CN106731562B - A kind of integrated conduct method and device of high concentration organic exhaust gas containing chlorine - Google Patents
A kind of integrated conduct method and device of high concentration organic exhaust gas containing chlorine Download PDFInfo
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- CN106731562B CN106731562B CN201510800826.0A CN201510800826A CN106731562B CN 106731562 B CN106731562 B CN 106731562B CN 201510800826 A CN201510800826 A CN 201510800826A CN 106731562 B CN106731562 B CN 106731562B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
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- B01D53/34—Chemical or biological purification of waste gases
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses a kind of integrated conduct methods of high concentration organic exhaust gas containing chlorine, including (1), and exhaust gas to be passed through in regenerative oxidation reactor and is aoxidized, and control oxidation bed flue gas exit temperature is at 100 DEG C or less；(2) high-temperature flue gas obtained after regenerative oxidation is removed for maintaining Self-heat-storage reaction energy balance external, and rest part is drawn from the middle part high-temperature region of reactor enters stirling generator, and flue gas exit temperature is at 100 DEG C or less after control power generation；(3) it is sent into lye absorption tower after mixing the flue gas that step (1) and (2) are discharged, the sour gas in flue gas is fully absorbed, and flue-gas temperature is made to be reduced to 60 DEG C hereinafter, purified gas qualified discharge；(4) it absorbs waste liquid and enters electrochemical regeneration device, regeneration lye returns to alkali cleaning absorption tower and recycles.Treated that purified gas can be with qualified discharge by the present invention, and not will cause the waste of a large amount of energy, and subsequent processing does not need setting cooling device yet, will not generate it is a large amount of absorb waste liquids, economy significantly improves.
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 high concentration organic exhaust gas containing chlorine
Manage method and device.
Background technique
In chlorine industry production process, organic exhaust gas containing chlorine can be generated.Organic exhaust gas containing chlorine is a kind of severe pollutant,
Wherein chlorinated aromatic hydrocarbons have bio-toxicity, and chemical property is stablized, it is difficult to be biodegradable, persistently be detained in the environment, to life
State environmental and human health impacts constitute a serious threat.The economic personal casualty loss due to caused by the leakage of organic exhaust gas containing chlorine exists in recent years
It happens occasionally all over the world.
Solid absorption-analytic method, catalytic oxidation, thermal decomposition method are roughly divided into for the processing technique of the organic exhaust gas containing chlorine
The methods of.Solid absorption-analytic method primary sorbent is active carbon, and absorbing the existing physical absorption of organic chloride also has chemistry
Absorption, MODEL OF CHEMICAL ABSORPTION PROCESS not only changes the functional group of active carbon, and destroys the structure of charcoal crystal, therefore actual
In industrial application, in order to keep higher removal rate, need to be continuously added fresh active carbon.The operation temperature of catalytic oxidation
Generally at 100-300 DEG C, dioxin generation is had at this temperature, is made a big impact to environmental and human health impacts.Thermal decomposition
Method carries out oxygenolysis to it using regenerative oxidation, and oxidizing temperature can reach 800 DEG C or more, can be avoided the life of dioxin
At.However, the HCl gas that oxidation generates is unable to direct emission, need to carry out alkali cleaning to it, can not only generate a large amount of absorb and give up
Liquid, and in organic exhaust gas containing chlorine organic concentration change its exhaust temperature after regenerative oxidation is handled and be all different, when
When chloride concentration is higher, inevitably cause the exhaust temperature generated after regenerative oxidation excessively high, high-temperature flue gas enters alkali cleaning
Unit can reduce absorption efficiency, cause the waste of big energy, it usually needs set special cooling device, cooling water is caused to disappear
Consumption is larger.
CN1883769 discloses the purification method and its device of a kind of chlorine contained exhaust gas, and this 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 on the top of first, second scrubbing tower, through stone
The chemical action of grey cream and the chlorine contained exhaust gas in tower, substantially reduces the chlorinity in chlorine contained exhaust gas, reaches purification chlorine contained exhaust gas
Effect, entering by purified exhaust gas for coming out from second scrubbing tower carries out gas-liquid separation in knockout tower, purified
Exhaust gas is sent to smoke stack emission through blower from the gas vent on knockout tower top.The invention in production can continuous operation, purification
Effect is good.But this method is used for the processing of high concentration chlorine contained exhaust gas, pharmaceutical use is big, less economical.
CN200910169676.2 discloses one kind burned waste gas flue gas emergency cooling process of waste liquid containing chlorine and its device, the technique
Chlorine waste liquid/exhaust gas will be contained to be sent in incinerator, reacted in incinerator under sufficient oxygen effect, it is therein organic
Object, which is oxidized, is decomposed into CO2、H2O, the Cl of HCl and denier2Deng high-temperature flue gas is directly entered chilling tower, in the work of cooling water
90 DEG C are quickly cooled under hereinafter, atmosphere then is discharged by chimney after carrying out alkali cleaning into packed tower.The equipment is main
Including incinerator, incinerator is connect with waste liquid/exhaust gas supply system, fuel system and combustion-supporting wind system, and incinerator tail portion is also straight
It connects and is connect with chilling tower, chilling tower sprays dilute hydrochloric acid by cooling water ring and cooled down to flue gas and absorb the HCl in flue gas；Chilling
Tower is connected with packed tower Alkali absorption system.The present invention can effectively reduce the generation of dioxin, meet environmental protection and want with energy-efficient
It asks.The invention can generate a large amount of absorption waste liquids, and incinerator discharge high-temperature flue gas needs to enter chilling tower for temperature cooling 90
DEG C hereinafter, need to be arranged special cooling device, and a large amount of cooling waters can be expended.
Teng Fuhua etc. (heat accumulation type thermal oxidation furnace handles doctorization exhaust gas, China environmental protection industry, the 4th phase in 2015) uses accumulation of heat
Formula thermal oxidation furnace (RTO) handles the volatile organic waste gas of doctorization industry discharge, and the exhaust gas that workshop generates is drawn after pretreatment by master
Blower send 1# caustic wash tower, removes most of hydrogen chloride, to reduce the corrosion to follow-up equipment；Then through fire arrester, blocking may
The tempering of generation, avoids safety accident；PP surge tank is entered back into, surge tank plays gas mixing, buffering and venting of dust explosion；Then it gives up
Gas send RTO to carry out burning disposal through air blower；Exhaust gas after burning is cooled down by water cooling tower, 2# caustic wash tower and removes acid
After property gas, exhaust tube qualified discharge is sent by outlet blower.VOCs on-line detector is installed on the general pipeline before main induced draft fan, when
When detecting exhaust gas inlet excessive concentration (more than 5000ppm), exhaust gas is set to send active carbon to inhale by main induced draft fan by valve transfer
Attached tower is met an urgent need through exhaust tube and is discharged.But the invention can not only generate a large amount of absorption waste liquids, but also high temperature cigarette is discharged in incinerator
Gas-liquid needs to enter water cooling tower, enters back into caustic wash tower, needs to be arranged special cooling device, and need to expend a large amount of cooling waters.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of integrated conduct method of high concentration organic exhaust gas containing chlorine and
Device.The present invention handles high concentration organic exhaust gas containing chlorine using regenerative oxidation, takes out part high-temperature gas and enters Stirling power generation
It is used for the electrochemical regeneration of subsequent absorption waste liquid afterwards, the lye regenerated to return to absorption tower and recycles, and purified gas can reach
Mark discharge, and not will cause the waste of a large amount of energy, subsequent processing does not need setting cooling device yet, will not generate a large amount of suctions
Waste liquid is received, economy significantly improves.
The integrated conduct method of high concentration organic exhaust gas containing chlorine of the present invention, including following content:
(1) high concentration organic exhaust gas containing chlorine is passed through in regenerative oxidation reactor and is aoxidized, control oxidation bed flue gas
Outlet temperature is at 100 DEG C or less；
(2) high-temperature flue gas obtained after regenerative oxidation is in addition to the energy balance for maintaining Self-heat-storage to react, remaining part
Divide to draw from high-temperature region in the middle part of regenerative oxidation reactor and enter stirling generator power generation, flue gas exit temperature exists after controlling power generation
100 DEG C or less；
(3) lye absorption tower is sent into after mixing the flue gas that step (1) and (2) are discharged, the sour gas in flue gas is complete
Hypersorption, and after so that flue-gas temperature is reduced to 60 DEG C or less, purified gas qualified discharge；
(4) the absorption waste liquid that step (3) generates enters electrochemical regeneration device, and the NaOH solution regenerated returns to alkali cleaning and inhales
Tower is received to recycle.
In the present invention, the total hydrocarbon concentration of the organic exhaust gas containing chlorine is greater than 6000mg/Nm3, preferably 7000-
15000mg/Nm3, organic exhaust gas containing chlorine is preferably the organic exhaust gas containing chlorobenzene.
In the present invention, regenerative oxidation reactor described in step (1) includes 2-3 accumulation of heat bed, can according to timing into
Row switching, to carry out accumulation of heat-exothermic process.According to the difference of chlorinated organics type and concentration in exhaust gas, oxidation can be changed
Temperature range, general control oxidizing temperature are 500-1200 DEG C, preferably 600-900 DEG C.In order to maintain Self-heat-storage to react
Energy balance, the temperature of exiting flue gas is unsuitable excessively high, and usually control oxidation bed flue gas exit temperature is 40-90 DEG C, preferably
50-80℃.Chlorinated organics in exhaust gas are obtained after exhaustive oxidation containing CO2、H2O, the acidic flue gas of HCl etc., in order to avoid two
Secondary pollution needs to be further processed.
In the present invention, the high-temperature flue gas obtained after regenerative oxidation in step (2) removes the energy for maintaining Self-heat-storage to react
Balance external is measured, stirling generator power generation can be drawn from the middle part high-temperature region of regenerative oxidation reactor and be entered to rest part,
Due to chlorinated organics type in exhaust gas and concentration difference, the high-temperature flue-gas obtained after complete oxidation is different, settable
Multiple Stirling generating sets make high-temperature flue-gas be reduced to 100 DEG C or less.Due to total in high concentration organic exhaust gas containing chlorine
Hydrocarbon concentration is higher, if the high-temperature flue gas after oxidation is completely used for subsequent exothermic process, flue gas exit temperature can be made excessively high, no
The waste of big energy during regenerative oxidation is only caused, and high-temperature flue gas enters caustic wash unit can reduce absorption efficiency,
It needs to be arranged special cooling equipment before into lye absorption tower, consumes a large amount of cooling water.For this purpose, the present invention is from regenerative oxidation
Stirling generator power generation is drawn and entered in the middle part high-temperature region of reactor, and the energy that can not only maintain accumulation of heat to react itself is flat
Weighing apparatus reduces exit gas temperature, and thermal energy can be converted to the regeneration that electric energy is used for subsequent absorption waste liquid, avoids energy
Waste.
In the present invention, the chlorinated organics in exhaust gas are obtained after exhaustive oxidation containing CO2、H2O, the acidic flue gas of HCl etc.,
Enter in lye 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 in desulfurization industry, such as packed tower, sieve-plate tower, void tower.It is preferable to use NaOH lye to carry out cooling absorption, inhales
It receives the control of liquid pH value to fully absorb the HCl gas in flue gas 7 or more, and after making flue-gas temperature be reduced to 60 DEG C or less,
Control the salinity of absorbing liquid within the scope of 5wt%-20wt%.
In the present invention, the electrochemical regeneration device in step (4) uses film electrolysis reactor, and anionic membrane is arranged in electrolytic cell
And cationic membrane, entire electrolytic cell is separated into anion slot, medial launder and cationic three regions of slot, the cation slot and
Positive electrode and negative electrode are placed in anion slot respectively, two electrodes are connected with the anode of DC power supply with cathode respectively.Step
(2) electric energy of stirling generator output uses after rectification voltage regulator is handled for above-mentioned electrolytic process.When electrolytic cell goes into operation,
The medial launder, anion slot be respectively initial concentration in cationic slot are 5wt%-20wt%NaCl solution, 0.4wt%-3wt%
NaOH solution and 0.3wt%-2wt%HCl solution.Electrolytic condition is as follows: temperature is room temperature, voltage 2.5-5V, and current density is
40-100A/m2.Keeping medial launder NaCl concentration by the amount that adjusting enters the absorption waste liquid of medial launder is 5wt%-20wt%.?
Anode reaction generates oxygen and hydrochloric acid, generates hydrogen and NaOH solution in cathode reaction, wherein regeneration NaOH solution concentration is 5%-
15%, it is recycled back to lye is carried out in step (3), it, can be with if the lye that regeneration obtains is unable to satisfy absorption when needing
It is absorbed after being mixed with a certain amount of fresh lye for lye, meets and absorb requirement.Wherein, anode in electrolytic cell, cathode
Specific reaction is as follows:
Wherein it is electrolysed the stirling generator that required electric energy is partly or fully originate from step (2).
The present invention uses the Integrated Processing Unit of high concentration organic exhaust gas containing chlorine of above-mentioned treatment process, including regenerative oxidation
Reactor, stirling generator, lye absorption tower and electrochemical regeneration device, wherein regenerative oxidation reactor contains chlorine for high concentration
The oxidation processes of organic exhaust gas, the high-temperature flue gas obtained after regenerative oxidation remove the energy balance for maintaining Self-heat-storage to react
Outside, rest part draws from the middle part high-temperature region of regenerative oxidation reactor and enters stirling generator power generation, lye absorption tower
Absorption processing, purified gas qualified discharge, electrification are carried out for the flue gas to regenerative oxidation reactor and stirling generator discharge
Learn the regeneration treatment that regenerator absorbs the absorption waste liquid generated for lye, the part or all of source of electric energy needed for electrolytic regeneration
In stirling generator, the NaOH solution regenerated returns to alkali cleaning absorption tower and recycles.The wherein regenerative oxidation reaction
Device includes 2-3 accumulation of heat bed.Since chlorinated organics type in exhaust gas and concentration are different, the high temperature obtained after complete oxidation
Flue-gas temperature is different, and settable multiple Stirling generating sets make high-temperature flue-gas be reduced to 100 DEG C or less.
Through the method for the present invention treated high concentration organic exhaust gas containing chlorine, chloride removal efficiency reaches 99.9% or more, non-
Methane total hydrocarbon emissions concentration is lower than 50mg/Nm3, dioxin concentration is lower than 0.2ngTEQ/m3.Again by self generating simultaneously
It is raw to absorb waste liquid, NaOH dosage, and by-product sulfuric acid, oxygen and hydrogen are greatly reduced, device operating cost is considerably reduced.
Sewage effluent salt content is lower 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
It sets, remaining flue gas is enough energy needed for maintaining regenerative oxidation to react, and the tail gas containing HCl and Stirling for aoxidizing generation generate after generating electricity
The mixing of discharge gas after enter lye absorption tower, the absorption waste liquid of generation enters electrochemical regeneration device, and the NaOH regenerated is molten
Liquid returns to alkali cleaning absorption cycle and utilizes.The present invention can produce more high-grade thermal energy while purifying exhaust gas and obtain economic effect
Benefit, the electric energy that wherein electrochemical regeneration needs remove the energy for maintaining accumulation of heat reaction to need during being mainly derived from regenerative oxidation
Outside, extra high-temperature flue gas enters the electric energy of Stirling generating set generation.Treatment process of the invention solves regenerative oxidation-
Alkali cleaning handles caused a large amount of energy dissipations when high concentration organic exhaust gas containing chlorine, absorption efficiency reduces and generates a large amount of absorption waste liquids
The problems such as, make entire exhaust treatment system with great optimization can have been obtained, greatly reduce exhaust-gas treatment cost.
Detailed description of the invention
Fig. 1 is a kind of process flow chart of the method for the present invention；
Wherein: 1- regenerative oxidation reactor, 2- stirling generator, 3- switch valve, 4- lye absorption tower, 5- rectification are adjusted
Depressor, 6- film electrolysis reactor, 7- cationic membrane, 8- anionic membrane, the fresh lye of 9-, 10- positive electrode, 11- negative electrode；12-
High concentration organic exhaust gas containing chlorine, 13- high-temperature flue gas, flue gas after 14- power generation discharge flue gas after 15- regenerative oxidation, and 16- is into absorption
Tower flue gas, the power generation of 17- Stirling, 18- purified gas, 19- absorption waste liquid, 20- discharge liquor, 21- hydrochloric acid, 22- oxygen, 23- hydrogen,
24- regenerates lye.
Specific embodiment
Below 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 high concentration organic exhaust gas containing chlorine is carried out using process as shown in Figure 1 and device.High concentration is contained
Chlorine organic exhaust gas 12 is passed through in regenerative oxidation reactor 1 and is aoxidized, and regenerative oxidation reactor 1 includes two accumulation of heat beds,
It is switched over according to timing by switching valve 3, to carry out accumulation of heat-exothermic process.According to chlorinated organics type in exhaust gas
Difference, can be changed oxidizing temperature range, 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, which removes, meets Self-heat-storage
Reaction energy balance external, remaining high-temperature flue gas 13 are passed through stirling generator 2 after taking out and generate electricity, flue gas after control power generation
14 temperature are controlled at 100 DEG C or less.Chlorinated organics in exhaust gas are obtained CO after exhaustive oxidation2、H2O, HCl etc., after power generation
The mixed flue gas 16 of flue gas 15 is discharged after flue gas 14 and regenerative oxidation to be sent into lye absorption tower 4, is carried out using NaOH lye
Cooling absorbs, and the HCl gas in flue gas is fully absorbed, and after so that flue-gas temperature is reduced to 60 DEG C or less, purifying smoke 18
Realize qualified discharge.7 or more, salinity controls within the scope of 5wt%-20wt% the control of absorbing liquid pH value.The absorption of generation is useless
Liquid 19 enters progress cell reaction in film electrolysis reactor 6, the interior setting cationic membrane 7 of electrolytic cell and anionic membrane 8 and will be entire
Electrolytic cell 6 is separated into three cationic slot, medial launder and anion slot regions, puts respectively in the anion slot and cationic slot
Negative electrode 10 and positive electrode 11 are set, two electrodes are connected with the cathode of DC power supply and anode respectively, stirling generator output
Electric energy by rectification voltage regulator 5 processing after for above-mentioned electrolytic process use.
When film electrolysis reactor 6 is run, the medial launder, anion slot, cationic slot are respectively that initial concentration is 5wt%-
20wt%NaCl solution, 0.4wt%-3wt%NaOH solution and 0.3wt%-2wt%HCl solution.Electrolytic condition is as follows: room temperature, voltage:
2.5-5V；Current density: 40-100A/m2.Enter the NaCl salt for 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, generates hydrogen 26 and regeneration lye in cathode reaction
24.When the lye 24 that regeneration obtains, which is unable to satisfy alkali cleaning, to be needed, a certain amount of fresh soda 9 is mixed into as supplement.
Embodiment 1
Certain chemical plant chlorobenzene vacuum pump emission, tolerance 7865Nm3/ h, temperature are room temperature, and pressure is normal pressure, exhaust gas
It forms as follows:
It is handled using the method for the present invention and device, exhaust gas enters regenerative oxidation reactor, oxidizing temperature 600 first
DEG C, oxidation bed flue gas exit temperature is that 50 DEG C of high-temperature flue gas a part obtained after aoxidizing are certainly flat for accumulation of heat reaction energy
Weighing apparatus, a part of high-temperature gas are discharged into stirling generator and generate electricity, and flue gas exit temperature is 50 DEG C after control power generation, generated energy
For 35kwh, this electricity is passed through the NaOH lye of renewable 10kg/h after film electrolysis reactor.And flue gas and Stirling after aoxidizing
Enter lye absorption tower after flue gas mixing after power generation, so that flue-gas temperature is reduced to 40 DEG C, purifying smoke qualified discharge；Required alkali
Amount is 5kg/h, can meet the needs of lye absorption completely.Wherein electrolytic cell medial launder, anion slot, cationic slot difference are initial
Concentration is that 5wt%NaCl solution, 1wt%NaOH solution and 1wt%HCl solution, electrolytic condition are as follows: room temperature；Voltage: 2.5V；Electric current
Density: 50A/m2.Keeping medial launder NaCl salinity by the absorption waste liquid amount that adjusting enters medial launder is 5wt%.Through the present invention
Treated exhaust gas, chloride removal efficiency reach 99.9% or more, and non-methane hydrocarbon emission concentration is lower than 50mg/Nm3, two dislike
English concentration of emission is lower than 0.2ngTEQ/m3.Simultaneously by self generating regenerable absorbent waste liquid, NaOH dosage is greatly reduced, and
By-product sulfuric acid, oxygen and hydrogen considerably reduce device operating cost；Sewage effluent salt content is lower than 0.1wt%, subtracts significantly
Secondary pollution is lacked.
Embodiment 2
Certain chemical plant chlor-alkali devices emission, tolerance 12000Nm3/ h, temperature are room temperature, and pressure is normal pressure, exhaust gas
It forms as follows:
It is handled using the method for the present invention and device, exhaust gas enters regenerative oxidation reactor, oxidizing temperature 700 first
DEG C, oxidation bed flue gas exit temperature is that 60 DEG C of high-temperature flue gas a part obtained after aoxidizing are certainly flat for accumulation of heat reaction energy
Weighing apparatus, a part of high-temperature gas are discharged into stirling generator and generate electricity, and flue gas exit temperature is 90 DEG C after control power generation, generated energy
For 93kwh, this electricity is passed through the NaOH lye of renewable 27kg/h after film electrolysis reactor.And flue gas and Stirling after aoxidizing
Enter lye absorption tower after flue gas mixing after power generation, so that flue-gas temperature is reduced to 50 DEG C, purifying smoke qualified discharge；Required alkali
Amount is 19kg/h, can meet the needs of lye absorption completely.Wherein medial launder, anion slot, cationic slot difference in electrolytic cell
Initial concentration is that 10wt%NaCl solution, 2wt%NaOH solution and 2wt%HCl solution, electrolytic condition are as follows: room temperature；Voltage: 3V；
Current density: 70A/m2.Keeping medial launder NaCl salinity by the absorption waste liquid amount that adjusting enters medial launder is 10wt%.Through
The present invention treated exhaust gas, chloride removal efficiency reach 99.9% or more, and non-methane hydrocarbon emission concentration is lower than 50mg/
Nm3, dioxin concentration is lower than 0.2ngTEQ/m3.Simultaneously by self generating regenerable absorbent waste liquid, NaOH is greatly reduced
Dosage, and by-product sulfuric acid, oxygen and hydrogen, considerably reduce device operating cost；Sewage effluent salt content is lower than 0.1wt%,
Greatly reduce secondary pollution.
Embodiment 3
Certain chemical plant chlor-alkali devices emission, tolerance 10000Nm3/ h, temperature are room temperature, and pressure is normal pressure, exhaust gas
It forms as follows:
It is handled using the method for the present invention and device, exhaust gas enters regenerative oxidation reactor first, and oxidizing temperature is
1000 DEG C, oxidation bed flue gas exit temperature is 80 DEG C, and the high-temperature flue gas a part obtained after oxidation is used for accumulation of heat reaction energy
Self-balancing, a part of high-temperature gas are discharged into stirling generator and generate electricity, and flue gas exit temperature is 80 DEG C after control power generation, hair
Electricity is 114kwh, this electricity is passed through the NaOH lye of renewable 32kg/h after film electrolysis reactor.And aoxidize after flue gas and
Enter lye absorption tower after flue gas mixing after Stirling power generation, so that flue-gas temperature is reduced to 50 DEG C, purifying smoke qualified discharge；
Institute's alkali needed is 20kg/h, can meet the needs of lye absorption completely.Wherein medial launder, anion slot, cation in electrolytic cell
It is that 20wt%NaCl solution, 3wt%NaOH solution and 2wt%HCl solution, electrolytic condition are as follows that slot, which distinguishes initial concentration: room temperature；Electricity
Pressure: 5V；Current density: 90A/m2.It is by the absorption waste liquid amount holding medial launder NaCl salinity that adjusting enters medial launder
20wt%.Exhaust gas after processed by the invention, chloride removal efficiency reach 99.9% or more, and non-methane hydrocarbon emission concentration is lower than
50mg/Nm3, dioxin concentration is lower than 0.2ngTEQ/m3.Simultaneously by self generating regenerable absorbent waste liquid, greatly reduce
NaOH dosage, and by-product sulfuric acid, oxygen and hydrogen, considerably reduce device operating cost；Sewage effluent salt content is lower than
0.1wt% greatly reduces secondary pollution.
Comparative example 1
Treatment process and operating condition with embodiment 1, the difference is that: do not take out part high-temperature gas and be discharged into Stirling
Electrical power generators, oxidation bed flue gas exit temperature are 150 DEG C, if being directly entered lye absorption tower, reduce flue-gas temperature
To 50 DEG C, purifying smoke qualified discharge, required fresh alkali number is 5kg/h, generates a large amount of absorption waste liquid, and salinity is high in waste liquid
Up to 10%.The technique not only wastes the amount of heat of oxidation process generation, but also also reduces lye absorption efficiency, increases alkali
Liquid consumption produces a large amount of high-salt wastewaters.
Comparative example 2
Treatment process and operating condition with embodiment 2, the difference is that: the concentration of chlorobenzene is in organic exhaust gas containing chlorine
0.42(5400mg/Nm3), oxidation bed flue gas exit temperature is 70 DEG C, since the temperature can be only used for the reaction of accumulation of heat fireworks
Energy self-balancing, therefore it is not suitable for this process.
Comparative example 3
Treatment process and operating condition with embodiment 3, the difference is that: electrolysis reactor does not use film cell reaction
Positive electrode and negative electrode is only arranged in device.Flue gas exit temperature is 80 DEG C, generated energy 114kwh after control power generation, this electricity is logical
The NaOH lye for entering renewable 12kg/h after film electrolysis reactor is not able to satisfy the requirement that subsequent institute's alkali needed is 20kg/h.
Claims (15)
1. a kind of integrated conduct method of high concentration organic exhaust gas containing chlorine, it is characterised in that including following content:
(1) high concentration organic exhaust gas containing chlorine is passed through in regenerative oxidation reactor and is aoxidized, control oxidation bed exhanst gas outlet
Temperature is at 100 DEG C or less；The total hydrocarbon concentration of the organic exhaust gas containing chlorine is greater than 6000mg/Nm3；
(2) high-temperature flue gas obtained after regenerative oxidation except for maintain Self-heat-storage react energy balance in addition to, rest part from
High-temperature region, which is drawn, in the middle part of regenerative oxidation reactor enters stirling generator power generation, and flue gas exit temperature is 100 after control power generation
DEG C or less；
(3) it is sent into lye absorption tower after mixing the flue gas that step (1) and (2) are discharged, the sour gas in flue gas is inhaled completely
It receives, and flue-gas temperature is made to be reduced to 60 DEG C hereinafter, purified gas qualified discharge；
(4) the absorption waste liquid that step (3) generates enters electrochemical regeneration device, and the NaOH solution regenerated returns to alkali cleaning absorption tower
It recycles.
2. according to the method described in claim 1, it is characterized by: the total hydrocarbon concentration of the organic exhaust gas containing chlorine is 7000-
15000mg/Nm3, organic exhaust gas containing chlorine is the organic exhaust gas containing chlorobenzene.
3. according to the method described in claim 1, it is characterized by: regenerative oxidation reactor described in step (1) includes 2-3
Accumulation of heat bed can be switched over according to timing, to carry out accumulation of heat-exothermic process.
4. according to the method described in claim 1, it is characterized by: in step (1) according to chlorinated organics type in exhaust gas and
The difference of concentration, control oxidizing temperature are 500-1200 DEG C, and control oxidation bed flue gas exit temperature is 40-90 DEG C.
5. according to the method described in claim 1, it is characterized by: step (1) in control oxidizing temperature be 600-900 DEG C,
Control oxidation bed flue gas exit temperature is 50-80 DEG C.
6. according to the method described in claim 1, it is characterized by: the middle multiple Stirling generating sets of setting of step (2), make height
Warm flue-gas temperature is reduced to 100 DEG C or less.
7. according to the method described in claim 1, it is characterized by: in step (3) lye absorption tower be packed tower, sieve-plate tower or
Void tower carries out cooling absorption using NaOH lye.
8. according to the method described in claim 1, it is characterized by: the control of absorbing liquid pH value is 7 or more in step (3), cigarette
HCl gas in gas fully absorbs, and after so that flue-gas temperature is reduced to 60 DEG C or less, while controls the salinity of absorbing liquid
Within the scope of 5wt%-20wt%.
9. according to the method described in claim 1, it is characterized by: the electrochemical regeneration device in step (4) is anti-using film electrolysis
Device is answered, entire electrolytic cell is separated into anion slot, medial launder and cation by setting anionic membrane and cationic membrane in electrolytic cell
Positive electrode and negative electrode are placed in the cation slot and anion slot in three regions of slot respectively, and two electrodes are respectively and direct current
The anode of power supply is connected with cathode.
10. according to the method described in claim 9, it is characterized by: when electrolytic cell goes into operation, the medial launder, anion slot, sun
Respectively initial concentration is 5wt%-20wt%NaCl solution, 0.4wt%-3wt%NaOH solution and 0.3wt%-2wt% in ion slot
HCl solution.
11. according to claim 1, method described in 9 or 10, it is characterised in that: electrolytic condition is as follows: temperature is room temperature, voltage
For 2.5-5V, current density 40-100A/m2。
12. method according to claim 9 or 10, it is characterised in that: by adjusting into the absorption waste liquid of medial launder
It is 5wt%-20wt% that amount, which 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 cathode
Reaction generates hydrogen and NaOH solution, wherein regeneration NaOH solution concentration is 5%-15%, follows back to lye is carried out in step (3)
Ring utilizes.
14. according to claim 1, method described in 9 or 10, it is characterised in that: be electrolysed the part or all of source of required electric energy
Stirling generator in step (2).
15. the Integrated Processing Unit of high concentration organic exhaust gas containing chlorine using any the method for claim 1-14, feature
It is to include regenerative oxidation reactor, stirling generator, lye absorption tower and electrochemical regeneration device, wherein regenerative oxidation reacts
Device is used for the oxidation processes of high concentration organic exhaust gas containing chlorine, and the high-temperature flue gas obtained after regenerative oxidation is removed for maintaining Self-heat-storage
Reaction energy balance external, rest part draw from the middle part high-temperature region of regenerative oxidation reactor and enter stirling generator hair
Electricity, lye absorption tower are used to carry out absorption processing, purified gas to the flue gas that regenerative oxidation reactor and stirling generator are discharged
Qualified discharge, electrochemical regeneration device absorb the regeneration treatment of the absorption waste liquid generated, electric energy needed for electrolytic regeneration for lye
It is partly or fully originate from stirling generator, the NaOH solution regenerated returns to alkali cleaning absorption tower and recycles.
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| CN102335553A (en) * | 2010-07-21 | 2012-02-01 | 中国石油化工股份有限公司 | Reproduction method for sodium-base flue gas desulfurization liquid |
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| CN203963957U (en) * | 2014-07-02 | 2014-11-26 | 上海嘉园环保科技有限公司 | Energy-saving organic waste gas treatment system |
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| US8142727B2 (en) * | 2008-12-09 | 2012-03-27 | Eisenmann Corporation | Valveless regenerative thermal oxidizer for treating closed loop dryer |
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| CN1369325A (en) * | 2001-02-16 | 2002-09-18 | 深圳市柯雷恩环境科技有限公司 | Desulfurizing process and apparats with regeneratable desulfurizing agent |
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