CN206823509U - A kind of processing system of the organic exhaust gas containing cyanogen - Google Patents
A kind of processing system of the organic exhaust gas containing cyanogen Download PDFInfo
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- CN206823509U CN206823509U CN201720388342.4U CN201720388342U CN206823509U CN 206823509 U CN206823509 U CN 206823509U CN 201720388342 U CN201720388342 U CN 201720388342U CN 206823509 U CN206823509 U CN 206823509U
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Abstract
The utility model discloses a kind of processing system of organic exhaust gas containing cyanogen, including cooler, first order absorption tower, second level absorption tower and the catalyst oxidation reactor being sequentially connected in series, the gas outlet of previous equipment connects the air inlet of next equipment, catalysis oxidizing tower is made up of the packing layer on top and beds two parts of bottom, the gas outlet of catalyst oxidation reactor and atmosphere.Organic exhaust gas containing cyanogen is handled using system of the present utility model, processing procedure does not produce or only produced a small amount of waste water, and HCN is oxidized to nontoxic N in waste gas2、CO2, HCN clearances are up to more than 99% so that cyanide qualified discharge in waste liquid, whole waste gas treatment process is simple, and treatment effect is preferable.
Description
Technical field
The utility model belongs to the processing system of technical field of waste gas treatment, the more particularly to organic exhaust gas containing cyanogen.
Background technology
Cyanogenation is the common reaction of chemical field, and caused HCN-containing gases have very strong toxicity in course of reaction,
Having to pass through after processing reaches discharge standard can just discharge.
Chinese patent application 201510687800X discloses a kind of HCN-containing gases processing method, and its step is:Cyanogen will be contained to give up
Gas inputs first order absorption tower through air blower and second level absorption tower, HCN-containing gases contact from bottom of towe to tower top with absorbing liquid, gives up
To liquid phase and NaClO absorbing liquids oxidation reaction occurs for the HCN mass transfers contained in gas, wherein, the PH controls on first order absorption tower exist
More than 11, the second level absorption tower pH control will sequentially input quartz 8~9 with the reacted absorbing liquid of HCN-containing gases through water pump
Sand filtering tank, regulating reservoir, then mixed with from Ozone Water caused by high-concentration ozone water all-in-one, then through static mixer,
Mixed liquid enters electron accelerator and carries out radiation treatment.
Chinese patent application 2012103946834 discloses a kind of electric power migration recovery and the device of purification HCN-containing gases
And its method.The device is made up of electronic emission-control equipment and cathode electro-Fenton device, wherein electronic emission-control equipment by
Anode chamber and cathode chamber composition, are separated by ion selectivity through film, and voltage is added at device both ends, and waste gas turns into cathode chamber
Turn to CN-Form, and enter anode chamber through amberplex under electromigration, high concentration HCN is obtained in anode chamber
Gas, reuse is collected by HCN recovery storage tanks.The device can be by various HCN-containing gases (such as carbon fiber tail gas, propylene cyanogen waste gas, electricity
Stone furnace gas, oven gas, yellow phosphoric tail gas etc.) in HCN recovery.Above-mentioned HCN-containing gases processing method complex process, processing cost are high.
The content of the invention
The purpose of this utility model is the processing system for providing a kind of organic exhaust gas containing cyanogen, will can contain in cyanogen organic exhaust gas
HCN is oxidized to nontoxic N2、CO2, non-secondary pollution, clearance reaches more than 99%, during absorbing liquid can also be remained
Middle cyanide ion is handled so that cyanide qualified discharge in waste liquid, whole waste gas treatment process is simple, treatment effect compared with
It is good.
To realize above-mentioned technical purpose, the utility model employs following technical scheme:
A kind of processing system of the organic exhaust gas containing cyanogen, including be sequentially connected in series cooler, first order absorption tower, the second level inhale
Tower and catalyst oxidation reactor are received, the gas outlet of previous equipment connects the air inlet of next equipment, and catalysis oxidizing tower is by top
Packing layer and beds two parts of bottom composition, the gas outlet of catalyst oxidation reactor and atmosphere.
Catalysis oxidizing tower top filler is ceramics or polytetrafluoroethylene (PTFE);The catalyst of bottom is loaded catalyst, with work
Property charcoal, NACF, aluminum oxide, molecular sieve or ceramics be used as carrier, with copper, the oxide of copper, iron, the oxide of iron, cobalt,
The oxide of cobalt, nickel, the oxide of nickel, titanium, titanyl compound, molybdenum, at least one of the oxide of molybdenum are used as active component.
Preferably, being additionally provided with demister between cooling device and first order absorption tower, catalyst oxidation reactor is catalysis
Oxidizing tower, catalysis oxidizing tower are added with chlorine dioxide device for formulating, transfer tank, auxiliary catalysis oxidation reaction tank, cooxidant
Device connects, and its stream is additionally provided with pH and concentration detector;Adsorption tower is further connected with behind catalysis oxidizing tower.
The packing layer on catalysis oxidizing tower top is filled with loaded catalyst for ceramics or polytetrafluoroethylene (PTFE), beds.
Waste gas enters in the middle part of tower, is absorbed with the solution that tower top sprays, and oxidative decomposition occurs finally by beds.
Spray-absorption liquid (oxidation solution) is the alkaline solution of the agent containing Chlorine Dioxide Oxidation, and wherein ClO 2 solution is matched somebody with somebody using system water outlet
Put, then mixed with previous stage alkali spray-absorption liquid (absorbing liquid 8), adjust and enter catalysis oxidizing tower after pH and spray.In spray liquid
Chlorine dioxide content is 0.2~2%, and it is 6~8 to control tower bottom water outlet pH, and waste gas flow velocity in packed tower is 0.5~3m/s.
The chemical reaction that the process occurs is as follows:
2ClO2+ CN-+H2O→CNO-+2ClO2 -+2H+
2CNO-+2ClO2+2H2O→2CO2↑+N2↑+4OH-+2Cl-
Combined reaction:2CN-+2ClO2→2CO2↑+N2↑+2Cl-
Adsorption tower carries supporting desorption and regeneration system.It can periodically realize that the regeneration cycle of activated carbon uses.Activated carbon is inhaled
Coupon member can be two sets of activated carbon casees or activated carbon tower, and automatic or manual switching is realized a set of using another set of desorption and regeneration
Function.Activated carbon is granular activated carbon or column-shaped active carbon, can be normal activated carbon or the activated carbon Jing Guo modification.Activity
Charcoal desorption and regeneration is using hot-air, hot nitrogen or vapours processing.
In the utility model, first order absorption tower (pickling tower) and second level absorption tower (caustic wash tower) is graphite or fiberglass
Corrosion-resistant filling tower, filler are ceramics or polytetrafluoroethylene (PTFE);Catalysis oxidizing tower is graphite or modified graphite resistant material falling liquid film
Absorption tower;The material of activated carbon adsorber is fiberglass or Fluorine-lined carbon steel material.
Using the method for processing system of the present utility model processing organic exhaust gas containing cyanogen, comprise the following steps:
(1) waste gas cools down through subcooler, obtains condensate liquid 1 and cooling gas 2, and condensate liquid 1 is back to production;
(2) cooling gas 2 is passed through first order absorption tower, is absorbed by absorbing liquid 3, obtains handling gas 4 and absorbing liquid 5;Institute
It is acid mineral solvent to state absorbing liquid 3;
(3) processing gas 4 is passed through second level absorption tower, is absorbed by absorbing liquid 6, obtains handling gas 7 and absorbing liquid 8;It is described
Absorbing liquid 6 is basic mineral solvent;
(4) processing gas 7 is passed through catalyst oxidation reactor, by the catalytic oxidation treatment of catalyst and oxidation solution, obtains everywhere
Qi-regulating 9 and treatment fluid 10;The oxidation solution is formed by chlorine dioxide, acidity regulator and the mixed preparing of absorbing liquid 8.
Preferably, the chilling temperature in step (1) is -15 DEG C~20 DEG C.
Preferably, absorbing liquid 3 is the aqueous hydrochloric acid solution of 2~12% mass fractions, liquid air volume is controlled in absorption process
Than for 1:4~6;Waste gas residence time in pickling tower is 5~60s, and obtained waste water solution is through appropriate pretreatment, evaporative crystallization
Recyclable industrial grade ammonium chloride;The chemical reaction that the process occurs is as follows:
NH3+ HCl=NH4Cl
Absorbing liquid 6 is the sodium hydrate aqueous solution of 5~15% mass fractions, and it is 1 that liquid air volume ratio is controlled in absorption process:
5~9;Waste gas residence time in caustic wash tower is 5~60s.The chemical reaction that the process occurs is as follows:
HCN+NaOH=NaCN+H2O
The weight/mass percentage composition of chlorine dioxide is 0.2~2% in oxidation solution;Catalyst is loaded catalyst, with activity
Charcoal, aluminum oxide, molecular sieve or ceramics be used as carrier, with copper, the oxide of copper, iron, the oxide of iron, cobalt, cobalt oxide,
Nickel, the oxide of nickel, titanium, titanyl compound, molybdenum, at least one of the oxide of molybdenum are used as active component.
Absorbing liquid 3 and absorbing liquid 6 recycle respectively, keep the pH of absorbing liquid 6 to be maintained at more than 9 in cyclic process.
Discharged preferably, step (4) obtains handling after gas 9 is adsorbed by acticarbon, acticarbon is adopted
With the activated carbon granule of random character or cylinder, activated carbon granule is made up of conventional activated carbon or modified activated carbon, adsorbs
The activated carbon of saturation is using hot-air, hot nitrogen or vapours regeneration.
A kind of processing method of organic exhaust gas containing cyanogen, specifically includes following steps:
(1) waste gas is handled by cooler and demister first after gas collection, and the high concentration in waste gas, higher boiling are had
Machine thing cools down, and the water after cooling is as reaction raw materials or solvent reclaiming into production process;
(2) organic matter of condensed waste gas HCN containing low concentration, ammonia and low concentration, into pickling tower, with liquid air volume
Than for 1:4~6 carry out pickling spray with acid solution, the ammonia and partial organic substances gone in removing exhaust gas;
(3) waste gas after pickling enters caustic wash tower, using liquid air volume ratio as 1:5~9 are sprayed with alkali lye, lye import pH controls
System controls alkali lye cyclic absorption 9~11, should during hydrogen cyanide and alkaline reaction generation Cymag the aqueous solution, part water
Soluble organism is by alkali liquor absorption;
(4) the low concentration organic exhaust gas containing cyanogen come out through caustic wash tower enters catalysis oxidizing tower, and catalysis oxidizing tower is by top
Filler and beds two parts of bottom composition;By in oxidant chlorine dioxide, acidity regulator and previous stage caustic wash tower
Absorbing liquid be made into spray liquid, from catalysis oxidation tower top to bottom of towe circulated sprinkling, liquid air volume ratio is 1:4~6, control tower middle part
8~9, waste gas enters water outlet pH in the middle part of catalysis oxidizing tower, spray liquid absorption spray by tower top, finally by catalysis
Oxidative decomposition occurs for agent bed;
(5) remainder of exhaust gas passes through high-altitude qualified discharge after activated carbon adsorber.
Include condensing unit, absorptive unit and absorbing unit, unit in waste gas processing method of the present utility model
It is combined into overall flow.Condensing unit is condensed using one-level, and absorptive unit is absorbed using three-level, and absorbing unit uses primary activity
Charcoal adsorbs.Waste gas is first cooled down higher concentration, higher boiling VOCs in waste gas by condensing unit cooler, demister,
Recovery uses;Then waste gas enters absorptive unit, removes ammonia and organic amine material by primary acids spray-absorption, then pass through
One-level Alkali absorption and one stage catalyzing oxidative absorption, which reach, removes hydrogen cyanide, catalysis oxidation decomposition VOCs effect, alkali during being somebody's turn to do
Absorbing reduces catalysis oxidizing tower load, from tower after being mixed with caused waste water solution with the Chlorine Dioxide Oxidation agent solution prepared
Push up and sprayed to bottom of towe, waste gas and Cyanide in Waste Water compound and VOCs materials are in the beds Jing Guo catalysis oxidizing tower during being somebody's turn to do
Efficient redox reaction can occur, reach the effect for reducing hydrogen cyanide toxicity and removing VOCs, do not produced during being somebody's turn to do useless
The secondary pollutions such as water;Remainder of exhaust gas adsorbs remaining VOCs, so as to qualified discharge finally by the adsorption tower of absorbing unit.
Alkali lye spray is combined with catalysis oxidation washing process in waste gas treatment process, mainly there is two technical advantages:First,
Alkali lye spray has preferable assimilation effect to hydrogen cyanide, can effectively reduce subsequent catalyst Effects Analysis load;Second, alkali lye spray system
The aqueous solution can be used for being configured to the spray liquid of the agent containing Chlorine Dioxide Oxidation in system, be used in internal system circulation, time, waste gas and
Cyanide in Waste Water compound, organic matter etc. can be decomposed thoroughly, not produce secondary pollution.
Waste gas processing method of the present utility model be particularly suitable for use in during dyestuff intermediate production cyanogenation produce it is useless
The processing of gas.Such as:Because of a large amount of solvent DMFs and liquid cyanogen in disperse dyes B60 production processes, while use one or more
Organic additive, during it is general also use ammoniacal liquor to adjust pH, during can produce it is organic containing hydrogen cyanide, ammonia and higher concentration
The mix waste gas of thing (DMF, aniline etc.), in this several pernicious gas, hydrogen cyanide toxicity is maximum, the improvement of such HCN-containing gases
Universal attention is caused.
In waste gas processing method of the present utility model, first order acid Sprayer Circulation liquid liquid uses aqueous hydrochloric acid solution;The second level
Alkali Sprayer Circulation liquid is used for third level catalysis oxidizing tower spray liquid after being mixed with aqueous oxidizing agent solution to suitable concn, pH scopes,
Wherein aqueous solution of chlorine dioxide is prepared using the water outlet of third level catalysis oxidizing tower;Tail gas after processing is by carrying regenerative system
Qualified discharge after charcoal absorption.Except first order pickling tower periodically discharges salt solution, evaporative crystallization after pretreatment in whole system
Reclaim chlorination ammonium salt;Follow-up system can keep lasting, high-efficiency operation, not produce the secondary pollutions such as waste water, final waste gas obtains entirely
The purified treatment in face.
Brief description of the drawings
Fig. 1 is the utility model schematic flow sheet.
Embodiment
Embodiment 1
Processing system as shown in Figure 1, including cooler 4, sour spray absorber 1, the alkali spray absorber 2 being sequentially connected
With catalysis oxidizing tower 3, the gas outlet of previous equipment connects the air inlet of next equipment, catalysis oxidizing tower 3 by top packing layer
Formed with beds two parts of bottom, the gas outlet of catalysis oxidizing tower 3 and atmosphere.The top of catalysis oxidizing tower 3 is filled out
Expect for ceramics;The catalyst of bottom is loaded catalyst, and using activated carbon as carrier, active component is used as using copper.
Catalysis oxidizing tower is connected with chlorine dioxide device for formulating 6 and transfer tank, auxiliary catalysis oxidation reaction tank, assisted oxidation
Agent adding set connects, and its stream is additionally provided with pH and concentration detector (accompanying drawing is not shown).Sour spray absorber 1, alkali spray are inhaled
Receive tower 2 and catalysis oxidizing tower 3 is connected with transfer tank.
Adsorption tower 5 is further connected with behind catalysis oxidizing tower.Adsorption tower 5 carries supporting desorption and regeneration system.Can periodically it realize
The regeneration cycle of activated carbon uses.Activated carbon adsorption unit can be that two sets of activated carbon casees or activated carbon tower, automatic or manual are cut
Change and realize a set of function using another set of desorption and regeneration.Activated carbon is granular activated carbon or column-shaped active carbon, can be common living
Property charcoal or the activated carbon Jing Guo modification.Activated carbon desorption and regeneration uses hot air treatment.
Embodiment 2:
Certain factory's disperse blue B60 production technology cyanogenation process is generated containing hydrogen cyanide, DMF and higher concentration ammonia, benzene
The mix waste gas of amine.Wherein hydrogen cyanide 330-350mg/m3, ammonia 180mg/m3, TVOC about 1200mg/m3。
Waste gas is with 2000m3/ h flow enters condenser, and condensation temperature is -10 DEG C, and condensed waste gas enters pickling
Tower, it is 10% counter-current absorption through hydrogen cloride concentration, liquid-gas ratio 6, hydrogen cyanide content about 280mg/m after absorption3, ammonia level is about
12mg/m3, TVOC about 980mg/m3。
Waste gas after pickling enters alkali spray column, is 12% sodium hydroxide counter-current absorption with mass fraction, alkali spray column
Liquid-gas ratio be 7, waste gas flow velocity be 0.8m/s, absorb temperature be 35 DEG C, hydrogen cyanide content about 80mg/m after absorption3, ammonia contains
Measure about 8mg/m3, TVOC about 400mg/m3。
The tower diameter of above water scrubber and caustic wash tower is 1m, packed height 3m.The waste gas come out from caustic wash tower is from tower
Tower is washed into catalysis oxidation by portion, washes inversely being contacted containing oxidizing agent solution for tower portion top spray leaching with from catalysis oxidation, sprinkle density is
20m3/m2H, exhaust gas residence time 12s, the ClO 2 solution mass fraction that catalysis oxidizing tower middle part is pumped into are 1.2%,
It is 35 DEG C that wherein packed tower, which absorbs temperature, and reaction bed temperature is 50 DEG C, and bed height about 450mm, air speed is about 0.5s-1。
Entering adsorption tower after vent gas treatment, waste gas is about 0.2m/s by adsorption tower flow velocity, after operation starts, every
120min surveys HCN, ammonia and TVOC numerical value in a tail gas, and hydrogen cyanide, which is examined, in the waste gas come out from adsorption tower does not measure, ammonia
2.2mg/m3, TVOCs is about 34mg/m3, gas high-altitude qualified discharge after processing, while catalysis oxidizing tower water outlet cyanide ion concentration
About 0.8mg/m3, cyanide reaches national grade one discharge standard in water outlet.
Embodiment 3:
Certain factory's disperse blue B60 production technology cyanogenation process generates-and the mixing containing hydrogen cyanide and low concentration ammonia gives up
Gas.Wherein hydrogen cyanide 220-250mg/m3, ammonia 140mg/m3, TVOC about 1000mg/m3。
Waste gas is with 1800m3/ h flow enters condenser, and condensation temperature is -10 DEG C, and condensed waste gas enters pickling
Tower, it is 10% counter-current absorption through hydrogen cloride concentration, liquid-gas ratio 6, hydrogen cyanide content about 180mg/m after absorption3, ammonia level is about
22mg/m3, TVOC about 870mg/m3。
Waste gas after pickling enters alkali spray column, is 12% sodium hydroxide counter-current absorption with mass fraction, alkali spray column
Liquid-gas ratio be 6.5, waste gas flow velocity be 0.6m/s, absorb temperature be 30 DEG C, hydrogen cyanide content about 60mg/m after absorption3, ammonia
Content about 12mg/m3, TVOC about 340mg/m3。
The tower diameter of above water scrubber and caustic wash tower is 1m, packed height 3.5m.The waste gas come out from caustic wash tower is from tower
Tower is washed in middle part into catalysis oxidation, and inversely being contacted containing oxidizing agent solution for tower portion top spray leaching, sprinkle density are washed with from catalysis oxidation
For 18m3/m2H, exhaust gas residence time 10s, the ClO 2 solution mass fraction that the catalysis oxidizing tower middle part is pumped into are
1.0%, it is 35 DEG C that wherein packed tower, which absorbs temperature, and reaction bed temperature is 50 DEG C, bed height about 450mm, and air speed is about
0.5s-1。
Entering adsorption tower after vent gas treatment, waste gas is about 0.2m/s by adsorption tower flow velocity, after operation starts, every
120min surveys HCN, ammonia and TVOC numerical value in a tail gas, and hydrogen cyanide, which is examined, in the waste gas come out from adsorption tower does not measure, ammonia
3.2-3.6mg/m3, TVOCs is about 40mg/m3, gas high-altitude qualified discharge after processing, while catalysis oxidizing tower water outlet cryanide ion
Concentration about 0.4mg/m3, cyanide reaches national grade one discharge standard in water outlet.
Embodiment 4:
Certain factory's disperse blue B60 production technology cyanogenation process is generated containing hydrogen cyanide, low concentration ammonia and higher concentration
The mix waste gas of aniline.Wherein hydrogen cyanide 420-450mg/m3, ammonia 220mg/m3, TVOC about 1400mg/m3。
Waste gas is with 1000m3/ h flow enters condenser, and condensation temperature is -10 DEG C, and condensed waste gas enters pickling
Tower, it is 10% counter-current absorption through hydrogen cloride concentration, liquid-gas ratio 5.5, hydrogen cyanide content about 320mg/m after absorption3, ammonia level
About 78mg/m3, TVOC about 760mg/m3。
Waste gas after pickling enters alkali spray column, is 15% sodium hydroxide counter-current absorption with mass fraction, alkali spray column
Liquid-gas ratio be 7, waste gas flow velocity be 0.6m/s, absorb temperature be 30 DEG C, hydrogen cyanide content about 60mg/m after absorption3, ammonia contains
Measure about 12mg/m3, TVOC about 340mg/m3。
The tower diameter of above water scrubber and caustic wash tower is 0.6m, packed height 3m.The waste gas come out from caustic wash tower is from tower
Tower is washed in middle part into catalysis oxidation, and inversely being contacted containing oxidizing agent solution for tower portion top spray leaching, sprinkle density are washed with from catalysis oxidation
For 20m3/m2H, exhaust gas residence time 10s, the ClO 2 solution mass fraction that the catalysis oxidizing tower middle part is pumped into are
1.4%, it is 35 DEG C that wherein packed tower, which absorbs temperature, and reaction bed temperature is 50 DEG C, bed height about 400mm, and air speed is about
0.5s-1.Enter adsorption tower after vent gas treatment, waste gas is about 0.2m/s by adsorption tower flow velocity, after operation starts, every 120min
HCN, ammonia and TVOC numerical value in a tail gas are surveyed, hydrogen cyanide, which is examined, in the waste gas come out from adsorption tower does not measure, ammonia 8-10mg/
m3, TVOCs is about 62mg/m3, gas high-altitude qualified discharge after processing, while catalysis oxidizing tower water outlet cyanide ion concentration is about
0.7mg/m3, cyanide reaches national grade one discharge standard in water outlet.
Claims (5)
- A kind of 1. processing system of organic exhaust gas containing cyanogen, it is characterised in that including be sequentially connected in series cooler, the first order absorb Tower, second level absorption tower and catalyst oxidation reactor, the gas outlet of previous equipment connect the air inlet of next equipment, catalysis oxidation Tower is made up of the packing layer on top and beds two parts of bottom, and gas outlet and the air of catalyst oxidation reactor connect It is logical.
- 2. processing system according to claim 1, it is characterised in that be additionally provided with and remove between cooler and first order absorption tower Foam device, catalyst oxidation reactor are catalysis oxidizing tower, catalysis oxidizing tower and chlorine dioxide device for formulating, transfer tank, auxiliary catalysis Oxidation reaction tank, cooxidant adding set are connected, and pH and concentration detector are additionally provided with its stream;Behind catalysis oxidizing tower It is further connected with adsorption tower.
- 3. processing system according to claim 2, it is characterised in that the packing layer on catalysis oxidizing tower top is filled with ceramics Or filler prepared by polytetrafluoroethylene (PTFE), beds are filled with loaded catalyst.
- 4. processing system according to claim 2, it is characterised in that adsorption tower carries supporting desorption and regeneration system.
- 5. processing system according to claim 2, it is characterised in that first order absorption tower and second level absorption tower are graphite Or fiberglass corrosion-resistant filling tower, filler are ceramics or polytetrafluoroethylene (PTFE);Catalysis oxidizing tower is that graphite or modified graphite are corrosion-resistant Material film-falling absorption tower;The material of activated carbon adsorber is fiberglass or Fluorine-lined carbon steel material.
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Cited By (2)
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CN107051144A (en) * | 2017-04-12 | 2017-08-18 | 浙江奇彩环境科技股份有限公司 | The processing method and system of a kind of organic exhaust gas containing cyanogen |
CN110124421A (en) * | 2018-02-02 | 2019-08-16 | 刘庆军 | Air cleaning system and air purification method |
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2017
- 2017-04-12 CN CN201720388342.4U patent/CN206823509U/en active Active
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107051144A (en) * | 2017-04-12 | 2017-08-18 | 浙江奇彩环境科技股份有限公司 | The processing method and system of a kind of organic exhaust gas containing cyanogen |
CN110124421A (en) * | 2018-02-02 | 2019-08-16 | 刘庆军 | Air cleaning system and air purification method |
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