then and directly contact, enter third level packing layer (15), liquid distribution device (14) more successively with absorbent; And the like, mix waste gas enters packing layer (15), the liquid distribution device (14) of next stage;
(4) when single tower progression is 3 grades, the serve as reasons mixing material of collection liquid three composition of the fresh absorbent that pumps into, regenerated liquid that mixed liquor separator (7) reclaims and this grade liquid collecting bucket (16) of the mixing material that the mixed liquor that the absorbent that second level liquid distribution device (14) adopts produces for the medial launder (6) of the mixed liquor that pumped into after heat exchanger (5) cooling by the bottom, absorption tower and the third level is formed, the absorbent that third level liquid distribution device (14) adopts; When single tower progression is N, and N was greater than 3 o'clock, the mixing material that the absorbents at different levels of the second level to the N-2 level are all formed for the collection liquid of the mixed liquor that produced by the medial launder (6) of next stage and this grade liquid collecting bucket (16), the absorbent of N-1 level is the collection liquid of N-1 level liquid collecting bucket (16), the absorbent of the N level mixing material that regenerated liquid that the fresh absorbent that pumps into, mixed liquor separator (7) reclaim is formed of serving as reasons.The fresh absorbent employing boiling point that pumps into is 180 ℃～400 ℃ strong oil-wet, a low volatility environment-friendly type organic solvent;
(5) gas after step (4) is handled enters demist layer (13), discharge by absorption tower (4) cat head, mixed liquor at the bottom of the absorption Tata is after heat exchanger (5) cooling, a part enters mixed liquor separator (7) as getting rid of liquid outward, remainder flows as absorbent through blowback, wherein, getting rid of liquid measure outward is 0.1m
3/ h～5m
3/ h, reflux ratio is artificial or adjustment automatically according to the gas concentration of absorption tower exhaust outlet;
(6) in the step (5) behind mixed liquor separator (7), separate the solvent that contains low pollutant levels obtain and pump into afterbody liquid distribution device (14) as regenerated liquid, separate the contaminant component that obtains and reclaim.
2. mixing organic waste-gas purification according to claim 1 and recycling processing method, it is characterized in that the fresh absorbent that pumps in the multistage absorption tower be in dibutyl phthalate, repefral, myristyl bromine or the diallyl phthalate any or several.
3. mixing organic waste-gas purification according to claim 1 and recycling processing method is characterized in that mix waste gas before filtration, the air-flow immixture that adopts collection chamber (1) or waste gas header road all with pollutant levels and flow.
4. mixing organic waste-gas purification according to claim 1 and recycling processing method is characterized in that filter (2) adopts woven wire or rolling porous type material filter.
5. mixing organic waste-gas purification according to claim 1 and recycling processing method is characterized in that the spray in the multistage absorption tower adopts single hop spray or multistage spray, and the spray mode is to arrange against airflow direction or with airflow direction.
6. mixing organic waste-gas purification according to claim 1 and recycling processing method, it is characterized in that the used filler of packing layers at different levels be in corrugated plating, woven wire, orifice plate, metal Raschig ring or the Pall ring any.
7., mixing organic waste-gas purification according to claim 1 and recycling processing method is characterized in that the outer liquid that gets rid of is to get rid of or directly from picking out to the appointed place at the bottom of the tower outside the branch road of circulating-pump outlet by band flowmeter and by-pass valve control carries out.
8. mixing organic waste-gas purification according to claim 1 and recycling processing method is characterized in that demist layer (13) adopts wire mesh packing.
9. mixing organic waste-gas purification according to claim 1 and recycling processing method is characterized in that liquid distribution device (14) and packing layer (15) progression are all 1～10 grade.
10. mixing organic waste-gas purification according to claim 1 and recycling processing method, the column bottom temperature that it is characterized in that the absorption tower are 35 ℃～70 ℃, and tower top temperature is 25 ℃～80 ℃.
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| CN100467097C CN100467097C (en) | 2009-03-11 |
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