CN102872690A - A device and method for recovering cyanide by electrodynamic migration/oxidation and recovering NH3 - Google Patents

A device and method for recovering cyanide by electrodynamic migration/oxidation and recovering NH3 Download PDF

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CN102872690A
CN102872690A CN2012103946730A CN201210394673A CN102872690A CN 102872690 A CN102872690 A CN 102872690A CN 2012103946730 A CN2012103946730 A CN 2012103946730A CN 201210394673 A CN201210394673 A CN 201210394673A CN 102872690 A CN102872690 A CN 102872690A
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hcn
tank
cathode
recovering
fluidized bed
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CN102872690B (en
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吴祖成
廖文
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

本发明公开了一种电动力迁移回收氰/氧化回收NH3的装置及其方法。装置由电动废气处理装置、阴极电芬顿装置、炭流化床组成，其中电动废气处理装置由阳极室和阴极室组成，由离子选择性透过膜隔开，在装置两端加上电压，废气进入阴极室转化为CN-形式，并在电迁移作用下透过离子交换膜进入阳极室，在阳极室内获得高浓度HCN气体，被HCN回收储罐中的清水吸收生成氢氰酸，氢氰酸在炭流化床中的催化剂的作用下被氧化为NH3，NH3被吸收罐中的酸吸收回用。该装置可将各种含氰废气（如碳纤维尾气、丙烯氰废气、电石炉气、焦炉气、黄磷尾气等）中的HCN回收，并合成NH3产品。

Figure 201210394673

The invention discloses a device and a method for recovering cyanide by electrodynamic migration/oxidation and recovering NH 3 . The device consists of an electric exhaust gas treatment device, a cathode electric Fenton device, and a carbon fluidized bed. The electric exhaust gas treatment device is composed of an anode chamber and a cathode chamber, separated by an ion-selective permeable membrane, and a voltage is applied to both ends of the device. The exhaust gas enters the cathode chamber and is converted into CN - form, and enters the anode chamber through the ion exchange membrane under the action of electromigration, and obtains high-concentration HCN gas in the anode chamber, which is absorbed by the clear water in the HCN recovery storage tank to generate hydrocyanic acid, hydrogen cyanide The acid is oxidized to NH 3 under the action of the catalyst in the carbon fluidized bed, and the NH 3 is absorbed by the acid in the absorption tank for reuse. The device can recover HCN from various cyanide-containing waste gases (such as carbon fiber tail gas, acrylcyanide waste gas, calcium carbide furnace gas, coke oven gas, yellow phosphorus tail gas, etc.) and synthesize NH3 products.

Figure 201210394673

Description

Cyanogen/oxid-reclamatiom NH is reclaimed in a kind of electric power migration 3Devices and methods therefor
Technical field
The present invention relates to a kind of electric power migration and reclaim cyanogen/oxid-reclamatiom NH 3Devices and methods therefor.
Background technology
The removal methods of HCN is mainly absorption process, absorption method and firing method.The method of several HCN of removing waste gas respectively has characteristics, and the pluses and minuses of every kind of processing method and the object that is suitable for processing thereof are had nothing in common with each other.During the HCN tail gas that produces in processing actual production, the factors such as cost of HCN concentration, contained other components of tail gas and discharging modes, existing equipment and processing method all can have influence on the selection of HCN removal methods.When adopting absorption method, some gas group branch affects active carbon to the suction-operated of HCN.For example when containing more steam in the waste gas, there are the competitive Adsorption phenomenon in steam and HCN, make the HCN desorb that is adsorbed and greatly reduce treatment effect.When the steam volume content surpassed 50 %, active carbon just no longer adsorbed HCN.Therefore when containing the component of influential absorption in the waste gas, tackle it and carry out necessary preliminary treatment.Consider that HCN tail gas in the production practices is mainly derived from the Pintsch process of coal and the high temperature carbonization of PAN charcoal fiber is processed, adopt Production by Catalytic Combustion Process to have larger advantage, but to the catalytic combustion research of HCN, have not yet to see the industrialization report of maturation, also mainly be in the laboratory research stage.Patent CN 201586472 U disclose a kind of cyanogen emission-control equipment that contains, contain cyanogen waste gas twice be fully absorbed after soda bath mixes, compare with operation of the prior art, absorptivity increases greatly, and reduced the caustic soda consumption amount, improved the safety in production level, but this method is faced with a large amount of chemical agent of consumption equally, and the generation secondary pollution can not be recycled.For this, adopt electric driving method that hydrogen cyanide waste gas is carried out abdominal muscle among the present invention and purify, the hydrogen cyanide in the waste gas is converted into hydrogen cyanide, and under catalytic action, reclaims and be converted into NH 3, the series connection absorption tower is to NH 3GAS ABSORPTION transfers (NH to 4) 2SO 4, NH 4NO 3, NH 4Cl and (NH 4) 3PO 4Deng chemicals, make it to transfer the poisonous and hazardous cyanogen waste gas that contains to high value-added product.
Summary of the invention
The objective of the invention is to overcome the deficiency of existing technology, provide a kind of electric power migration to reclaim cyanogen/oxid-reclamatiom NH 3Devices and methods therefor.
Cyanogen/oxid-reclamatiom NH is reclaimed in the electric power migration 3Device comprise that exhaust gas centralized gas hood, pressure controller, electronic emission-control equipment, HCN reclaim storage tank, other gas processing devices, by-pass valve control, on-line monitoring device, charcoal fluid bed, fluid bed filler, air steel cylinder, air blast, tourie, spray liquid pool, sprinkling equipment, anode flow container, negative electrode flow container, neutralization pond, cathodic electricity Fenton device, the first dc source; Electronic emission-control equipment comprises the ion selectivity exchange membrane, the anode chamber, cathode chamber, the inertia filler, first anode plate, the first minus plate, electronic this body and function of emission-control equipment ion selectivity exchange membrane is separated into the anode chamber, cathode chamber, be filled with the inertia filler in anode chamber and the cathode chamber, be provided with first anode plate in the anode chamber, first anode plate links to each other with the first dc power anode, be provided with the first minus plate in the cathode chamber, the first minus plate links to each other with the first dc power cathode, the exhaust gas centralized gas hood links to each other with the cathode chamber of electronic emission-control equipment through pressure controller, the top, anode chamber is reclaimed storage tank through pressure controller with HCN and is linked to each other, HCN reclaims tank top through by-pass valve control, the on-line monitoring device links to each other with charcoal fluid bed bottom, the air steel cylinder links to each other with the charcoal fluid bed through air blast, the fluid bed outlet links to each other with tourie through by-pass valve control, the spray liquid pool is through by-pass valve control, on-line monitoring device and sprinkling equipment divide two-way, wherein, one the tunnel links to each other with the top, anode chamber, another road links to each other with the cathode chamber top, the outlet of cathode chamber top links to each other with other gas treatment equipments, the bottom, anode chamber is through the on-line monitoring device, by-pass valve control links to each other with the anolyte tank top, the anolyte pot bottom links to each other with the neutralization pond top through by-pass valve control, the cathode chamber bottom links to each other with the catholyte tank top through the on-line monitoring device, the water outlet of negative electrode flow container divides two-way, one the tunnel links to each other with the neutralization pond top through by-pass valve control, another road links to each other with cathodic electricity Fenton device top through by-pass valve control, neutralization pond links to each other with the spray liquid pool, in the charcoal fluid bed filler is arranged, cathodic electricity Fenton device comprises the second plate plate, the second minus plate, the second dc source, the second plate plate links to each other with the positive pole of the second dc source, and the second minus plate links to each other with the second dc power cathode.
Be provided with filler in the described charcoal fluid bed, filler is in straw charcoal or the coconut husk charcoal one or more, filler Surface mulch one deck catalyst, catalyst is by in metallic catalyst, metal oxide catalyst, complex compound catalyst, rare earth catalyst, the molecular sieve catalyst one or more, metal in the described metallic catalyst is Cu, Ni, Pt, Fe, and the oxide in the metal oxide catalyst is ZrO 2, TiO 2, WO 3, Al 2O 3, Fe 2O 3, complex compound catalyst is polyvinyl siloxane-platinum complex, titanium chelate, molecular sieve catalyst is natural zeolite, aluminum phosphate.
Be provided with clear water in the described HCN absorption plant; Be provided with sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid in the tourie; The ion selectivity exchange membrane is homogeneous-phase anion exchange film or out-phase anion-exchange membrane.
The material of described first anode plate and second plate plate is graphite, active carbon fiber felt, active carbon fiber fabrics and is coated with PbO 2, RuO 2, IrO 2, TiO 2, MnO 2In at least a conducting metal or metal oxide, the material of the first minus plate (24) is stainless steel electrode, graphite, active carbon fiber felt, active carbon fiber fabrics and is coated with PbO 2, RuO 2, IrO 2, TiO 2, MnO 2In at least a conducting metal or metal oxide, the material of the second minus plate is Activated Carbon Fiber Electrodes, graphite electrode, graphite gas-diffusion electrode, active carbon gas-diffusion electrode, multiple-wall carbon nanotube electrode, netted, the poroid or wire grid shape of being shaped as of battery lead plate.
Described inertia filler is one or more in convex-concave trenches openings porcelain ball, active porcelain ball, Pored ceramic ball, micropore porcelain ball, accumulation of heat porcelain ball, grinding porcelain ball, three shape porous porcelains, the resin extender.
Cyanogen/oxid-reclamatiom NH is reclaimed in the electric power migration 3Method be: electronic emission-control equipment produces direct current more than 20V, impel in the anode chamber to produce a large amount of H +, form acid atmosphere, pH≤1.0, cathode chamber produces a large amount of OH -, form alkaline atmosphere, pH 〉=14.0; After containing cyanogen waste gas and absorbed by spray liquid in electronic emission-control equipment in the exhaust gas centralized gas hood, cyanogen is converted into CN more than 99% in cathode chamber -Then under electro ultrafiltration, move, enter the anode chamber through anion-exchange membrane, and generate pure HCN gas, the HCN gas that generates enters HCN and reclaims storage tank, absorbed generation hydrogen cyanide by clear water, hydrogen cyanide solution enters the charcoal fluid bed, oxidized generation NH under the effect of the catalyst in the charcoal fluid bed 3, the catalyst on the filler in the charcoal fluid bed can be accelerated oxidation HCN and generate NH 3, improve and process ability and the recovery NH that HCN pollutes 3Efficient, reaction equation is
Figure 2012103946730100002DEST_PATH_IMAGE002
, the NH of generation 3Enter tourie, the acid that is absorbed in the tank absorbs, and is converted into (NH 4) 2SO 4, NH 4Cl or (NH 4) 3P 3O 4Product; Initial spray liquid in the spray liquid pool is for containing NaCl, Na 2SO 4, Na 3PO 4, Na 2HPO 4, NaNO 3In at least a brackish water, salt content is 0.01% ~ 10%, carry out the HCN in intermittence or the continuous electronic emission-control equipment of spray-absorption, spray head is the spiral spray assembly of wing, spray liquid tangentially disperses to form tiny cloud point, HCN is dissolved in and forms efficient absorption efficiency in these cloud points, the anolyte that produces in electronic emission-control equipment and catholyte are drawn, enter respectively anode flow container, negative electrode flow container, liquid storage in anode flow container and the negative electrode flow container enters the neutralization pond neutralization, and neutralizer is used for replenishing the spray liquid in the spray pond; Residual low concentration contains CN after electronic emission-control equipment is processed -Solution enters electric Fenton device, with CN -Be converted into CO 2
Compared with prior art, the present invention has the following advantages:
1) stable without interruption purification contains cyanogen waste gas continuously, reclaims simultaneously cyanogen, is used for commercial Application;
2) neutralizer can replenish spray liquid, forms circulation;
3) with the changing waste into resources utilization, reclaim the HCN in the waste gas, as the raw material of producing Inorganic Ammonium (ammonium sulfate, ammonium chloride, ammonium phosphate etc.);
4) low concentration CN -Adopt electric Fenton device with CN -Be converted into CO 2, realize the cyanogen zero-emission.
Description of drawings
Fig. 1 is that cyanogen/oxid-reclamatiom NH is reclaimed in the electric power migration 3The apparatus structure schematic diagram;
Fig. 2 is that cyanogen/oxid-reclamatiom NH is reclaimed in the electric power migration 3Method And Principle figure;
Among the figure: exhaust gas centralized gas hood 1, pressure controller 2, electronic emission-control equipment 3, HCN reclaims storage tank 4, other gas processing devices 5, by-pass valve control 6, on-line monitoring device 7, charcoal fluid bed 8, fluid bed filler 9, air steel cylinder 10, air blast 11, tourie 12, spray liquid pool 13, sprinkling equipment 14, anode flow container 15, negative electrode flow container 16, neutralization pond 17, cathodic electricity Fenton device 18, ion selectivity exchange membrane 19, inertia filler 20, anode chamber 21, cathode chamber 22, first anode plate 23, the first minus plate 24, the first dc source 25, second plate plate 26, the second minus plate 27, the second dc source 28.
The specific embodiment
As shown in Figure 1, cyanogen/oxid-reclamatiom NH is reclaimed in the electric power migration 3Device comprise exhaust gas centralized gas hood 1, pressure controller 2, electronic emission-control equipment 3, HCN reclaims storage tank 4, other gas processing devices 5, by-pass valve control 6, on-line monitoring device 7, charcoal fluid bed 8, fluid bed filler 9, air steel cylinder 10, air blast 11, tourie 12, spray liquid pool 13, sprinkling equipment 14, anode flow container 15, negative electrode flow container 16, neutralization pond 17, cathodic electricity Fenton device 18, ion selectivity exchange membrane 19, inertia filler 20, anode chamber 21, cathode chamber 22, first anode plate 23 and second plate plate 26, the first minus plate 24 and the second minus plate 27, the first dc source 25 and the second dc source 28; Electronic emission-control equipment 3 comprises ion selectivity exchange membrane 19, anode chamber 21, cathode chamber 22, inertia filler 20, first anode plate 23, the first minus plate 24,3 body and function ion selectivities of electronic emission-control equipment exchange membrane 19 is separated into anode chamber 21, cathode chamber 22, be filled with inertia filler 20 in anode chamber 21 and the cathode chamber 22, be provided with first anode plate 23 in the anode chamber 21, first anode plate 23 and 25 anodal linking to each other of the first dc source, be provided with the first minus plate 24 in the cathode chamber 22, the first minus plate 24 links to each other with the first dc source 25 negative poles, exhaust gas centralized gas hood 1 links to each other with the cathode chamber 22 of electronic emission-control equipment 3 through pressure controller 2,21 tops, anode chamber are reclaimed storage tank 4 through pressure controller 2 with HCN and are linked to each other, HCN reclaims storage tank 4 tops through by-pass valve control 6, on-line monitoring device 7 links to each other with charcoal fluid bed 6 bottoms, air steel cylinder 10 links to each other with charcoal fluid bed 8 through air blast 11, fluid bed 8 outlets link to each other with tourie 12 through by-pass valve control 6, spray liquid pool 13 is through by-pass valve control 6,14 minutes two-way of on-line monitoring device 7 and sprinkling equipment, wherein, one the tunnel links to each other with 22 tops, anode chamber, another road links to each other with cathode chamber 22 tops, the outlet of cathode chamber 24 tops links to each other with other gas treatment equipments 5,21 bottoms, anode chamber are through on-line monitoring device 7, by-pass valve control 6 links to each other with anode flow container 15 tops, anode flow container 15 bottoms link to each other with neutralization pond 16 tops through by-pass valve control 6, cathode chamber 22 bottoms link to each other with negative electrode flow container 16 tops through on-line monitoring device 7, negative electrode flow container 16 goes out the moisture two-way, one the tunnel links to each other with neutralization pond 15 tops through by-pass valve control 6, another road links to each other with cathodic electricity Fenton device 18 tops through by-pass valve control 6, neutralization pond 17 links to each other with spray liquid pool 13, filler 9 is arranged in the charcoal fluid bed 8, cathodic electricity Fenton device 18 comprises second plate plate 26, the second minus plate 27, the second dc source 28, second plate plate 26 links to each other with the positive pole of the second dc source 28, and the second minus plate 27 links to each other with the second dc source 28 negative poles.
Be provided with filler 9 in the described charcoal fluid bed 8, filler is in straw charcoal or the coconut husk charcoal one or more, filler Surface mulch one deck catalyst, catalyst is by in metallic catalyst, metal oxide catalyst, complex compound catalyst, rare earth catalyst, the molecular sieve catalyst one or more, metal in the described metallic catalyst is Cu, Ni, Pt, Fe, and the oxide in the metal oxide catalyst is ZrO 2, TiO 2, WO 3, Al 2O 3, Fe 2O 3, complex compound catalyst is polyvinyl siloxane-platinum complex, titanium chelate, molecular sieve catalyst is natural zeolite, aluminum phosphate.
Be provided with clear water in the described HCN absorption plant 4; Be provided with sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid in the tourie 12; Ion selectivity exchange membrane 19 is homogeneous-phase anion exchange film or out-phase anion-exchange membrane.
The material of described first anode plate 23 and second plate plate 26 is graphite, active carbon fiber felt, active carbon fiber fabrics and is coated with PbO 2, RuO 2, IrO 2, TiO 2, MnO 2In at least a conducting metal or metal oxide, the material of the first minus plate 24 is stainless steel electrode, graphite, active carbon fiber felt, active carbon fiber fabrics and is coated with PbO 2, RuO 2, IrO 2, TiO 2, MnO 2In at least a conducting metal or metal oxide, the material of the second minus plate 27 is Activated Carbon Fiber Electrodes, graphite electrode, graphite gas-diffusion electrode, active carbon gas-diffusion electrode, multiple-wall carbon nanotube electrode, netted, the poroid or wire grid shape of being shaped as of battery lead plate.
Described inertia filler 20 is one or more in convex-concave trenches openings porcelain ball, active porcelain ball, Pored ceramic ball, micropore porcelain ball, accumulation of heat porcelain ball, grinding porcelain ball, three shape porous porcelains, the resin extender.
As shown in Figure 2, put the electric power migration and reclaim cyanogen/oxid-reclamatiom NH 3Method be: electronic emission-control equipment 3 produces direct current more than 20V, impel a large amount of H of anode chamber's 21 interior generations +, form acid atmosphere, pH≤1.0, cathode chamber 22 produces a large amount of OH -, form alkaline atmosphere, pH 〉=14.0; After containing cyanogen waste gas and absorbed by spray liquid in electronic emission-control equipment 3 in the exhaust gas centralized gas hood 1, cyanogen is converted into CN more than 99% in cathode chamber 22 -Then under electro ultrafiltration, move, enter anode chamber 21 through anion-exchange membrane 19, and generate pure HCN gas, the HCN gas that generates enters HCN and reclaims storage tank 4, absorbed generation hydrogen cyanide by clear water, hydrogen cyanide solution enters charcoal fluid bed 8, oxidized generation NH under the effect of the catalyst in charcoal fluid bed 8 3, the catalyst on the filler in the charcoal fluid bed 8 can be accelerated oxidation HCN and generate NH 3, improve and process ability and the recovery NH that HCN pollutes 3Efficient, reaction equation is , the NH of generation 3Enter tourie 12, the acid that is absorbed in the tank 12 absorbs, and is converted into (NH 4) 2SO 4, NH 4Cl or (NH 4) 3P 3O 4Product; Initial spray liquid in the spray liquid pool 13 is for containing NaCl, Na 2SO 4, Na 3PO 4, Na 2HPO 4, NaNO 3In at least a brackish water, salt content is 0.01% ~ 10%, carry out the HCN in intermittence or the continuous electronic emission-control equipment 3 of spray-absorption, spray head 14 is the spiral spray assembly of wing, spray liquid tangentially disperses to form tiny cloud point, HCN is dissolved in and forms efficient absorption efficiency in these cloud points, the anolyte and the catholyte that produce in electronic emission-control equipment 3 are drawn, enter respectively anode flow container 15, negative electrode flow container 16, liquid storage in anode flow container 15 and the negative electrode flow container 16 enters neutralization pond 17 neutralizations, and neutralizer is used for replenishing the spray liquid in the spray pond 13; Residual low concentration contains CN after electronic emission-control equipment 3 is processed -Solution enters electric Fenton device 18, with CN -Be converted into CO 2
Embodiment 1
Adopt a kind of electric power migration as shown in Figure 1 to reclaim cyanogen/oxid-reclamatiom NH 3Device reclaim carbon fiber and contain HCN in the cyanogen waste gas.HCN concentration is 30mg/m in the waste gas 3, flow is 100m 3/ h, the time of staying is 10min, the migration of process electric power can obtain the HCN gas that purity is 98%-99.5% at HCN recovery storage tank after reclaiming and purify the device that contains cyanogen waste gas, the clear water that is reclaimed in the storage tank by HCN absorbs generation hydrogen cyanide, is oxidized to pure NH under the effect of the metal oxide catalyst of hydrogen cyanide in coconut husk charcoal fluid bed 3, it is 75%～78% H that concentration is arranged in the tourie 2SO 4, can obtain at last purity and be (the NH more than 98.5% 3) 2SO 4The content of HCN is lower than 0.05mg/Nm in the gas of discharging after cathodic electricity Fenton device is processed 3, be 0.3mg/Nm well below HCN GB maximum permissible concentration 3Wherein, electronic emission-control equipment is of a size of 3m*4m*10m, and anode is titanium plating ruthenium mesh electrode, and negative electrode is the netted electrode of stainless steel, and the inertia filler is active porcelain ball.
Embodiment 2
Adopt two groups of electronic emission-control equipments series connection to reclaim HCN in the calcium carbide furnace gas among the embodiment 2, operating procedure, that HCN reclaims principle is identical with embodiment 1.HCN concentration is 2.45g/m in the waste gas 3, flow is 1000m 3/ h, furnace gas divide two-way to enter the electronic emission-control equipment of two-stage, and the time of staying is 20min, and cyanogen/oxid-reclamatiom NH is reclaimed in migration through electric power 3Device after, reclaim storage tank at HCN and can obtain the HCN gas that purity is 97%-98.5%, reclaimed clear water in the storage tank by HCN and absorb and generate hydrogen cyanide, be oxidized to pure NH under the effect of the nonmetal oxide catalyst of hydrogen cyanide in the straw charcoal fluid bed 3, it is 90%～93% H that concentration is arranged in the tourie 2SO 4, (the NH more than 99.9% that can obtain at last purity and be 3) 2SO 4The content of HCN is lower than 0.25mg/Nm in the gas of discharging after cathodic electricity Fenton device is processed 3, being lower than HCN GB maximum permissible concentration is 0.3mg/Nm 3Wherein, every grade of electronic emission-control equipment is of a size of 5m*4m*10m, and anode is titanium plating ruthenium mesh electrode, and negative electrode is the netted electrode of stainless steel, and the inertia filler is active porcelain ball.
Embodiment 3
Adopt two groups of electronic emission-control equipments series connection to reclaim HCN in the calcium carbide furnace gas among the embodiment 3, operating procedure, that HCN reclaims principle is identical with embodiment 1.HCN concentration is 2.45g/m in the waste gas 3, a minute two-way enters the electronic emission-control equipment of two-stage, and after the migration of process electric power was reclaimed and purified and contains the device of cyanogen waste gas, the HCN clean gas contacted with the HCl absorption liquid is reverse, and the migration of process electric power is reclaimed hydrogen cyanide and is prepared NH 4Behind the device of Cl, in products pot, can obtain the NH that purity is 97%-98.5% 4The Cl product.

Claims (6)

1. 一种电动力迁移回收氰/氧化回收NH3的装置，其特征在于包括废气集气罩（1）、压力控制器（2）、电动废气处理装置（3）、HCN回收储罐（4）、其他气体处理设备（5）、控制阀门（6）、在线监控器（7）、炭流化床（8）、流化床填充物（9）、空气钢瓶（10）、鼓风机（11）、吸收罐（12）、喷淋液池（13）、喷淋设备（14）、阳极液罐（15）、阴极液罐（16）、中和池（17）、阴极电芬顿装置（18）、第一直流电源（25）；电动废气处理装置（3）包括离子选择性交换膜（19）、阳极室（21）、阴极室（22）、惰性填充物（20）、第一阳极板（23）、第一阴极板（24），电动废气处理装置（3）本体用离子选择性交换膜（19）分隔成阳极室（21）、阴极室（22），阳极室（21）和阴极室（22）内填充有惰性填充物（20），阳极室（21）内设有第一阳极板（23），第一阳极板（23）与第一直流电源（25）正极相连，阴极室（22）内设有第一阴极板（24），第一阴极板（24）与第一直流电源（25）负极相连，废气集气罩（1）经压力控制器（2）与电动废气处理装置（3）的阴极室（22）相连，阳极室（21）顶部经压力控制器（2）与HCN回收储罐（4）相连，HCN回收储罐（4）顶部经控制阀门（6）、在线监控器（7）与炭流化床（6）底部相连，空气钢瓶（10）经鼓风机（11）与炭流化床（8）相连，流化床（8）出口经控制阀门（6）与吸收罐（12）相连，喷淋液池（13）经控制阀门（6）、在线监控器（7）及喷淋设备（14）分两路，其中，一路与阳极室（22）顶部相连，另一路与阴极室（22）顶部相连，阴极室24上部出口与其他气体处理装置（5）相连，阳极室（21）下部经在线监控器（7）、控制阀门（6）与阳极液罐（15）顶部相连，阳极液罐（15）底部经控制阀门（6）与中和池（16）顶部相连，阴极室（22）底部经在线监控器（7）与阴极液罐（16）顶部相连，阴极液罐（16）出水分两路，一路经控制阀门（6）与中和池（15）顶部相连，另一路经控制阀门（6）与阴极电芬顿装置（18）上部相连，中和池（17）与喷淋液池（13）相连，炭流化床（8）内有填充物（9），阴极电芬顿装置（18）包括第二阳极板（26）、第二阴极板（27）、第二直流电源（28），第二阳极板（26）与第二直流电源（28）的正极相连，第二阴极板（27）与第二直流电源（28）负极相连。 1. A device for recovery of cyanide by electrodynamic migration/oxidation recovery of NH 3 , characterized in that it comprises a waste gas collecting hood (1), a pressure controller (2), an electric waste gas treatment device (3), an HCN recovery storage tank (4 ), other gas treatment equipment (5), control valve (6), online monitor (7), carbon fluidized bed (8), fluidized bed filler (9), air cylinder (10), blower (11) , absorption tank (12), spray pool (13), spray equipment (14), anolyte tank (15), catholyte tank (16), neutralization pool (17), cathodic electro-Fenton device (18 ), the first DC power supply (25); the electric exhaust gas treatment device (3) includes an ion selective exchange membrane (19), an anode chamber (21), a cathode chamber (22), an inert filler (20), a first anode plate (23), the first cathode plate (24), the body of the electric exhaust gas treatment device (3) is divided into an anode chamber (21), a cathode chamber (22), an anode chamber (21) and The cathode chamber (22) is filled with an inert filler (20), the anode chamber (21) is provided with a first anode plate (23), and the first anode plate (23) is connected to the positive pole of the first DC power supply (25), The cathode chamber (22) is provided with a first cathode plate (24), the first cathode plate (24) is connected to the negative pole of the first DC power supply (25), and the exhaust gas collection hood (1) is connected to the The cathode chamber (22) of the electric exhaust gas treatment device (3) is connected, the top of the anode chamber (21) is connected with the HCN recovery storage tank (4) through the pressure controller (2), and the top of the HCN recovery storage tank (4) is connected through the control valve ( 6), the on-line monitor (7) is connected to the bottom of the carbon fluidized bed (6), the air cylinder (10) is connected to the carbon fluidized bed (8) through the blower (11), and the outlet of the fluidized bed (8) is passed through the control valve (6) It is connected with the absorption tank (12), and the spray liquid pool (13) is divided into two paths through the control valve (6), the online monitor (7) and the spray equipment (14), wherein, one path is connected with the anode chamber (22 ), the other is connected to the top of the cathode chamber (22), the upper outlet of the cathode chamber 24 is connected to other gas treatment devices (5), and the lower part of the anode chamber (21) is connected to the The top of the anolyte tank (15) is connected, the bottom of the anolyte tank (15) is connected to the top of the neutralization tank (16) through the control valve (6), and the bottom of the cathode chamber (22) is connected to the catholyte tank ( 16) The top is connected, the catholyte tank (16) has two water outlets, one is connected to the top of the neutralization pool (15) through the control valve (6), and the other is connected to the cathode electro-Fenton device (18) through the control valve (6) The upper part is connected, the neutralization pool (17) is connected with the spray liquid pool (13), the carbon fluidized bed (8) has a filler (9), and the cathode electro-Fenton device (18) includes a second anode plate (26) , the second cathode plate (27), the second DC power supply (28), the second anode plate (26) is connected to the positive pole of the second DC power supply (28), and the second cathode plate (27) is connected to the second DC power supply (28). The negative pole of the power supply (28) is connected. 2. 根据权利要求1所述的一种电动力迁移回收氰/氧化回收NH3的装置，其特征在于所述的炭流化床（8）内设有填充物（9），填充物为秸秆木炭或椰壳炭中一种或几种，填充物表层覆盖一层催化剂，催化剂由金属催化剂、金属氧化物催化剂、络合物催化剂、稀土催化剂、分子筛催化剂中的一种或多种，所述金属催化剂中的金属为Cu、Ni、Pt、Fe，金属氧化物催化剂中的氧化物为ZrO2、TiO2、WO3、Al2O3、Fe2O3，络合物催化剂为聚乙烯基硅氧烷-铂络合物、钛螯合物，分子筛催化剂为天然沸石、磷酸铝。 2. A device for recovering cyanide by electrodynamic migration/recovering NH3 by oxidation according to claim 1, characterized in that the carbon fluidized bed (8) is provided with fillers (9), and the fillers are straw One or more of charcoal or coconut shell charcoal, the surface layer of the filler is covered with a catalyst, and the catalyst is one or more of metal catalysts, metal oxide catalysts, complex catalysts, rare earth catalysts, and molecular sieve catalysts. The metal in the metal catalyst is Cu, Ni, Pt, Fe, the oxide in the metal oxide catalyst is ZrO 2 , TiO 2 , WO 3 , Al 2 O 3 , Fe 2 O 3 , the complex catalyst is polyethylene Siloxane-platinum complex, titanium chelate, and molecular sieve catalysts are natural zeolite and aluminum phosphate. 3. 根据权利要求1所述的一种电动力迁移回收氰/氧化回收NH3的装置，其特征在于所述的HCN吸收装置（4）内设有清水；吸收罐（12）内设有硫酸、硝酸、盐酸或磷酸；离子选择性交换膜（19）为均相阴离子交换膜或异相阴离子交换膜。 3. A device for recovering cyanide by electromotive migration/oxidation and recovering NH3 according to claim 1, characterized in that said HCN absorption device (4) is provided with clean water; the absorption tank (12) is provided with sulfuric acid , nitric acid, hydrochloric acid or phosphoric acid; the ion selective exchange membrane (19) is a homogeneous anion exchange membrane or a heterogeneous anion exchange membrane. 4. 根据权利要求1所述的一种电动力迁移回收氰/氧化回收NH3的装置，其特征在于所述的第一阳极板（23）和第二阳极板（26）的材料为石墨、活性炭纤维毡、活性炭纤维布以及涂敷有PbO2、RuO2、IrO2、TiO2、MnO2中至少一种导电金属或金属氧化物，第一阴极板（24）的材料为不锈钢电极、石墨、活性炭纤维毡、活性炭纤维布以及涂敷有PbO2、RuO2、IrO2、TiO2、MnO2中至少一种的导电金属或金属氧化物，第二阴极板（27）的材料为活性炭纤维电极、石墨电极、石墨气体扩散电极、活性炭气体扩散电极、多壁纳米碳管电极，电极板的形状为网状、孔状或丝栅状。 4. A device for recovering cyanide by electromotive migration/recovering NH3 by oxidation according to claim 1, characterized in that the materials of the first anode plate (23) and the second anode plate (26) are graphite, Activated carbon fiber felt, activated carbon fiber cloth, and at least one conductive metal or metal oxide coated with PbO 2 , RuO 2 , IrO 2 , TiO 2 , MnO 2 , the material of the first cathode plate (24) is stainless steel electrode, graphite , activated carbon fiber felt, activated carbon fiber cloth, and conductive metal or metal oxide coated with at least one of PbO 2 , RuO 2 , IrO 2 , TiO 2 , MnO 2 , and the material of the second cathode plate (27) is activated carbon fiber Electrode, graphite electrode, graphite gas diffusion electrode, activated carbon gas diffusion electrode, multi-wall carbon nanotube electrode, the shape of the electrode plate is mesh, hole or wire grid. 5. 根据权利要求1所述的一种电动力迁移回收氰/氧化回收NH3的装置，其特征在于所述的惰性填充物（20）为凸凹沟槽开孔瓷球、活性瓷球、开孔瓷球、微孔瓷球、蓄热瓷球、研磨瓷球、三形多孔瓷质、树脂填料中的一种或多种。 5. A device for recovery of cyanide by electrodynamic migration/oxidation recovery of NH 3 according to claim 1, characterized in that the inert filler (20) is ceramic balls with convex and concave grooves, active ceramic balls, open One or more of porous ceramic balls, microporous ceramic balls, thermal storage ceramic balls, grinding ceramic balls, three-shaped porous ceramics, and resin fillers. 6. 一种使用如权利要求1所述装置的电动力迁移回收氰/氧化回收NH3的方法，其特征在于电动废气处理装置（3）在20V以上产生直流电，促使阳极室（21）内产生大量H+，形成酸性氛围，pH≤1.0，阴极室（22）产生大量OH-，形成碱性氛围，pH≥14.0；废气集气罩（1）中的含氰废气在电动废气处理装置（3）中被喷淋液吸收后，氰在阴极室（22）内99%以上转化为CN-，然后在电作用下迁移，经过阴离子交换膜（19）进入阳极室（21），并生成纯净的HCN气体，生成的HCN气体进入HCN回收储罐（4），被清水吸收生成氢氰酸，氢氰酸溶液进入炭流化床（8），在炭流化床（8）中的催化剂的作用下被氧化生成NH3，炭流化床（8）内的填充物上的催化剂能够加快氧化HCN生成NH3，提高处理HCN污染的能力以及回收NH3的效率，反应式为                                               
Figure 2012103946730100001DEST_PATH_IMAGE002
，生成的NH3进入吸收罐（12），被吸收罐（12）中的酸吸收，转化为(NH4)2SO4、NH4Cl或(NH4)3P3O4产物；喷淋液池（13）内的初始喷淋液为含NaCl、Na2SO4、Na3PO4、Na2HPO4、NaNO3中至少一种的含盐水，含盐量为0.01%~10%，进行间歇或连续喷淋吸收电动废气处理装置（3）中的HCN，喷淋头（14）为翅翼的螺旋式喷淋组件，喷淋液沿切线方向分散形成细小的雾点，HCN溶解于这些雾点中形成高效的吸收效率，在电动废气处理装置（3）中产生的阳极液和阴极液被引出，分别进入阳极液罐（15）、阴极液罐（16），阳极液罐15和阴极液罐16内的储液进入中和池（17）中和，中和液用于补充喷淋池（13）内的喷淋液；经电动废气处理装置（3）处理后残留的低浓度含CN-溶液进入电芬顿装置（18），将CN-转化为CO2。 6. A method for recovering cyanide by electromotive transfer or recovering NH3 by oxidation using the device as claimed in claim 1, characterized in that the electric waste gas treatment device (3) generates direct current above 20V to promote the generation of A large amount of H + forms an acidic atmosphere, pH ≤ 1.0, and the cathode chamber (22) produces a large amount of OH - , forming an alkaline atmosphere, pH ≥ 14.0; the cyanide-containing exhaust gas in the exhaust gas collection hood (1) is discharged in the electric exhaust gas treatment device (3 ) after being absorbed by the spray liquid, more than 99% of cyanogen is converted into CN - in the cathode chamber (22), and then migrates under the action of electricity, enters the anode chamber (21) through the anion exchange membrane (19), and generates pure HCN gas, the generated HCN gas enters the HCN recovery storage tank (4), is absorbed by clean water to generate hydrocyanic acid, and the hydrocyanic acid solution enters the carbon fluidized bed (8), and the role of the catalyst in the carbon fluidized bed (8) The carbon fluidized bed (8) is oxidized to generate NH 3 , and the catalyst on the filling in the carbon fluidized bed (8) can accelerate the oxidation of HCN to generate NH 3 , improve the ability to deal with HCN pollution and the efficiency of recovering NH 3 , the reaction formula is
Figure 2012103946730100001DEST_PATH_IMAGE002
, the generated NH 3 enters the absorption tank (12), is absorbed by the acid in the absorption tank (12), and is converted into (NH 4 ) 2 SO 4 , NH 4 Cl or (NH 4 ) 3 P 3 O 4 products; spray The initial spray liquid in the liquid pool (13) is brine containing at least one of NaCl, Na 2 SO 4 , Na 3 PO 4 , Na 2 HPO 4 , and NaNO 3 , with a salt content of 0.01% to 10%. Perform intermittent or continuous spraying to absorb HCN in the electric exhaust gas treatment device (3), the spray head (14) is a spiral spray assembly with wings, the spray liquid disperses along the tangential direction to form fine fog spots, and the HCN is dissolved in High absorption efficiency is formed in these fog spots, and the anolyte and catholyte generated in the electric exhaust gas treatment device (3) are drawn out and enter the anolyte tank (15), catholyte tank (16), anolyte tank 15 and The storage liquid in the catholyte tank 16 enters the neutralization tank (17) for neutralization, and the neutralization liquid is used to supplement the spray liquid in the spray tank (13); The solution containing CN - enters the electro-Fenton device (18) to convert CN - into CO 2 .
CN201210394673.0A 2012-10-17 2012-10-17 A device and method for recovering cyanogen by electrodynamic migration/oxidizing and recovering NH3 Expired - Fee Related CN102872690B (en)

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CN114849706A (en) * 2021-09-23 2022-08-05 北京化工大学 Process method for treating carbon fiber production process waste gas by using molecular sieve catalyst

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CN107913594A (en) * 2016-10-09 2018-04-17 中国石油化工股份有限公司 The removal methods of HCN-containing gases
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CN114849706A (en) * 2021-09-23 2022-08-05 北京化工大学 Process method for treating carbon fiber production process waste gas by using molecular sieve catalyst

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