CN107029526A - A kind of incineration tail gas denitration advanced treatment process integrated with Tuo bioxin - Google Patents

A kind of incineration tail gas denitration advanced treatment process integrated with Tuo bioxin Download PDF

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Publication number
CN107029526A
CN107029526A CN201710304597.2A CN201710304597A CN107029526A CN 107029526 A CN107029526 A CN 107029526A CN 201710304597 A CN201710304597 A CN 201710304597A CN 107029526 A CN107029526 A CN 107029526A
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tail gas
bioxin
incineration tail
treatment process
gas
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Inventor
李溪
王祥
沈丽娜
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ENVIROMENTAL TECHNOLOGY Co Ltd NANJING UNIVERSITY OF TECHNOLOGY
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ENVIROMENTAL TECHNOLOGY Co Ltd NANJING UNIVERSITY OF TECHNOLOGY
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Priority to CN201710304597.2A priority Critical patent/CN107029526A/en
Publication of CN107029526A publication Critical patent/CN107029526A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/32Separation 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 by electrical effects other than those provided for in group B01D61/00
    • B01D53/323Separation 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 by electrical effects other than those provided for in group B01D61/00 by electrostatic effects or by high-voltage electric fields
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/007Separation 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 by irradiation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8621Removing nitrogen compounds
    • B01D53/8625Nitrogen oxides
    • B01D53/8631Processes characterised by a specific device
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8668Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/10Oxidants
    • B01D2251/104Ozone
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/80Type of catalytic reaction
    • B01D2255/802Photocatalytic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/80Type of catalytic reaction
    • B01D2255/806Electrocatalytic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2259/00Type of treatment
    • B01D2259/12Methods and means for introducing reactants
    • B01D2259/122Gaseous reactants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2259/00Type of treatment
    • B01D2259/80Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/804UV light

Abstract

The invention belongs to exhaust-gas treatment field, it is related to a kind of out of stock advanced treatment process integrated with Tuo bioxin of incineration tail gas.A kind of out of stock advanced treatment process integrated with Tuo bioxin of incineration tail gas, enter high-energy discharge reactor after the incineration tail gas of nitrogen-containing oxide and bioxin is mixed with ozone and carry out electrochemical catalysis, photocatalysis and ozone cooperative effect processing, tail gas after processing further removes denitrification into caustic scrubber, so as to be removed while realizing nitrogen oxides and bioxin.The present invention integrates electrochemical catalysis, photocatalysis and ozone catalytic, processing rotary kiln incineration tail gas nitrogen oxide and bioxin, realizes multiple concerted catalysis, can greatly improve the density of free radical, can thoroughly decompose bioxin, while NO is oxidized into NO2, it is further that nitrogen oxides changing into nitrate removal purification efficiency is high, easy to operate that the waste gas after processing passes through alkali cleaning.

Description

A kind of incineration tail gas denitration advanced treatment process integrated with Tuo bioxin
Technical field
The invention belongs to exhaust-gas treatment field, it is related to a kind of incineration tail gas denitration depth science and engineering integrated with de- bioxin Skill.
Background technology
A large amount of solid waste are also easy to produce in chemical industry production process, for example:Rectifying still is residual, centrifuge mother liquor, useless activity Charcoal, biochemical sludge etc., largely belong to dangerous solid waste and are centrally disposed, it is necessary to send dangerous waste to dispose center.But with dangerous waste amount day Benefit increases, and existing dangerous waste disposal center processing ability is substantially not enough, and enterprise's dangerous waste processing outlet turns into the one of puzzlement enterprise development Hang-up.
The self-built incinerator of increasing enterprise handles the dangerous waste of itself generation, on the one hand alleviates in current dangerous waste disposal The load of the heart, on the other hand, dangerous waste Bu Chu enterprises reduce the wind that the secondary pollutions such as leakage are there may be in dangerous waste transportation Danger.Most of chemical enterprise, for example:Containing materials such as chlorine and organic nitrogens in agricultural chemicals, medicine etc., its dangerous waste, in burning process Tail gas in can containing nitrogen oxides He the pollutant such as dioxin.Its normal handling process is as follows:
Rotary kiln --- dual firing chamber's --- SNCR (denitration) --- chilling --- dry type depickling --- bag-type dust --- alkali Wash --- blower fan --- chimney.
Dangerous waste incinerator requires that dual firing chamber's incineration temperature is more than 1100 DEG C, wherein can produce nitrogen oxygen except organic nitrogen itself is burned Outside compound, the N2 in air can also generate nitrogen oxides on this condition, from SNCR denitration from the point of view of the control measure of current tail gas Effect only has 50%, it is difficult to reach emission request, most enterprises use SCR (catalytic denitration) technique, but operating cost is high, catalysis The problems such as agent is easily poisoned, tail gas nitrogen oxide is unable to stably reaching standard.
Bioxin is many benzene organic compounds, and it is the material of severe toxicity, and chloride waste material is produced in combustion.Two Evil heroic spirits body is decomposed more than 700 DEG C, and flue gas has a small amount of synthesis again at 500~200 DEG C.According to Thermal Power Engineering system of Tsing-Hua University Qian Yuanji et al. (《The working condition and control strategy of waste incineration Zhong bioxin》) research show , bioxin control process bags The stage of being initially generated, pyrolytic stage and later stage synthesis three phases are included, wherein chilling can reduce the yield of bioxin, do The activated carbon sprayed into formula depickling can also handle generation bioxin on a small quantity, but the discharge of , bioxin according to the actual fact is dense Degree still causes anxiety, although can reach《Dangerous waste incineration contamination control standard》(GB18484-2011) 0.5ng/m3Mark Standard, but as what exhaust emissions was required increasingly increases, especially new discharge standard《Dangerous waste incineration contamination control mark It is accurate》(GB18484-2014) concentration of emission≤0.1ng/m3 of the concentration of nitrogen oxides≤400mg/m3 , bioxin in.
Therefore, the integration removing treatment technology of the new denitration of exploitation and Tuo bioxin, for entering in rotary kiln exhaust gas The denitration of row depth and Chu bioxin are significant.
The content of the invention
The technical problem to be solved in the invention is:For nitrogen-containing oxide and Er Evil in current rotary kiln incineration tail gas The treatment technology efficiency of English is low, cost is high, fluctuation of service the problems such as, and can stablize, efficiently at low cost there is provided one kind Rotary kiln incineration nitrogen oxide in tail gas is handled He the technique of bioxin.
A kind of out of stock advanced treatment process integrated with Tuo bioxin of incineration tail gas, including by nitrogen-containing oxide and Er Evil The incineration tail gas of English enters high-energy discharge reactor and carries out electrochemical catalysis, photocatalysis and ozone cooperative work after being mixed with ozone With processing, the tail gas after processing further removes denitrification into caustic scrubber, so as to realize nitrogen oxides and bioxin While remove.
Described incineration tail gas main component is:Nitrogen oxides and bioxin etc..
As a preference of the present invention, the electrode of described high-energy discharge reactor is made up of high-pressure side and low-pressure end, high pressure Hold as 0.1~0.4mm of diameter titaniums silk, low-pressure end is the hollow metal pipe of inwall loaded optic catalyst;Incineration tail gas and ozone The mixed gas of composition from hollow metal circular tube by carrying out, the high energy particle on the one hand produced by high-energy discharge reactor with The photochemical catalyst and additional ozone cooperative of its ultraviolet optical drive excited are degraded to pollutant direct oxidation, are on the other hand produced Active particle including O, OH further decomposes into nontoxic compound to contaminant molecule.
As a preference of the present invention, the photochemical catalyst of wall loading is selected from high-field electrode:TiO2/Ni、TiO2/Pt、SnO/ One kind in Ni, SnO/Pt.
As a preference of the present invention, described high-energy discharge reactor assembly frequency continuously adjustabe, frequency range is 1~ 1000Hz, 1~3Kw of power bracket
As a preference of the present invention, the amount of described mixing ozone is 5%~10% (V/V) of incineration tail gas total amount.
As a preference of the present invention, 2~4m of sprinkle density of described caustic scrubber3/(m2, h), the alkali lye used is selected from NaOH, Ca (OH) 2 or KOH solution, the concentration of lye 8-15%wt used, preferably 10wt%.
A kind of device for being used to carry out the out of stock advanced treating integrated with Tuo bioxin of incineration tail gas, is mainly occurred by ozone Device, gas mixer system, high capacity power source, reactor assembly, the electrode composition of inwall coating photochemical catalyst;Ozone generator with Connected between gas mixing system by flanged (FLGD) pipeline, connection tail gas admission line in gas mixer system one end is another Hold Ligature device system;Some electrodes are set in reactor assembly;Electrode is made up of low-pressure end and high-pressure side, and low-pressure end is Inwall coats the hollow metal pipe of photochemical catalyst, and high-pressure side is the titanium silk of insertion die, and pipe inside leads to for the air-flow of tail gas Road, tail gas is processed in gas channel;Reactor assembly collectively forms high-energy discharge reactor with high capacity power source, therebetween Connected by high-tension bus-bar;The gas vent of reactor assembly connects the air inlet of the caustic scrubber of next step by pipeline.
The described a diameter of 0.1~0.4mm of high-pressure side titanium silk.
Described low-pressure end material is 316L stainless steels, and the photochemical catalyst of its interior wall loading is selected from:TiO2/Ni、TiO2/Pt、 One kind in SnO/Ni, SnO/Pt.
Described gas mixer internal system is provided with some blast fences for making gas produce baffling.
Beneficial effect:
1st, the present invention integrates electrochemical catalysis, photocatalysis and ozone catalytic, handles rotary kiln incineration tail gas nitrogen oxygen Compound and bioxin, realize multiple concerted catalysis, can greatly improve the density of free radical, can thoroughly decompose bioxin, NO is oxidized to NO simultaneously2, the waste gas after processing is by alkali cleaning further by nitrogen oxides changing into nitrate removal purification efficiency It is high, easy to operate.Exhaust emissions after processing meets《Dangerous waste incineration contamination control standard》(GB18484-2014) arranged in Put standard.
2nd, the active high, long lifespan of support type photocatalysis high-field electrode.
3rd, the anti-load impact ability of device is strong, and operation stability is high, the low advantage of operating cost.
Brief description of the drawings
Denitration and Tuo bioxin integrated apparatus schematic diagrames that Fig. 1, the present invention are used
Wherein, 1 is ozone generator, and 2 be gas mixer system, and 3 be high capacity power source, 4 reactor assemblies, and 5 be inwall Coat the electrode of photochemical catalyst.
Fig. 2, the profile for reactor assembly
Some electrodes 5 that photochemical catalyst is coated with inwall, inwall coating light are provided with reactor assembly 4 as seen from Figure 2 The electrode 5 of catalyst is made up of the titanium silk of hollow circular tube and die.
Embodiment
Xuzhou chemical enterprise tail gas from incinerator:Nitrogen oxides 450mg/m3, bioxin 0.35ng/m3
A kind of incineration tail gas denitration advanced treatment process integrated with Tuo bioxin, by nitrogen-containing oxide and bioxin Incineration tail gas enters high-energy discharge reactor (Fig. 1, similarly hereinafter) after being mixed with ozone and carries out electrochemical catalysis, photocatalysis and ozone Synergy processing, the tail gas after processing further removes denitrification into caustic scrubber so that realize nitrogen oxides and Removed while bioxin.
Following examples are handled Xuzhou chemical enterprise tail gas from incinerator according to the method described above:
Embodiment 1
The photochemical catalyst of wall loading is TiO in high-energy discharge reactor assembly low-field electrode2/ Ni, high-pressure side titanium silk diameter For 0.2mm, frequency is 500Hz, power 3Kw;The amount for mixing ozone is 10% (V/V) of waste gas total amount, and the spray of scrubbing tower is close Spend 2m3/(m2, h), use 10wt% NaOH solution.
Coating cloud nitrogen oxides 90mg/m after processing3, bioxin 0.0252ng/m3, discharge meets《Dangerous waste incineration is dirty Contaminate control standard》(GB18484-2014).
Embodiment 2
The photochemical catalyst of wall loading is TiO in high-energy discharge reactor assembly low-field electrode2/ Pt, high-pressure side titanium silk diameter For 0.4mm, frequency is 1000Hz, power 1Kw;The amount for mixing ozone is 5% (V/V) of waste gas total amount, and the spray of scrubbing tower is close Spend 4m3/(m2, h), use 8wt% Ca (OH)2Solution.
Coating cloud nitrogen oxides 110mg/m after processing3, bioxin 0.0312ng/m3, discharge meets《Dangerous waste incineration is dirty Contaminate control standard》(GB18484-2014).
Embodiment 3
The photochemical catalyst of wall loading is SnO/Ni in high-energy discharge reactor assembly low-field electrode, and high-pressure side titanium silk is a diameter of 0.1mm, frequency is 600Hz, power 2Kw;The amount for mixing ozone is 8% (V/V) of waste gas total amount, the sprinkle density of scrubbing tower 3m3/(m2, h), use 12wt% KOH solution.
Nitrogen oxides 100mg/m after processing3, bioxin 0.0282ng/m3, discharge meets《Dangerous waste incineration pollution control Standard processed》(GB18484-2014).
Embodiment 4
The photochemical catalyst of wall loading is SnO/Pt in high-energy discharge reactor assembly low-field electrode, and high-pressure side titanium silk is a diameter of 0.3mm, frequency is 800Hz, power 3Kw;The amount for mixing ozone is 10% (V/V) of waste gas total amount, the sprinkle density of scrubbing tower 3m3/(m2, h), use 10wt% NaOH solution.
Nitrogen oxides 80mg/m after processing3, bioxin 0.0232ng/m3, discharge meets《Dangerous waste incineration pollution control Standard processed》(GB18484-2014).

Claims (10)

1. a kind of out of stock advanced treatment process integrated with Tuo bioxin of incineration tail gas, it is characterised in that including by nitrogen-containing oxide And the incineration tail gas of bioxin mixed with ozone after enter high-energy discharge reactor and carry out electrochemical catalysis, photocatalysis and smelly The processing of oxygen synergy, the tail gas after processing further removes denitrification into caustic scrubber so that realize nitrogen oxides with Removed while Ji bioxin.
2. the out of stock advanced treatment process integrated with Tuo bioxin of incineration tail gas according to claim 1, it is characterised in that The electrode of described high-energy discharge reactor is made up of high-pressure side and low-pressure end, and high-pressure side is 0.1~0.4mm of diameter titaniums silk, low Pressure side is the hollow metal pipe of inwall loaded optic catalyst;The mixed gas that incineration tail gas and ozone are constituted is from hollow round metal By carrying out in pipe, the photocatalysis for the ultraviolet optical drive that the high energy particle on the one hand produced by high-energy discharge reactor is excited with it Agent and additional ozone cooperative are degraded to pollutant direct oxidation, on the other hand produce the active particle including O, OH Nontoxic compound is further decomposed into contaminant molecule.
3. the out of stock advanced treatment process integrated with Tuo bioxin of incineration tail gas according to claim 2, it is characterised in that The photochemical catalyst of the low-pressure end hollow metal round tube inner wall load of high-field electrode is selected from:TiO2/Ni、TiO2/Pt、SnO/Ni、SnO/ One kind in Pt.
4. the out of stock advanced treatment process integrated with Tuo bioxin of incineration tail gas according to claim 1, it is characterised in that Described high-energy discharge reactor frequency continuously adjustabe, frequency range is 1~1000Hz, 1~3Kw of power bracket.
5. the out of stock advanced treatment process integrated with Tuo bioxin of incineration tail gas according to claim 1, it is characterised in that The amount of the ozone of mixing is 5%~10% (V/V) of incineration tail gas total amount.
6. the out of stock advanced treatment process integrated with Tuo bioxin of incineration tail gas according to claim 1, it is characterised in that The sprinkle density of described caustic scrubber is 2~4m3/(m2, h), the alkali lye used is selected from NaOH, Ca (OH)2Or KOH solution, alkali Liquid concentration is 8-15%wt.
7. the out of stock advanced treatment process integrated with Tuo bioxin of incineration tail gas according to claim 6, it is characterised in that Described concentration of lye is 10%wt.
8. a kind of be used to carry out the device of the out of stock advanced treating integrated with Tuo bioxin of incineration tail gas, it is characterised in that mainly by Ozone generator (1), gas mixer system (2), high capacity power source (3), reactor assembly (4), inwall coating photochemical catalyst Electrode (5) is constituted;It is connected between ozone generator and gas mixing system (2) by flanged (FLGD) pipeline, gas mixer system System (2) one end connection tail gas admission line, other end Ligature device system (4);Some electricity are set in reactor assembly (4) Pole (5);Electrode (5) is made up of low-pressure end and high-pressure side, and low-pressure end is the hollow metal pipe that inwall coats photochemical catalyst, high pressure Hold to insert the gas channel inside the titanium silk of die, pipe for tail gas, tail gas is processed in gas channel;Reactor assembly (4) high-energy discharge reactor is collectively formed with high capacity power source (3), is connected by high-tension bus-bar therebetween;Reactor assembly (4) Gas vent pass through pipeline connect next step caustic scrubber air inlet.
9. the device according to claim 8 for being used to carry out the out of stock advanced treating integrated with Tuo bioxin of incineration tail gas, It is characterized in that the described a diameter of 0.1~0.4mm of high-pressure side titanium silk.
10. the device according to claim 8 for being used to carry out the out of stock advanced treating integrated with Tuo bioxin of incineration tail gas, It is characterized in that described low-pressure end material is 316L stainless steels, the photochemical catalyst of its interior wall loading is selected from:TiO2/Ni、TiO2/ One kind in Pt, SnO/Ni, SnO/Pt.
CN201710304597.2A 2017-05-03 2017-05-03 A kind of incineration tail gas denitration advanced treatment process integrated with Tuo bioxin Pending CN107029526A (en)

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CN108786788A (en) * 2018-06-21 2018-11-13 上海理工大学 A kind of removing dioxin in flue gas and NOxCatalyst and preparation method and application
CN111744346A (en) * 2020-07-02 2020-10-09 天津市英格环保科技有限公司 Tail gas purification method for lysine granulation system
CN111744347A (en) * 2020-07-02 2020-10-09 天津市英格环保科技有限公司 Waste gas treatment process for threonine production

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CN207137652U (en) * 2017-05-03 2018-03-27 南京益农环境科技有限公司 A kind of incineration tail gas denitration advanced treatment apparatus integrated with Tuo bioxin

Cited By (4)

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CN108786788A (en) * 2018-06-21 2018-11-13 上海理工大学 A kind of removing dioxin in flue gas and NOxCatalyst and preparation method and application
CN108786788B (en) * 2018-06-21 2021-05-11 上海理工大学 Method for removing dioxin and NO in flue gasxCatalyst, preparation method and application
CN111744346A (en) * 2020-07-02 2020-10-09 天津市英格环保科技有限公司 Tail gas purification method for lysine granulation system
CN111744347A (en) * 2020-07-02 2020-10-09 天津市英格环保科技有限公司 Waste gas treatment process for threonine production

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Application publication date: 20170811