CN110280104A - A kind of phosphorus ammonium method processing catalyst ammonia-contaminated gas and ammonia reclaiming process - Google Patents

A kind of phosphorus ammonium method processing catalyst ammonia-contaminated gas and ammonia reclaiming process Download PDF

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Publication number
CN110280104A
CN110280104A CN201910549158.7A CN201910549158A CN110280104A CN 110280104 A CN110280104 A CN 110280104A CN 201910549158 A CN201910549158 A CN 201910549158A CN 110280104 A CN110280104 A CN 110280104A
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CN
China
Prior art keywords
ammonia
contaminated gas
tower
hydrogen
phosphoric acid
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CN201910549158.7A
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Chinese (zh)
Inventor
赵旭
申涛
王慧
周铁桩
谢晓玲
窦岩
王建刚
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Tianhua Institute of Chemical Machinery and Automation Co Ltd
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Tianhua Institute of Chemical Machinery and Automation Co Ltd
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Priority to CN201910549158.7A priority Critical patent/CN110280104A/en
Publication of CN110280104A publication Critical patent/CN110280104A/en
Pending legal-status Critical Current

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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
    • B01D53/14Separation 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 absorption
    • B01D53/1418Recovery of products
    • 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
    • B01D53/14Separation 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 absorption
    • B01D53/1425Regeneration of liquid absorbents
    • 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
    • B01D53/14Separation 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 absorption
    • B01D53/1493Selection of liquid materials for use as absorbents
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01CAMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00Ammonia; Compounds thereof
    • C01C1/02Preparation, purification or separation of ammonia
    • C01C1/022Preparation of aqueous ammonia solutions, i.e. ammonia water
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01CAMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00Ammonia; Compounds thereof
    • C01C1/02Preparation, purification or separation of ammonia
    • C01C1/026Preparation of ammonia from inorganic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2252/00Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10Inorganic absorbents
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals

Abstract

The present invention relates to a kind of phosphorus ammonium method processing catalyst ammonia-contaminated gas and ammonia reclaiming process, comprising the following steps: (1) clear water is transported in scrubbing tower, circulation washing, dedusting is carried out to ammonia-contaminated gas, obtains dustless ammonia-contaminated gas;(2) dustless ammonia-contaminated gas carries out reverse contact absorption through one hydrogen ammonia of phosphoric acid, ammonium di-hydrogen phosphate mixed solution spray, respectively obtains clean gas and biphosphate ammonia solution after absorbing;(3) biphosphate ammonia solution enters desorber through heat exchange, forms one hydrogen ammonia solution of dense ammonia steam and phosphoric acid;(4) dense ammonia steam forms concentrated ammonia liquor and is input in tank used for storing ammonia through condensation;(5) one hydrogen ammonia solution of phosphoric acid and steam heat-exchanging, one hydrogen ammonia solution of phosphoric acid and steam condensate after respectively obtaining heat exchange;(6) the one hydrogen ammonia solution of phosphoric acid after exchanging heat is warming up to 140 DEG C of rear portions and enters desorber, and another part exchanges heat with biphosphate ammonia solution, and the one hydrogen ammonia solution of phosphoric acid after heat exchange absorbs ammonia-contaminated gas.The present invention is energy-efficient and investment is small.

Description

A kind of phosphorus ammonium method processing catalyst ammonia-contaminated gas and ammonia reclaiming process
Technical field
The present invention relates to catalyst production field more particularly to a kind of phosphorus ammonium method processing catalyst ammonia-contaminated gas and recovery ammonia Technique.
Background technique
Catalyst production industry can generate a large amount of ammonia-contaminated gas, and conventional process ammonia-contaminated gas technique all has device and do not save Can, it discharge the problems such as not up to standard, operating cost is high, personal safety.
Processing for ammonia-contaminated gas, domestic and international existing technology mainly have Physical Absorption, chemical absorbing, catalytic decomposition, It is catalyzed aerobic breakdown, biodegradable several method.It is mainly sulphur ammonium method in the ammonia-contaminated gas processing technique of catalyst industry application, Chemical absorbing is carried out to ammonia using dilute sulfuric acid, then the ammonium sulfate after absorption is concentrated, crystallizes, be centrifugated, finally Obtain solid ammonium sulfate.Since the technology is using dilute sulfuric acid, equipment material needed for most processes is 316L, preceding Phase equipment investment is big, and technique is cumbersome, complicated, and plant maintenance is difficult;Required raw material dilute sulfuric acid need to uninterruptedly be put into, using dilute sulphur Acid also needs for moisture therein to be evaporated after absorbing, and the public work amount of coming into operation is big, and economic benefit is low.
Summary of the invention
It invests small, energy-efficient phosphorus ammonium method processing catalyst technical problem to be solved by the invention is to provide a kind of and contains Ammonia exhaust gas and ammonia reclaiming process.
To solve the above problems, a kind of phosphorus ammonium method processing catalyst ammonia-contaminated gas of the present invention and ammonia reclaiming process, The following steps are included:
(1) clear water is transported in scrubbing tower, while ammonia-contaminated gas is located at the scrubbing tower by external blower or compressor The ammonia-contaminated gas conveyance conduit I of bottom side is sent into the scrubbing tower;The clear water in tower is placed in the scrubbing tower tower at this time The circulating pump I at bottom is delivered to tower top and carries out circulation washing, dedusting to the ammonia-contaminated gas, obtains dustless ammonia-contaminated gas;
(2) the dustless ammonia-contaminated gas enters the absorption tower through the ammonia-contaminated gas conveyance conduit II of absorb the bottom of the tower side, together When, one hydrogen ammonia of phosphoric acid, ammonium di-hydrogen phosphate mixed solution in the absorption tower are delivered to tower top through circulating pump III, and to the nothing The ammonia-contaminated gas of dirt carries out reverse contact by spray and absorbs, and respectively obtains the clean gas after absorbing and ammonium di-hydrogen phosphate is molten Liquid;Clean gas after the absorption passes through the gas discharge outlet safety dumping at the top of the absorption tower;
(3) the biphosphate ammonia solution is transported in heat exchanger I through the circulating pump II at the absorbing tower bottom and exchanges heat, this The temperature of Shi Suoshu biphosphate ammonia solution rises to 130 DEG C from room temperature, and enters from the middle part of desorber, and the ammonium di-hydrogen phosphate is molten Liquid is respectively formed one hydrogen ammonia solution of dense ammonia steam and phosphoric acid through the desorber;
(4) the dense ammonia steam goes out tower from the tower top of the desorber and enters overhead condenser, while cooling water enters the tower It pushes up in condenser, through condensation, forms concentrated ammonia liquor, which is input in tank used for storing ammonia;
(5) the one hydrogen ammonia solution of phosphoric acid is delivered to heat exchanger II through the circulating pump IV of the desorber tower bottom, is simultaneously from battery limit (BL) Steam be delivered to the heat exchanger II and exchange heat with the one hydrogen ammonia solution of phosphoric acid, one hydrogen of phosphoric acid after respectively obtaining heat exchange Ammonia solution and steam condensate;The steam condensate returns to battery limit (BL);
(6) the one hydrogen ammonia solution of phosphoric acid after the heat exchange is warming up to 140 DEG C of rear portions into the desorber, another part into The biphosphate ammonia solution for entering the heat exchanger I and entering in it exchanges heat, and the one hydrogen ammonia solution of phosphoric acid after heat exchange is from described The top on absorption tower enters the absorption tower and absorbs to ammonia-contaminated gas.
(1) middle clear water refers to tap water or deionized water to the step.
The step (1) in ammonia-contaminated gas ammonia level≤30000mg/m3
(2) middle absorption tower refers in level-one packed absorber, second level packed absorber or multistage packed absorber the step One kind.
The step (2) in gas discharge outlet be chimney pattern.
(3) (5) middle heat exchanger II each means plate heat exchanger, pipe shell type heat exchange to the step for middle heat exchanger I and the step One of device or double pipe heat exchanger.
The step (1) in circulating pump I, the step (2) in circulating pump III, the step (3) in circulating pump II, the step Suddenly (5) middle circulating pump IV each means conventional formula centrifugal pump.
Compared with the prior art, the present invention has the following advantages:
1, the present invention uses one hydrogen ammonia solution circulating technology of phosphoric acid, absorbs the one hydrogen ammonia solution of phosphoric acid after desorption as absorption tower The hand cleanser of ammonia is recycled, and therefore, in the present invention need to only provide phosphoric acid necessary to driving when system is driven, when operation Phosphoric acid is hardly supplemented, greatly reduces filling into for phosphoric acid compared to traditional sulphur ammonium method.
2, it after using the method for the present invention, discharges and does not contain ammonia in exhaust gas, realize the zero-emission of ammonia, and treated Gas is better than national standard reference;The concentration for the ammonium hydroxide produced simultaneously is 20%, and the ammonium hydroxide supply that can be used in factory uses.
3, compared with traditional sulphur ammonium method, reduce the processes such as multiple-effect evaporation, concentration, crystallization, make steamed vapour and recycle cold But the dosage of water greatly reduces.
4, compared with traditional sulphur ammonium method, present invention process process is simple, reduces the processing of catalyst industry ammonia-contaminated gas Equipment input cost and maintenance cost, to ammonia-contaminated gas processing have great importance.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 is process flow chart of the invention.
In figure: 1-scrubbing tower;2-circulating pumps I;3-absorption towers;4-circulating pumps II;5-circulating pumps III;6-heat exchangers Ⅰ;7-desorbers;8-circulating pumps IV;9-overhead condensers;10-heat exchanger IIs;11-tank used for storing ammonia.
Specific embodiment
As shown in Figure 1, a kind of phosphorus ammonium method processing catalyst ammonia-contaminated gas and ammonia reclaiming process, comprising the following steps:
(1) clear water is transported in scrubbing tower 1, while ammonia-contaminated gas is located at 1 bottom of scrubbing tower by external blower or compressor The ammonia-contaminated gas conveyance conduit I of portion side is sent into scrubbing tower 1;The clear water in tower is through being placed in the circulation of 1 tower bottom of scrubbing tower at this time It pumps I 2 and is delivered to tower top and circulation washing, dedusting are carried out to ammonia-contaminated gas, obtain dustless ammonia-contaminated gas.
Wherein: clear water refers to tap water or deionized water.Ammonia level≤30000mg/m of ammonia-contaminated gas3
Circulating pump I 2 refers to conventional formula centrifugal pump.
(2) dustless ammonia-contaminated gas enters absorption tower 3 through the ammonia-contaminated gas conveyance conduit II of 3 bottom side of absorption tower, together When, one hydrogen ammonia of phosphoric acid, ammonium di-hydrogen phosphate mixed solution in absorption tower 3 are delivered to tower top through circulating pump III 5, and contain to dustless Ammonia exhaust gas carries out reverse contact by spray and absorbs, and respectively obtains clean gas and biphosphate ammonia solution after absorbing;It absorbs The gas discharge outlet safety dumping that clean gas afterwards passes through 3 top of absorption tower.
Wherein: absorption tower 3 refers to one in level-one packed absorber, second level packed absorber or multistage packed absorber Kind.
Circulating pump III 5 refers to conventional formula centrifugal pump.
Gas discharge outlet is chimney pattern.
(3) biphosphate ammonia solution is transported in heat exchanger I 6 through the circulating pump II 4 of 3 tower bottom of absorption tower and exchanges heat, at this time The temperature of biphosphate ammonia solution rises to 130 DEG C from room temperature, and enters from the middle part of desorber 7, biphosphate ammonia solution warp Desorber 7 is respectively formed one hydrogen ammonia solution of dense ammonia steam and phosphoric acid.
Wherein: heat exchanger I 6 refers to one of plate heat exchanger, shell-and-tube heat exchanger or double pipe heat exchanger.
Circulating pump II 4 refers to conventional formula centrifugal pump.
(4) dense ammonia steam goes out tower from the tower top of desorber 7 and enters overhead condenser 9, while cooling water enters overhead condensation In device 9, through condensation, concentrated ammonia liquor is formed, which is input in tank used for storing ammonia 11 and stores, can be used in factory The supply of concentrated ammonia liquor.
(5) one hydrogen ammonia solution of phosphoric acid is delivered to heat exchanger II 10 through the circulating pump IV 8 of 7 tower bottom of desorber, is simultaneously from battery limit (BL) Steam be delivered to heat exchanger II 10 and exchange heat with one hydrogen ammonia solution of phosphoric acid, the one hydrogen ammonia solution of phosphoric acid after respectively obtaining heat exchange And steam condensate;Steam condensate returns to battery limit (BL).
Wherein: heat exchanger II 10 refers to one of plate heat exchanger, shell-and-tube heat exchanger or double pipe heat exchanger.
Circulating pump IV 8 refers to conventional formula centrifugal pump.
(6) the one hydrogen ammonia solution of phosphoric acid after exchanging heat is warming up to 140 DEG C of rear portions and enters desorber 7, and another part, which enters, to be changed Hot device I 6 exchanges heat with the biphosphate ammonia solution entered in it, top of the one hydrogen ammonia solution of phosphoric acid after heat exchange from absorption tower 3 Portion enters absorption tower 3 and absorbs to ammonia-contaminated gas.

Claims (7)

1. a kind of phosphorus ammonium method processing catalyst ammonia-contaminated gas and ammonia reclaiming process, comprising the following steps:
(1) clear water is transported in scrubbing tower (1), while ammonia-contaminated gas is located at described wash by external blower or compressor The ammonia-contaminated gas conveyance conduit I for washing tower (1) bottom side is sent into the scrubbing tower (1);The clear water in tower is through being placed at this time The circulating pump I (2) for stating scrubbing tower (1) tower bottom is delivered to tower top and carries out circulation washing, dedusting to the ammonia-contaminated gas, obtains dustless Ammonia-contaminated gas;
(2) the dustless ammonia-contaminated gas enters the absorption tower through the ammonia-contaminated gas conveyance conduit II of absorption tower (3) bottom side (3), meanwhile, one hydrogen ammonia of phosphoric acid, ammonium di-hydrogen phosphate mixed solution in the absorption tower (3) are delivered to tower through circulating pump III (5) Top, and reverse contact is carried out by spray to the dustless ammonia-contaminated gas and is absorbed, respectively obtain the clean gas after absorbing and Biphosphate ammonia solution;Clean gas after the absorption passes through the gas discharge outlet safety dumping at the top of the absorption tower (3);
The biphosphate ammonia solution through the circulating pump II (4) of the absorption tower (3) tower bottom be transported in heat exchanger I (6) into Row heat exchange, the temperature of the biphosphate ammonia solution rises to 130 DEG C from room temperature at this time, and enters from the middle part of desorber (7), should Biphosphate ammonia solution is respectively formed one hydrogen ammonia solution of dense ammonia steam and phosphoric acid through the desorber (7);
(4) the dense ammonia steam goes out tower from the tower top of the desorber (7) and enters overhead condenser (9), while cooling water enters In the overhead condenser (9), through condensation, concentrated ammonia liquor is formed, which is input in tank used for storing ammonia (11);
(5) the one hydrogen ammonia solution of phosphoric acid is delivered to heat exchanger II (10) through the circulating pump IV (8) of the desorber (7) tower bottom, together When the steam from battery limit (BL) be delivered to the heat exchanger II (10) and exchange heat with the one hydrogen ammonia solution of phosphoric acid, respectively obtain and change One hydrogen ammonia solution of phosphoric acid and steam condensate after heat;The steam condensate returns to battery limit (BL);
(6) the one hydrogen ammonia solution of phosphoric acid after the heat exchange is warming up to 140 DEG C of rear portions into the desorber (7), another part Into the heat exchanger I (6) and enter its in biphosphate ammonia solution exchange heat, the one hydrogen ammonia solution of phosphoric acid after heat exchange from The top of the absorption tower (3) enters the absorption tower (3) and absorbs to ammonia-contaminated gas.
2. a kind of phosphorus ammonium method processing catalyst ammonia-contaminated gas as described in claim 1 and ammonia reclaiming process, it is characterised in that: institute Stating step, (1) middle clear water refers to tap water or deionized water.
3. a kind of phosphorus ammonium method processing catalyst ammonia-contaminated gas as described in claim 1 and ammonia reclaiming process, it is characterised in that: institute State step (1) in ammonia-contaminated gas ammonia level≤30000mg/m3
4. a kind of phosphorus ammonium method processing catalyst ammonia-contaminated gas as described in claim 1 and ammonia reclaiming process, it is characterised in that: institute Stating step, (2) middle absorption tower (3) refers to one of level-one packed absorber, second level packed absorber or multistage packed absorber.
5. a kind of phosphorus ammonium method processing catalyst ammonia-contaminated gas as described in claim 1 and ammonia reclaiming process, it is characterised in that: institute State step (2) in gas discharge outlet be chimney pattern.
6. a kind of phosphorus ammonium method processing catalyst ammonia-contaminated gas as described in claim 1 and ammonia reclaiming process, it is characterised in that: institute State step (3) in heat exchanger I (6) and the step (5) in heat exchanger II (10) each mean plate heat exchanger, shell-and-tube heat exchanger or One of double pipe heat exchanger.
7. a kind of phosphorus ammonium method processing catalyst ammonia-contaminated gas as described in claim 1 and ammonia reclaiming process, it is characterised in that: institute State step (1) in circulating pump I (2), the step (2) in circulating pump III (5), the step (3) in circulating pump II (4), the step (5) middle circulating pump IV (8) each means conventional formula centrifugal pump.
CN201910549158.7A 2019-06-24 2019-06-24 A kind of phosphorus ammonium method processing catalyst ammonia-contaminated gas and ammonia reclaiming process Pending CN110280104A (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1056665A (en) * 1990-05-24 1991-12-04 冶金工业部鞍山热能研究院 Reclaim ammonia and produce the method for strong aqua or anhydrous ammonia
CN101531379A (en) * 2009-04-17 2009-09-16 天津天达联合工程技术有限公司 Method for producing anhydrous ammonia by absorbing ammonium phosphate
CN101531380A (en) * 2009-03-03 2009-09-16 德纳(南京)化工有限公司 Ammonia reclaiming technology in process of preparing m-dicyanobenzene by using ammonia oxidation method
CN102530868A (en) * 2010-12-28 2012-07-04 李宽义 Environmental-protection process method for removing ammonia from ammoxidation synthesis gas
CN104689703A (en) * 2015-03-30 2015-06-10 攀钢集团西昌钢钒有限公司 Ammonium phosphate ammonia-washing tail gas treatment technology and ammonium phosphate ammonia-washing system
CN105645436A (en) * 2016-03-18 2016-06-08 安徽省化工设计院 Novel system for recycling ammonia from waste gas produced by benzene and cyanogen device
CN106823692A (en) * 2017-03-22 2017-06-13 天华化工机械及自动化研究设计院有限公司 A kind of ammonia-contaminated gas zero-emission and ammonia reclaiming process
RU2645999C1 (en) * 2017-05-04 2018-02-28 Публичное акционерное общество "Северсталь" Method of purifying coke oven gas from ammonia by circular phosphate method
CN108926962A (en) * 2018-08-10 2018-12-04 重庆天原化工有限公司 Ammonia-containing exhaust recovery and treatment method

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1056665A (en) * 1990-05-24 1991-12-04 冶金工业部鞍山热能研究院 Reclaim ammonia and produce the method for strong aqua or anhydrous ammonia
CN101531380A (en) * 2009-03-03 2009-09-16 德纳(南京)化工有限公司 Ammonia reclaiming technology in process of preparing m-dicyanobenzene by using ammonia oxidation method
CN101531379A (en) * 2009-04-17 2009-09-16 天津天达联合工程技术有限公司 Method for producing anhydrous ammonia by absorbing ammonium phosphate
CN102530868A (en) * 2010-12-28 2012-07-04 李宽义 Environmental-protection process method for removing ammonia from ammoxidation synthesis gas
CN104689703A (en) * 2015-03-30 2015-06-10 攀钢集团西昌钢钒有限公司 Ammonium phosphate ammonia-washing tail gas treatment technology and ammonium phosphate ammonia-washing system
CN105645436A (en) * 2016-03-18 2016-06-08 安徽省化工设计院 Novel system for recycling ammonia from waste gas produced by benzene and cyanogen device
CN106823692A (en) * 2017-03-22 2017-06-13 天华化工机械及自动化研究设计院有限公司 A kind of ammonia-contaminated gas zero-emission and ammonia reclaiming process
RU2645999C1 (en) * 2017-05-04 2018-02-28 Публичное акционерное общество "Северсталь" Method of purifying coke oven gas from ammonia by circular phosphate method
CN108926962A (en) * 2018-08-10 2018-12-04 重庆天原化工有限公司 Ammonia-containing exhaust recovery and treatment method

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