CN106731562A - A kind of integrated conduct method and device of the chloride organic exhaust gas of high concentration - Google Patents
A kind of integrated conduct method and device of the chloride organic exhaust gas of high concentration Download PDFInfo
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- CN106731562A CN106731562A CN201510800826.0A CN201510800826A CN106731562A CN 106731562 A CN106731562 A CN 106731562A CN 201510800826 A CN201510800826 A CN 201510800826A CN 106731562 A CN106731562 A CN 106731562A
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
- B01D53/70—Organic halogen compounds
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/206—Organic halogen compounds
- B01D2257/2064—Chlorine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
Abstract
The invention discloses a kind of integrated conduct method of the chloride organic exhaust gas of high concentration, including（1）Waste gas is passed through in regenerative oxidation reactor and is aoxidized, control oxidation bed flue gas exit temperature is below 100 DEG C；（2）The high-temperature flue gas obtained after regenerative oxidation are except for maintaining Self-heat-storage reaction energy balance external, remainder to be drawn from the middle part high-temperature region of reactor and enter stirling generator, flue gas exit temperature is below 100 DEG C after control generating；（3）By step（1）With（2）Alkali liquor absorption tower is sent into after the flue gas mixing of discharge, the sour gas in flue gas is fully absorbed, and flue-gas temperature is reduced to less than 60 DEG C, purified gas qualified discharge；（4）Absorb waste liquid and enter electrochemical regeneration device, regeneration alkali lye returns to alkali cleaning absorption tower and recycles.Purified gas after present invention treatment with qualified discharge, and can not result in the waste of big energy, subsequent treatment also without cooling device is set, will not produce it is a large amount of absorb waste liquids, economy is significantly improved.
Description
Technical field
The invention belongs to environmentally friendly technical field of waste gas treatment, and in particular to a kind of General Office of the chloride organic exhaust gas of high concentration
Reason method and device.
Background technology
In chlorine industry production process, chloride organic exhaust gas can be produced.Chloride organic exhaust gas are a kind of severe pollutants,
Wherein chlorinated aromatic hydrocarbons have bio-toxicity, and stable chemical nature, it is difficult to be biodegradable, and are persistently detained in the environment, opposite
State environmental and human health impacts constitute a serious threat.In recent years because the economic personal casualty loss caused by the leakage of chloride organic exhaust gas exists
Happen occasionally all over the world.
Treatment technology for chloride organic exhaust gas is roughly divided into solid absorption-analytic method, catalytic oxidation, thermal decomposition method
Etc. method.Solid absorption-analytic method primary sorbent is activated carbon, and it absorbs the existing physical absorption of organic chloride also chemistry
Absorption, MODEL OF CHEMICAL ABSORPTION PROCESS not only changes the functional group of activated carbon, and destroys the structure of charcoal crystal, therefore in reality
In commercial Application, in order to keep clearance higher, it is necessary to be continuously added fresh activated carbon.The operation temperature of catalytic oxidation
It is general to have bioxin generation at this temperature at 100-300 DEG C, environmental and human health impacts are made a big impact.Thermal decomposition
Method carries out oxidation Decomposition using regenerative oxidation to it, and its oxidizing temperature can reach more than 800 DEG C, can avoid the life of bioxin
Into.However, the HCl gases that oxidation is produced can not be discharged directly, it is necessary to carry out alkali cleaning to it, can not only produce and substantial amounts of absorb useless
Liquid, and with chloride organic exhaust gas organic concentration change its through regenerative oxidation process after exhaust temperature differ, when
When chloride concentration is higher, inevitably cause that the exhaust temperature produced after regenerative oxidation is too high, high-temperature flue gas enter alkali cleaning
Unit can reduce absorption efficiency, cause the waste of big energy, it usually needs set special cooling device, cause cooling water to disappear
Consumption is larger.
CN1883769 discloses the purification method and its device of a kind of chlorine contained exhaust gas, and the method is to introduce chlorine contained exhaust gas
The device that two scrubbing towers and a knockout tower are serially connected, sprays milk of lime, through stone on first, second top of scrubbing tower
The chemical action of the chlorine contained exhaust gas in grey breast and tower, substantially reduces the chlorinity in chlorine contained exhaust gas, reaches purification chlorine contained exhaust gas
Effect, from second scrubbing tower out by the waste gas after purification into carrying out gas-liquid separation in knockout tower, after purification
Waste gas is sent to smoke stack emission from the gas vent on knockout tower top through blower fan.The invention can continuously run aborning, purification
Effect is good.But, the method is used for the treatment of high concentration chlorine contained exhaust gas, and medicament usage amount is big, less economical.
CN200910169676.2 discloses a kind of chloride waste liquid burned waste gas flue gas emergency cooling process and its device, the technique
Chloride waste liquid/waste gas is sent in incinerator, is reacted under being acted on sufficient oxygen in incinerator, it is therein organic
Thing is oxidized and is decomposed into CO2、H2The Cl of O, HCl and denier2Deng high-temperature flue gas are directly entered chilling tower, in the work of cooling water
Less than 90 DEG C are quickly cooled under, air is then discharged by chimney after alkali cleaning is carried out into packed tower.The equipment is main
Including incinerator, incinerator is connected with waste liquid/waste gas supply system, fuel system and combustion-supporting wind system, and incinerator afterbody is also straight
Connect and be connected with chilling tower, chilling tower sprays watery hydrochloric acid and flue gas is cooled down and the HCl in flue gas is absorbed by cooling water ring；Chilling
Tower is connected with packed tower Alkali absorption system.The present invention can effectively reduce the generation of bioxin, meet wanting for environmentally friendly and energy-conservation
Ask.The invention can produce a large amount of absorption waste liquids, and incinerator discharge high-temperature flue gas need to enter chilling tower by temperature cooling 90
, it is necessary to set special cooling device below DEG C, and a large amount of cooling waters can be expended.
Teng Fuhua etc.（Heat accumulation type thermal oxidation stove processes doctorization waste gas, China environmental protection industry, the 4th phase in 2015）Using accumulation of heat
Formula thermal oxidation furnace（RTO）The volatile organic waste gas for the treatment of doctorization industry discharge, the waste gas that workshop produces is drawn after pretreatment by master
Blower fan send 1# caustic wash towers, most of hydrogen chloride is removed, to reduce the corrosion to follow-up equipment；Then through spark arrester, blocking may
The tempering of generation, it is to avoid security incident；PP surge tanks are entered back into, surge tank plays gas mixing, buffering and venting of dust explosion；Then give up
Gas send the RTO to carry out burning disposal through air blower；Waste gas after burning is sour through lowering the temperature and removing by water cooling tower, 2# caustic wash towers
After property gas, aiutage qualified discharge is sent by outlet blower fan.VOCs on-line detectors are installed on the house steward before main induced draft fan, when
Detect exhaust gas inlet excessive concentration（More than 5000ppm）When, make waste gas send activated carbon to inhale by main induced draft fan by valve transfer
Attached tower, through the emergent discharge of aiutage.But, the invention can not only produce a large amount of absorption waste liquids, and incinerator discharge high temperature cigarette
Gas-liquid needs to enter water cooling tower, enters back into caustic wash tower, it is necessary to set special cooling device, and need to expend a large amount of cooling waters.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of chloride organic exhaust gas of high concentration integrated conduct method and
Device.The present invention processes the chloride organic exhaust gas of high concentration using regenerative oxidation, takes out part high-temperature gas and is generated electricity into Stirling
It is used for the electrochemical regeneration of subsequent absorption waste liquid afterwards, the alkali lye that regeneration is obtained returns to absorption tower and recycles, and purified gas can reach
Mark discharge, and the waste of big energy is not resulted in, subsequent treatment will not produce a large amount of suctions also without cooling device is set
Waste liquid is received, economy is significantly improved.
The integrated conduct method of the chloride organic exhaust gas of high concentration of the present invention, including following content：
（1）The chloride organic exhaust gas of high concentration are passed through in regenerative oxidation reactor and are aoxidized, control oxidation bed exhanst gas outlet
Temperature is below 100 DEG C；
（2）The high-temperature flue gas obtained after regenerative oxidation except for maintain Self-heat-storage react energy balance in addition to, remainder from
Regenerative oxidation reactor middle part high-temperature region is drawn and enters stirling generator generating, and flue gas exit temperature is 100 after controlling to generate electricity
Below DEG C；
（3）By step（1）With（2）Alkali liquor absorption tower is sent into after the flue gas mixing of discharge, the sour gas in flue gas is inhaled completely
Receive, and after flue-gas temperature is reduced to less than 60 DEG C, purified gas qualified discharge；
（4）Step（3）The absorption waste liquid of generation enters electrochemical regeneration device, and the NaOH solution that regeneration is obtained returns to alkali cleaning absorption tower
Recycle.
In the present invention, the total hydrocarbon concentration of described chloride organic exhaust gas is more than 6000mg/Nm3, preferably 7000-
15000mg/Nm3, chloride organic exhaust gas are preferably the organic exhaust gas containing chlorobenzene.
In the present invention, step（1）Described in regenerative oxidation reactor include 2-3 accumulation of heat bed, can enter according to sequential
Row switching, so as to carry out accumulation of heat-exothermic process.According to the difference of chlorinated organics species and concentration in waste gas, oxidation can be changed
Temperature range, general control oxidizing temperature is 500-1200 DEG C, preferably 600-900 DEG C.In order to maintain what Self-heat-storage reacted
Energy balance, the temperature of exiting flue gas is unsuitable too high, and it is 40-90 DEG C generally to control oxidation bed flue gas exit temperature, preferably
50-80℃.Chlorinated organics in waste gas are obtained containing CO after exhaustive oxidation2、H2The acidic flue gas of O, HCl etc., in order to avoid two
Secondary pollution is, it is necessary to further treatment.
In the present invention, step（2）The high-temperature flue gas obtained after middle regenerative oxidation are except the energy for maintaining Self-heat-storage to react
Amount balance external, remainder can draw from the middle part high-temperature region of regenerative oxidation reactor and enter stirling generator and generate electricity,
Because chlorinated organics species is different with concentration in waste gas, the high-temperature flue-gas obtained after its complete oxidation are different, can be set
Multiple Stirling generating sets, make high-temperature flue-gas be reduced to less than 100 DEG C.It is total in due to the chloride organic exhaust gas of high concentration
Hydrocarbon concentration is higher, if the high-temperature flue gas after oxidation are completely used for follow-up exothermic process, can cause that flue gas exit temperature is too high, no
The waste of big energy during regenerative oxidation is only caused, and high-temperature flue gas can reduce absorption efficiency into caustic wash unit,
Need to set special cooling device before into alkali liquor absorption tower, consume substantial amounts of cooling water.Therefore, the present invention is from regenerative oxidation
The middle part high-temperature region of reactor is drawn and enters stirling generator generating, can not only be maintained accumulation of heat to react the energy of itself and be put down
Weighing apparatus, reduces exit gas temperature, and heat energy can be changed into electric energy for the regeneration of subsequent absorption waste liquid, it is to avoid energy
Waste.
In the present invention, chlorinated organics in waste gas are obtained containing CO after exhaustive oxidation2、H2The acidic flue gas of O, HCl etc.,
Enter in alkali liquor absorption tower after the flue gas that regenerative oxidation reactor and stirling generator are discharged is mixed, can be flue gas wet type
Various common forms, such as packed tower, sieve-plate tower, void tower in desulfurization industry.Preferably using NaOH alkali lye carries out cooling absorption, inhales
The control of liquid pH value is received more than 7, the HCl gases in flue gas are fully absorbed, and after flue-gas temperature is reduced to less than 60 DEG C,
The salinity of absorbing liquid is set to control in the range of 5wt%-20wt% simultaneously.
In the present invention, step（4）In electrochemical regeneration device use film electrolysis reactor, anionic membrane is set in electrolytic cell
And cationic membrane, whole electrolytic cell is separated into anion groove, three regions of medial launder and cation groove, the cation groove and
Positive electrode and negative electrode are placed in anion groove respectively, two electrodes are connected with the positive pole and negative pole of dc source respectively.Step
（2）The electric energy of stirling generator output is used by after rectification voltage regulator treatment for above-mentioned electrolytic process.When electrolytic cell goes into operation,
It is 5wt%-20wt%NaCl solution, 0.4wt%-3wt% that initial concentration is respectively in the medial launder, anion groove, cation groove
NaOH solution and 0.3wt%-2wt%HCl solution.Electrolytic condition is as follows：Temperature is normal temperature, and voltage is 2.5-5V, and current density is
40-100A/m2.The amount for entering the absorption waste liquid of medial launder by adjusting keeps medial launder NaCl concentration for 5wt%-20wt%.
Anode reaction generates oxygen and hydrochloric acid, and hydrogen and NaOH solution are generated in cathode reaction, wherein regeneration NaOH solution concentration is 5%-
15%, return to step（3）In carry out alkali lye and recycle, if the alkali lye that regeneration is obtained cannot meet absorption needs, can be with
It is used for alkali liquor absorption after mixing with a certain amount of fresh alkali lye, meets and absorb requirement.Wherein, in electrolytic cell anode, negative electrode
Specific reaction is as follows：
Electric energy needed for being wherein electrolysed is partly or fully originate from step（2）In stirling generator.
The present invention uses the Integrated Processing Unit of the chloride organic exhaust gas of high concentration of above-mentioned handling process, including regenerative oxidation
It is chloride that reactor, stirling generator, alkali liquor absorption tower and electrochemical regeneration device, wherein regenerative oxidation reactor are used for high concentration
The oxidation processes of organic exhaust gas, the high-temperature flue gas obtained after regenerative oxidation are except the energy balance for maintaining Self-heat-storage to react
Outward, remainder is drawn from the middle part high-temperature region of regenerative oxidation reactor and enters stirling generator generating, alkali liquor absorption tower
For carrying out absorption treatment, purified gas qualified discharge, electrification to the flue gas that regenerative oxidation reactor and stirling generator are discharged
Learning regenerator is used for the regeneration treatment of the absorption waste liquid that alkali liquor absorption is produced, and the electric energy needed for electrolytic regeneration is partly or entirely originated
In stirling generator, the NaOH solution that regeneration is obtained returns to alkali cleaning absorption tower and recycles.Wherein described regenerative oxidation reaction
Device includes 2-3 accumulation of heat bed.Because chlorinated organics species is different with concentration in waste gas, the high temperature obtained after its complete oxidation
Flue-gas temperature is different, and multiple Stirling generating set can be set, and high-temperature flue-gas is reduced to less than 100 DEG C.
The chloride organic exhaust gas of high concentration after being processed through the inventive method, its chloride removal efficiency reaches more than 99.9%, non-
Methane total hydrocarbon emissions concentration is less than 50mg/Nm3, dioxin emissions concentration is less than 0.2ngTEQ/m3.Simultaneously self generating by again
It is raw to absorb waste liquid, NaOH consumptions, and by-product sulfuric acid, oxygen and hydrogen are greatly reduced, considerably reduce plant running cost.
Sewage effluent salt content is less than 0.1wt%, greatly reduces secondary pollution.
The present invention generates electricity into Stirling and fills from the middle part high-temperature region extension high-temperature flue gas of regenerative oxidation reactor
Put, remaining flue gas is enough to maintain regenerative oxidation to react required energy, produced after aoxidizing the tail gas containing HCl and Stirling generating for producing
The mixing of discharge gas after enter alkali liquor absorption tower, the absorption waste liquid of generation enters electrochemical regeneration device, and the NaOH that regeneration is obtained is molten
Liquid returns to alkali cleaning absorption cycle and utilizes.The present invention can produce more high-grade heat energy and obtain economic effect while waste gas is purified
The electric energy that benefit, wherein electrochemical regeneration need removes the energy for maintaining accumulation of heat reaction to need during being mainly derived from regenerative oxidation
Outward, unnecessary high-temperature flue gas enter the electric energy that Stirling generating set is produced.Handling process of the invention solve regenerative oxidation-
Caused a large amount of energy dissipations, absorption efficiency reduction and produce and a large amount of absorb waste liquids during the alkali cleaning treatment chloride organic exhaust gas of high concentration
The problems such as, the use of whole exhaust treatment system has been obtained great optimization, greatly reduce exhaust-gas treatment cost.
Brief description of the drawings
Fig. 1 is a kind of process chart of the inventive method；
Wherein：1- regenerative oxidation reactors, 2- stirling generators, 3- switch valves, 4- alkali liquor absorption towers, 5- rectifying and pressure-regulatings
Device, 6- film electrolysis reactors, 7- cationic membranes, 8- anionic membranes, the fresh alkali lye of 9-, 10- positive electrodes, 11- negative electrodes；12- is high
The chloride organic exhaust gas of concentration, 13- high-temperature flue gas, flue gas after 14- generatings discharges flue gas after 15- regenerative oxidations, 16- enters absorption tower
Flue gas, 17- Stirlings generate electricity, 18- purified gas, 19- absorption waste liquids, 20- discharge liquors, 21- hydrochloric acid, 22- oxygen, 23- hydrogen,
24- regenerates alkali lye.
Specific embodiment
With reference to embodiment the present invention is furture elucidated method and effect.In the present invention, wt% is mass fraction.
The integrated treatment of the chloride organic exhaust gas of high concentration is carried out using flow and device as shown in Figure 1.High concentration is contained
Chlorine organic exhaust gas 12 are aoxidized in being passed through regenerative oxidation reactor 1, and regenerative oxidation reactor 1 includes two accumulation of heat beds,
Switched over by switching valve 3 according to sequential, so as to carry out accumulation of heat-exothermic process.According to chlorinated organics species in waste gas
Difference, can change oxidizing temperature scope, and general oxidizing temperature is 500-1200 DEG C, preferably 600-900 DEG C.Regenerative oxidation heel row
The temperature for putting flue gas 15 is 40-90 DEG C, preferably 50-80 DEG C.The high-temperature flue gas obtained after regenerative oxidation are removed and meet Self-heat-storage
Reaction energy balance external, remaining high-temperature flue gas 13 are passed through stirling generator 2 and are generated electricity after taking out, flue gas after control generating
14 temperature controls are below 100 DEG C.Chlorinated organics in waste gas are obtained CO after exhaustive oxidation2、H2O, HCl etc., after generating
Discharged after flue gas 14 and regenerative oxidation in the mixed feeding alkali liquor absorption of flue gas 16 tower 4 of flue gas 15, carried out using NaOH alkali lye
Cooling is absorbed, and the HCl gases in flue gas are fully absorbed, and after flue-gas temperature is reduced to less than 60 DEG C, purifying smoke 18
Realize qualified discharge.Absorbing liquid pH value is controlled more than 7, and salinity is controlled in the range of 5wt%-20wt%.The absorption of generation is given up
Liquid 19 carries out setting cationic membrane 7 and anionic membrane 8 in cell reaction, electrolytic cell and by entirely into film electrolysis reactor 6 is interior
Electrolytic cell 6 is separated into cation groove, three regions of medial launder and anion groove, is put respectively in the anion groove and cation groove
Negative electrode 10 and positive electrode 11 are put, two electrodes are connected with the negative pole and positive pole of dc source respectively, stirling generator output
Electric energy by rectification voltage regulator 5 treatment after used for above-mentioned electrolytic process.
When film electrolysis reactor 6 runs, the medial launder, anion groove, cation groove are respectively initial concentration for 5wt%-
20wt%NaCl solution, 0.4wt%-3wt%NaOH solution and 0.3wt%-2wt%HCl solution.Electrolytic condition is as follows：Normal temperature, voltage：
2.5-5V；Current density：40-100A/m2.Enter the NaCl salt of the amount holding medial launder that medial launder absorbs waste liquid 19 by adjusting
Concentration is 5wt%-20wt%.Hydrochloric acid 21 and oxygen 22 are generated in anode reaction, in cathode reaction generation hydrogen 26 and regeneration alkali lye
24.When the alkali lye 24 that regeneration is obtained cannot meet alkali cleaning needs, a certain amount of fresh soda 9 is mixed into as supplement.
Embodiment 1
Certain chemical plant chlorobenzene vavuum pump emission, tolerance is 7865Nm3/ h, temperature is normal temperature, and pressure is normal pressure, waste gas composition
It is as follows：
Processed using the inventive method and device, waste gas enters regenerative oxidation reactor first, oxidizing temperature is 600 DEG C,
Oxidation bed flue gas exit temperature is 50 DEG C of high-temperature flue gas parts obtained after aoxidizing for accumulation of heat reaction energy self-balancing, one
Part high-temperature gas enters stirling generator and is generated electricity, and flue gas exit temperature is 50 DEG C after controlling to generate electricity, and generated energy is
35kwh, this electricity is passed through the NaOH alkali lye of renewable 10kg/h after film electrolysis reactor.And flue gas and the Stirling hair after aoxidizing
Enter alkali liquor absorption tower after flue gas mixing after electricity, flue-gas temperature is reduced to 40 DEG C, purifying smoke qualified discharge；Institute's alkali needed
It is 5kg/h, the need for can meeting alkali liquor absorption completely.Wherein electrolytic cell medial launder, anion groove, cation groove are initial dense respectively
It is 5wt%NaCl solution, 1wt%NaOH solution and 1wt%HCl solution to spend, and electrolytic condition is as follows：Normal temperature；Voltage：2.5V；Electric current is close
Degree：50A/m2.The absorption waste liquid amount for entering medial launder by adjusting keeps medial launder NaCl salinity for 5wt%.At the present invention
Waste gas after reason, its chloride removal efficiency reaches more than 99.9%, and non-methane hydrocarbon emission concentration is less than 50mg/Nm3, bioxin
Concentration of emission is less than 0.2ngTEQ/m3.Simultaneously by self generating regenerable absorbent waste liquid, NaOH consumptions are greatly reduced, and it is secondary
Sulfuric acid, oxygen and hydrogen are produced, plant running cost is considerably reduced；Sewage effluent salt content is less than 0.1wt%, greatly reduces
Secondary pollution.
Embodiment 2
Certain chemical plant chlor-alkali devices emission, tolerance is 12000Nm3/ h, temperature is normal temperature, and pressure is normal pressure, waste gas composition
It is as follows：
Processed using the inventive method and device, waste gas enters regenerative oxidation reactor first, oxidizing temperature is 700 DEG C,
Oxidation bed flue gas exit temperature is 60 DEG C of high-temperature flue gas parts obtained after aoxidizing for accumulation of heat reaction energy self-balancing, one
Part high-temperature gas enters stirling generator and is generated electricity, and flue gas exit temperature is 90 DEG C after controlling to generate electricity, and generated energy is
93kwh, this electricity is passed through the NaOH alkali lye of renewable 27kg/h after film electrolysis reactor.And flue gas and the Stirling hair after aoxidizing
Enter alkali liquor absorption tower after flue gas mixing after electricity, flue-gas temperature is reduced to 50 DEG C, purifying smoke qualified discharge；Institute's alkali needed
It is 19kg/h, the need for can meeting alkali liquor absorption completely.Medial launder, anion groove, cation groove are first respectively wherein in electrolytic cell
Beginning concentration is 10wt%NaCl solution, 2wt%NaOH solution and 2wt%HCl solution, and electrolytic condition is as follows：Normal temperature；Voltage：3V；Electricity
Current density：70A/m2.The absorption waste liquid amount for entering medial launder by adjusting keeps medial launder NaCl salinity for 10wt%.Through this
Waste gas after invention treatment, its chloride removal efficiency reaches more than 99.9%, and non-methane hydrocarbon emission concentration is less than 50mg/Nm3,
Dioxin emission concentration is less than 0.2ngTEQ/m3.Simultaneously by self generating regenerable absorbent waste liquid, NaOH use is greatly reduced
Amount, and by-product sulfuric acid, oxygen and hydrogen, considerably reduce plant running cost；Sewage effluent salt content is less than 0.1wt%, greatly
Reduce secondary pollution greatly.
Embodiment 3
Certain chemical plant chlor-alkali devices emission, tolerance is 10000Nm3/ h, temperature is normal temperature, and pressure is normal pressure, waste gas composition
It is as follows：
Processed using the inventive method and device, waste gas enters regenerative oxidation reactor first, oxidizing temperature is 1000 DEG C,
Oxidation bed flue gas exit temperature is 80 DEG C, and the high-temperature flue gas part obtained after oxidation is used for accumulation of heat reaction energy self-balancing,
A part of high-temperature gas enters stirling generator and is generated electricity, and flue gas exit temperature is 80 DEG C after controlling to generate electricity, and generated energy is
114kwh, this electricity is passed through the NaOH alkali lye of renewable 32kg/h after film electrolysis reactor.And flue gas and Stirling after aoxidizing
Enter alkali liquor absorption tower after flue gas mixing after generating, flue-gas temperature is reduced to 50 DEG C, purifying smoke qualified discharge；Required alkali
It is 20kg/h to measure, the need for can meeting alkali liquor absorption completely.Medial launder, anion groove, cation groove difference wherein in electrolytic cell
Initial concentration is 20wt%NaCl solution, 3wt%NaOH solution and 2wt%HCl solution, and electrolytic condition is as follows：Normal temperature；Voltage：5V；
Current density：90A/m2.The absorption waste liquid amount for entering medial launder by adjusting keeps medial launder NaCl salinity for 20wt%.Through
Waste gas after present invention treatment, its chloride removal efficiency reaches more than 99.9%, and non-methane hydrocarbon emission concentration is less than 50mg/
Nm3, dioxin emissions concentration is less than 0.2ngTEQ/m3.Simultaneously by self generating regenerable absorbent waste liquid, NaOH is greatly reduced
Consumption, and by-product sulfuric acid, oxygen and hydrogen, considerably reduce plant running cost；Sewage effluent salt content is less than 0.1wt%,
Greatly reduce secondary pollution.
Comparative example 1
With operating condition with embodiment 1, difference is handling process：Part high-temperature gas is not taken out enters Stirling generating
Machine generates electricity, and oxidation bed flue gas exit temperature is 150 DEG C, if being directly entered alkali liquor absorption tower, flue-gas temperature is reduced to 50
DEG C, purifying smoke qualified discharge, required fresh alkali number is 5kg/h, produces substantial amounts of absorption waste liquid, and salinity is up in waste liquid
10%.The technique not only wastes the amount of heat of oxidizing process generation, and also reduces alkali liquor absorption efficiency, increases alkali lye
Consumption, generates a large amount of high-salt wastewaters.
Comparative example 2
With operating condition with embodiment 2, difference is handling process：The concentration of chlorobenzene is 0.42 in chloride organic exhaust gas
(5400mg/Nm3), oxidation bed flue gas exit temperature is 70 DEG C, because the temperature can be only used for accumulation of heat fireworks reaction energy
Self-balancing, therefore it is not suitable for this PROCESS FOR TREATMENT.
Comparative example 3
With operating condition with embodiment 3, difference is handling process：Electrolysis reactor does not use film electrolysis reactor, only
Positive electrode and negative electrode are set.Flue gas exit temperature is 80 DEG C after controlling to generate electricity, and generated energy is 114kwh, and this electricity is passed through film electricity
The NaOH alkali lye of renewable 12kg/h after solution reactor, it is impossible to meet the requirement that follow-up institute's alkali needed is 20kg/h.
Claims (15)
1. the integrated conduct method of the chloride organic exhaust gas of a kind of high concentration, it is characterised in that including following content：
（1）The chloride organic exhaust gas of high concentration are passed through in regenerative oxidation reactor and are aoxidized, control oxidation bed exhanst gas outlet
Temperature is below 100 DEG C；
（2）The high-temperature flue gas obtained after regenerative oxidation except for maintain Self-heat-storage react energy balance in addition to, remainder from
Regenerative oxidation reactor middle part high-temperature region is drawn and enters stirling generator generating, and flue gas exit temperature is 100 after controlling to generate electricity
Below DEG C；
（3）By step（1）With（2）Alkali liquor absorption tower is sent into after the flue gas mixing of discharge, the sour gas in flue gas is inhaled completely
Receive, and flue-gas temperature is reduced to less than 60 DEG C, purified gas qualified discharge；
（4）Step（3）The absorption waste liquid of generation enters electrochemical regeneration device, and the NaOH solution that regeneration is obtained returns to alkali cleaning absorption tower
Recycle.
2. method according to claim 1, it is characterised in that：The total hydrocarbon concentration of described chloride organic exhaust gas is 7000-
15000mg/Nm3, chloride organic exhaust gas are the organic exhaust gas containing chlorobenzene.
3. method according to claim 1, it is characterised in that：Step（1）Described in regenerative oxidation reactor include 2-3
Accumulation of heat bed, can switch over according to sequential, so as to carry out accumulation of heat-exothermic process.
4. method according to claim 1, it is characterised in that：Step（1）It is middle according to chlorinated organics species in waste gas and
The difference of concentration, controls oxidizing temperature for 500-1200 DEG C, and it is 40-90 DEG C to control oxidation bed flue gas exit temperature.
5. method according to claim 1, it is characterised in that：Step（1）It is middle that to control oxidizing temperature be 600-900 DEG C,
It is 50-80 DEG C to control oxidation bed flue gas exit temperature.
6. method according to claim 1, it is characterised in that：Step（2）It is middle that multiple Stirling generating sets are set, make height
Warm flue-gas temperature is reduced to less than 100 DEG C.
7. method according to claim 1, it is characterised in that：Step（3）Middle alkali liquor absorption tower be packed tower, sieve-plate tower or
Void tower, cooling absorption is carried out using NaOH alkali lye.
8. method according to claim 1, it is characterised in that：Step（3）Middle absorbing liquid pH value is controlled more than 7, cigarette
HCl gases in gas are fully absorbed, and after flue-gas temperature is reduced to less than 60 DEG C, while controlling the salinity of absorbing liquid
In the range of 5wt%-20wt%.
9. method according to claim 1, it is characterised in that：Step（4）In electrochemical regeneration device it is anti-using film electrolysis
Answer and anionic membrane and cationic membrane are set in device, electrolytic cell, whole electrolytic cell is separated into anion groove, medial launder and cation
Three regions of groove, place positive electrode and negative electrode respectively in the cation groove and anion groove, two electrodes are respectively and direct current
Positive pole and the negative pole connection of power supply.
10. method according to claim 9, it is characterised in that：When electrolytic cell goes into operation, the medial launder, anion groove, sun
It is 5wt%-20wt%NaCl solution, 0.4wt%-3wt%NaOH solution and 0.3wt%-2wt% that initial concentration is respectively in ion groove
HCl solution.
11. method according to claim 1,9 or 10, it is characterised in that：Electrolytic condition is as follows：Temperature is normal temperature, voltage
It is 2.5-5V, current density is 40-100A/m2。
12. method according to claim 9 or 10, it is characterised in that：Enter the absorption waste liquid of medial launder by adjusting
It is 5wt%-20wt% that amount keeps medial launder NaCl concentration.
13. method according to claim 9 or 10, it is characterised in that：Oxygen and hydrochloric acid are generated in anode reaction, in negative electrode
Reaction generation hydrogen and NaOH solution, wherein regeneration NaOH solution concentration is 5%-15%, return to step（3）In carry out alkali lye and follow
Ring is utilized.
14. method according to claim 1,9 or 10, it is characterised in that：Electric energy needed for electrolysis is partly or entirely originated
In step（2）In stirling generator.
The Integrated Processing Unit of the 15. chloride organic exhaust gas of high concentration for using the claim any methods describeds of 1-14, its feature
It is to include regenerative oxidation reactor, stirling generator, alkali liquor absorption tower and electrochemical regeneration device, wherein regenerative oxidation reaction
Device is used for the oxidation processes of the chloride organic exhaust gas of high concentration, and the high-temperature flue gas obtained after regenerative oxidation are except for maintaining Self-heat-storage
Reaction energy balance external, remainder is drawn from the middle part high-temperature region of regenerative oxidation reactor and enters stirling generator hair
Electricity, alkali liquor absorption tower is used to carry out absorption treatment, purified gas to the flue gas that regenerative oxidation reactor and stirling generator are discharged
Qualified discharge, electrochemical regeneration device is used for the regeneration treatment of the absorption waste liquid that alkali liquor absorption is produced, the electric energy needed for electrolytic regeneration
Stirling generator is partly or fully originate from, the NaOH solution that regeneration is obtained returns to alkali cleaning absorption tower and recycles.
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| CN108726740A (en) * | 2018-06-11 | 2018-11-02 | 山东龙安泰环保科技有限公司 | A kind of high sodium chloride waste water Zero discharge treatment method |
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