CN103785263A - Ammonia-containing tail gas treatment recycling method - Google Patents
Ammonia-containing tail gas treatment recycling method Download PDFInfo
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- CN103785263A CN103785263A CN201410050253.XA CN201410050253A CN103785263A CN 103785263 A CN103785263 A CN 103785263A CN 201410050253 A CN201410050253 A CN 201410050253A CN 103785263 A CN103785263 A CN 103785263A
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- ammonia
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- tail gas
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- acid
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention relates to a technology for treating ammonia-containing tail gas generated by ammonium paratungstate calcining in the tungsten powder metallurgy industry and in particular relates to a method for recycling tungsten oxide dust and ammonia in an ammonia-containing tail gas treatment process through a dust collection and acid spray absorption method. The treated tail gas reaches the emission standard. The method comprises the following steps: (1) dust collection; (2) water spray and dust collection; (3) condensation; (4) acid absorption; and (5) evaporative crystallization. The ammonia-containing tail gas of different concentrations can be treated, the ammonia-containing tail gas containing other combustible materials also can be treated, and the ammonia-containing tail gas generated in a converter is treated, so that the tungsten oxide dust in the tail gas can be totally recycled, the ammonia gas can be totally converted into ammonia sulfate (or ammonium chloride and ammonium nitrate) crystals, and the problems of ammonia pollution and secondary environmental pollution are solved.
Description
Technical field
The present invention relates to ammonium paratungstate in tungsten powder smelting industry and calcine the ammonia vent gas treatment technology producing, in particular, relate to the recovery that realizes tungsten oxide dust and ammonia in ammonia vent gas treatment process by gathering dust with the method for sour spray-absorption, tail gas qualified discharge after processing.
Background technology
Tungsten powder is smelted in production process at home, uses converter calcining ammonium paratungstate to produce and makes tungsten oxide product, contains 5% ammonia in ammonium paratungstate, produces tail gas in the time of calcining and decomposing, contains NH in tail gas
3, H
2o, O
2, N
2with tungsten oxide dust, ammonia is colourless, the alkaline irritative gas of high water soluble, and after discharge, stench is pungent, trees withered or died, infringement people's respiratory system and skin, it is atmosphere pollution not only, and can make body eutrophication after formation rainwater, polluted source, causes serious environmental pollution.At present, aspect processing converter calcining ammonium paratungstate generation ammonia tail gas, some enterprises adopt water spraying method to process ammonia, this method can not absorb ammonia completely, can not effectively reclaim the tungsten powder dirt in converter calcination process, absorption liquid enters waste water, causes the ammonia-nitrogen content in industrial wastewater to exceed standard, and has produced new secondary pollution.Along with the progress for the treatment of tail gas technology, the processing of ammonia tail gas is had now to the new technologies such as biological filtering tower combined working technology and incineration technology, biological filtering tower combined working technology is mainly used in the ammonia nitrogen processing in waste water, and incineration technology also only adapts to process containing the high petrochemical industry of ammonia concentration, and need consume fuel gas to provide combustion heat energy for it, and with CO
2deng the discharge of tail gas.
Chinese patent " ammonia-containing tail gas treating furnace " (patent No. 2009101153431), discloses one ammonia is placed in to high temperature, catalyst, has H
2in the situation of O, make the equipment of its catalytic decomposition, its reactive group present principles is:
2NH
3=N
2﹢3H
2
2H
2﹢ O
2=2H
2o+ heat
Utilize it to process ammonia tail gas, shortcoming one is there is no comprehensively to reclaim the ammonia in ammonia tail gas, but it is directly decomposed to discharge, has caused the waste of resource; The 2nd, tungsten oxide dust in ammonia tail gas is not collected, can not effectively improve the rate of recovery of tungsten; The 3rd, in catalytic process, need high temperature, produce thermal pollution, and related to combustion of hydrogen acquisition energy, increase the potential safety hazard such as blast, fire.
Summary of the invention
The object of the invention is to provide a kind of method that ammonia vent gas treatment reclaims, it can accomplish to discharge without Tail Gas, converter calcining ammonium paratungstate be can also effectively reclaim and ammonia and the tungsten powder dirt of in tungsten oxide product process, discharging with tail gas produced, both accomplished secondary resource comprehensive utilization, also the impact of having avoided ammonia emission to cause atmospheric environment, realize the environmental requirement of polluting without ammonia, not only environmental protection but also economy.
Technical solution of the present invention: a kind of method that ammonia vent gas treatment reclaims, comprises the following steps:
(1) gather dust
Producing with converter calcining ammonium paratungstate the ammonia tail gas discharging in tungsten oxide product process delivers to and in dust collecting system, carries out cyclone dust collection or gravity gather dust (also can adopt cyclone dust collection to add gravity gathers dust), effectively to reclaim the tungsten oxide dust in the ammonia-containing exhaust that converter produces, and purify ammonia-containing exhaust;
(2) water spray gathers dust
In ammonia tail gas larger particles tungsten oxide dust through step (1) major part remove, wherein in ammonia tail gas, remaining fine grained tungsten oxide dust passes through Venturi tube or absorption tower water spray-absorption again, after absorption liquid reaches capacity, allow crystal structure separate out by the method cooling, solution circulation uses, and tail gas enters next step and carries out advanced treating;
(3) condensation
Ammonia tail gas after water spray gathers dust is passed in condenser, its temperature is controlled to 30-80 ℃, can collect and obtain high concentration ammoniacal liquor in condensation chamber, the ammoniacal liquor obtaining can fully utilize or sell, thus protection of the environment;
(4) acid absorbs
Through water spray gather dust and condensed ammonia tail gas by absorption tower, with a kind of spray-absorption in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid be ammonium salt solution, tail gas directly discharges.Reaction equation is:
2NH
3+H
2SO
4=(NH
4)
2SO
4
NH
3+HCl=NH
4Cl
NH
3+HNO
3=NH
4NO
3；
(5) evaporative crystallization
One in ammonia tail gas and pH value≤6 sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid is constantly reacted, when pH value reaches neutrality, obtain the sulfate of ammoniac solution of saturated concentration or ammonium chloride, ammonium nitrate, ammonium phosphate solution, by solution evaporative crystallization, the water that obtains of evaporation is back to step (2) to carry out secondary water spray and gathers dust, the sulfate of ammoniac obtaining or ammonium chloride, ammonium nitrate crystals, as byproduct, can be used for the raw materials for production of composite fertilizer, accomplish resource comprehensive recycling.
Beneficial effect of the present invention: the ammonia-containing exhaust that can process variable concentrations, also can process the ammonia-containing exhaust that contains other combustible, the ammonia tail gas that converter produces after treatment, tungsten oxide dust in tail gas can all reclaim, ammonia can all be converted into sulfate of ammoniac (or ammonium chloride, ammonium nitrate) crystal, no longer produces that ammonia pollutes and the problem of secondary environmental pollution; Cost of investment is low, and processing method is simple, and byproduct ammoniacal liquor can be used for other smelting chemical field, and sulfate of ammoniac (or ammonium chloride, ammonium nitrate etc.) can be used for composite fertilizer field, has not only accomplished protection of the environment, and has accomplished the comprehensive utilization of resource.
Accompanying drawing explanation
Accompanying drawing is embodiment of the present invention process chart.
The specific embodiment
Below in conjunction with embodiment, the present invention is further illustrated, and institute's use equipment is prior art.
Embodiment 1: the present invention includes one-level and gather dust, secondary water spray gathers dust, condensation, three grades of sprays of sulfuric acid (pH value≤6), evaporative crystallization is prepared high-purity sulphuric acid ammonia crystal step, gather dust in step in above-mentioned one-level, first by producing in converter high-temperature calcination decomposition ammonium paratungstate, ammonia-containing exhaust carries out cyclone dust collection or gravity gathers dust, gather dust and can fully reclaim the bulky grain tungsten oxide dust in ammonia-containing exhaust by one-level cyclone dust collection or gravity, also can strengthen next step water and spray the effect of gathering dust, gather dust in step at secondary water spray subsequently, ammonia tail gas after dedusting is carried out to secondary and gathered dust by the spray tower that gathers dust, further remove granule tungsten oxide dust, after condensing steps, collect again ammoniacal liquor, remaining ammonia tail gas is through three grades of sprays of persulfuric acid, last ammonia tail gas reaches the discharge standard of national regulation, by exhaust blower, gas is entered to atmosphere, the one-level tungsten oxide dust that ammonia-containing exhaust is carried out in step to the larger particles of collecting after cyclone settling or gravitational settling that gathers dust returns to converter feeding mouth, finishes to enter down one step, ammonia tail gas after one-level is gathered dust passes in water spray dust arrester installation, and spray gathers dust in process, guarantees that water droplet is by high atomisation, carries out after atomizing spray gathers dust, finishing to enter down one step, ammonia tail gas after secondary water spray is gathered dust passes in condenser, and temperature is controlled to 50 ℃, until condensator outlet is emerged without steam, finishes to enter down one step, condensed ammonia-containing exhaust is passed into three grades of sour spray equipments, the ejection from top to down of acid spray, ammonia-containing exhaust is discharged from bottom to top, and both reverse abundant haptoreactions finish to enter down one step, ammonia-containing exhaust after three grades of acid sprays is entered to atmosphere by exhaust blower, described ammonia-containing exhaust≤5mg/m
3, described ammonia-containing exhaust is through the ammoniacal liquor of water spray and condensation gained, and the concentration of its free ammonia is 28g/L, and the concentration of tungstenic is 55g/L, completely can be by the analyzing step for APT production process after benefit ammonia, described ammonia-containing exhaust is to spray neutralization reaction by acid, thus need to change eo-acid according to the pH value of reactant liquor, to maintain the acid degree in spray column, when described spray liquid pH value reaches neutrality, obtain the sulfate of ammoniac solution that concentration is saturated, by solution evaporative crystallization, the water that evaporation obtains is back to secondary water spray and gathers dust, the sulfate of ammoniac crystal obtaining, as byproduct, can be used for the raw materials for production of composite fertilizer, accomplishes resource comprehensive recycling.
Embodiment 2: the present invention includes one-level and gather dust, secondary water spray gathers dust, condensation, three grades of sprays of nitric acid (pH value≤6), evaporative crystallization is prepared high pure nitric acid ammonia crystal step, gather dust in step in above-mentioned one-level, first by producing in converter high-temperature calcination decomposition ammonium paratungstate, ammonia-containing exhaust carries out cyclone dust collection or gravity gathers dust, gather dust and can fully reclaim the bulky grain tungsten oxide dust in ammonia-containing exhaust by one-level cyclone dust collection or gravity, also can strengthen next step water and spray the effect of gathering dust, gather dust in step at secondary water spray subsequently, ammonia tail gas after dedusting is carried out to secondary and gathered dust by the spray tower that gathers dust, further remove granule tungsten oxide dust, after condensing steps, collect again ammoniacal liquor, remaining ammonia tail gas is through three grades of sprays of pernitric acid, last ammonia tail gas reaches the discharge standard of national regulation, by exhaust blower, gas is entered to atmosphere, the described ammonia-containing exhaust one-level tungsten oxide dust that ammonia-containing exhaust is carried out in step to the larger particles of collecting after cyclone settling or gravitational settling that gathers dust returns to converter feeding mouth, finishes to enter down one step, ammonia tail gas after one-level is gathered dust passes in water spray dust arrester installation, and spray gathers dust in process, guarantees that water droplet is by high atomisation, carries out after atomizing spray gathers dust, finishing to enter down one step, ammonia tail gas after secondary water spray is gathered dust passes in condenser, and temperature is controlled to 40 ℃, until condensator outlet is emerged without steam, finishes to enter down one step, condensed ammonia-containing exhaust is passed into three grades of sour spray equipments, the ejection from top to down of acid spray, ammonia-containing exhaust is discharged from bottom to top, and both reverse abundant haptoreactions finish to enter down one step, ammonia-containing exhaust after three grades of acid sprays is entered to atmosphere by exhaust blower, described ammonia-containing exhaust≤4mg/m
3, described ammonia-containing exhaust is through the ammoniacal liquor of water spray and condensation gained, and the concentration of its free ammonia is 32g/L, and the concentration of tungstenic is 70g/L, completely can be by the analyzing step for APT production process after benefit ammonia, described ammonia-containing exhaust is to spray neutralization reaction by acid, thus need to change eo-acid according to the pH value of reactant liquor, to maintain the acid degree in spray column, when described spray liquid pH value reaches neutrality, obtain the nitric acid ammonia solution that concentration is saturated, by solution evaporative crystallization, the water that evaporation obtains is back to secondary water spray and gathers dust, the nitric acid ammonia crystal obtaining, as byproduct, can be used for the raw materials for production of composite fertilizer, accomplishes resource comprehensive recycling.
Claims (2)
1. the method that ammonia vent gas treatment reclaims, is characterized in that: comprise the following steps:
(1) gather dust
Produce with converter calcining ammonium paratungstate the ammonia tail gas discharging in tungsten oxide product process and deliver to and in dust collecting system, carry out cyclone dust collection or gravity gathers dust, effectively to reclaim the tungsten oxide dust in the ammonia-containing exhaust that converter produces, and purify ammonia-containing exhaust;
(2) water spray gathers dust
In ammonia tail gas larger particles tungsten oxide dust through step (1) major part remove, wherein in ammonia tail gas, remaining fine grained tungsten oxide dust passes through Venturi tube or absorption tower water spray-absorption again, after absorption liquid reaches capacity, allow crystal structure separate out by the method cooling, solution circulation uses, and tail gas enters next step and carries out advanced treating;
(3) condensation
Ammonia tail gas after water spray gathers dust is passed in condenser, its temperature is controlled to 30-80 ℃, in condensation chamber, can collect and obtain high concentration ammoniacal liquor;
(4) acid absorbs
Through water spray gather dust and condensed ammonia tail gas by absorption tower, with a kind of spray-absorption in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid be ammonium salt solution, tail gas directly discharges, reaction equation is:
2NH
3+H
2SO
4=(NH
4)
2SO
4
Or NH
3+ HCl=NH
4cl
Or NH
3+ HNO
3=NH
4nO
3;
(5) evaporative crystallization
One in ammonia tail gas and pH value≤6 sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid is constantly reacted, when pH value reaches neutrality, obtain the sulfate of ammoniac solution of saturated concentration or ammonium chloride, ammonium nitrate, ammonium phosphate solution, by solution evaporative crystallization, the water that obtains of evaporation is back to step (2) to carry out secondary water spray and gathers dust, and the sulfate of ammoniac obtaining or ammonium chloride, ammonium nitrate crystals are as byproduct.
2. the method that a kind of ammonia vent gas treatment according to claim 1 reclaims, it is characterized in that: Best Applying Condition is: comprise that one-level gathers dust, secondary water spray gathers dust, condensation, three grades of sprays of pH value≤6 sulfuric acid, evaporative crystallization is prepared high-purity sulphuric acid ammonia crystal step, gather dust in step in above-mentioned one-level, first carry out cyclone dust collection by producing ammonia-containing exhaust in converter high-temperature calcination decomposition ammonium paratungstate, can fully reclaim the bulky grain tungsten oxide dust in ammonia-containing exhaust by one-level cyclone dust collection, also can strengthen next step water and spray the effect of gathering dust, gather dust in step at secondary water spray subsequently, ammonia tail gas after dedusting is carried out to secondary and gathered dust by the spray tower that gathers dust, further remove granule tungsten oxide dust, after condensing steps, collect again ammoniacal liquor, remaining ammonia tail gas is through three grades of sprays of persulfuric acid, last ammonia tail gas reaches the discharge standard of national regulation, by exhaust blower, gas is entered to atmosphere, the one-level tungsten oxide dust that ammonia-containing exhaust is carried out in step to the larger particles of collecting after cyclone settling that gathers dust returns to converter feeding mouth, ammonia tail gas after one-level is gathered dust passes in water spray dust arrester installation, and spray gathers dust in process, guarantees that water droplet is by high atomisation, carries out after atomizing spray gathers dust, finishing to enter down one step, ammonia tail gas after secondary water spray is gathered dust passes in condenser, and temperature is controlled to 50 ℃, until condensator outlet is emerged without steam, finishes to enter down one step, condensed ammonia-containing exhaust is passed into three grades of sour spray equipments, the ejection from top to down of acid spray, ammonia-containing exhaust is discharged from bottom to top, and both reverse abundant haptoreactions finish to enter down one step, ammonia-containing exhaust after three grades of acid sprays is entered to atmosphere by exhaust blower, described ammonia-containing exhaust≤5mg/m
3, described ammonia-containing exhaust is through the ammoniacal liquor of water spray and condensation gained, and the concentration of its free ammonia is 28g/L, and the concentration of tungstenic is 55g/L, completely can be by the analyzing step for APT production process after benefit ammonia, described ammonia-containing exhaust is to spray neutralization reaction by acid, thus need to change eo-acid according to the pH value of reactant liquor, to maintain the acid degree in spray column, when described spray liquid pH value reaches neutrality, obtain the sulfate of ammoniac solution that concentration is saturated, by solution evaporative crystallization, the water that evaporation obtains is back to secondary water spray and gathers dust, and the sulfate of ammoniac crystal obtaining is as byproduct.
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Cited By (16)
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|---|---|---|---|---|
| CN104630490A (en) * | 2015-02-10 | 2015-05-20 | 江西稀有金属钨业控股集团有限公司 | Method for preparing ammonium tungstate |
| CN105236446A (en) * | 2015-11-24 | 2016-01-13 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling waste hydrochloric acid |
| CN107089685A (en) * | 2017-06-26 | 2017-08-25 | 江西省修水赣北钨业有限公司 | A kind of circulation utilization method for producing ammine in ammonium paratungstate gas |
| CN110170222A (en) * | 2019-05-14 | 2019-08-27 | 江西理工大学 | A kind of processing method and system of Tungsten smelting exhaust gas |
| CN110963508A (en) * | 2020-01-15 | 2020-04-07 | 河南申越检测技术有限公司 | Device and process for preparing solid ammonium chloride from ammonia-containing waste gas |
| CN111442968A (en) * | 2020-05-27 | 2020-07-24 | 北京航天益来电子科技有限公司 | Denitration tail gas online monitoring and ammonia removal device and method |
| CN111482059A (en) * | 2020-03-26 | 2020-08-04 | 厦门钨业股份有限公司 | Treatment method of ammonia-containing tail gas and ammonia-containing tail gas treatment system |
| CN112354328A (en) * | 2020-10-29 | 2021-02-12 | 山东合力泰化工有限公司 | Tail gas absorption process and device in melamine production process |
| CN112933940A (en) * | 2021-03-03 | 2021-06-11 | 江苏科技大学 | Ammonia gas recovery and ammonium sulfate crystallization system and working method thereof |
| CN113429314A (en) * | 2021-06-22 | 2021-09-24 | 四川金象赛瑞化工股份有限公司 | Ammonium nitrate and xylylenediamine coproduction method and heat exchange network |
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| CN114515499A (en) * | 2022-02-21 | 2022-05-20 | 新泰市日进化工科技有限公司 | Intelligent ammonia-containing tail gas recovery control system and method for acid sprayer |
| CN114984733A (en) * | 2022-05-10 | 2022-09-02 | 成都虹波钼业有限责任公司 | Method for treating mixed gas containing carbon dioxide and ammonia |
| CN115057568A (en) * | 2022-06-08 | 2022-09-16 | 厦门钨业股份有限公司 | Method for treating ammonium paratungstate crystallization mother liquor |
| WO2023222433A1 (en) | 2022-05-17 | 2023-11-23 | Basf Se | Process for preparing ammonium chloride |
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| CN104630490A (en) * | 2015-02-10 | 2015-05-20 | 江西稀有金属钨业控股集团有限公司 | Method for preparing ammonium tungstate |
| CN105236446A (en) * | 2015-11-24 | 2016-01-13 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling waste hydrochloric acid |
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| CN110170222B (en) * | 2019-05-14 | 2022-09-23 | 江西理工大学 | Treatment method and system for tungsten smelting waste gas |
| CN110170222A (en) * | 2019-05-14 | 2019-08-27 | 江西理工大学 | A kind of processing method and system of Tungsten smelting exhaust gas |
| CN110963508A (en) * | 2020-01-15 | 2020-04-07 | 河南申越检测技术有限公司 | Device and process for preparing solid ammonium chloride from ammonia-containing waste gas |
| CN111482059A (en) * | 2020-03-26 | 2020-08-04 | 厦门钨业股份有限公司 | Treatment method of ammonia-containing tail gas and ammonia-containing tail gas treatment system |
| CN111442968A (en) * | 2020-05-27 | 2020-07-24 | 北京航天益来电子科技有限公司 | Denitration tail gas online monitoring and ammonia removal device and method |
| CN112354328A (en) * | 2020-10-29 | 2021-02-12 | 山东合力泰化工有限公司 | Tail gas absorption process and device in melamine production process |
| CN112933940A (en) * | 2021-03-03 | 2021-06-11 | 江苏科技大学 | Ammonia gas recovery and ammonium sulfate crystallization system and working method thereof |
| CN112933940B (en) * | 2021-03-03 | 2022-08-19 | 江苏科技大学 | Ammonia gas recovery and ammonium sulfate crystallization system and working method thereof |
| CN113429314A (en) * | 2021-06-22 | 2021-09-24 | 四川金象赛瑞化工股份有限公司 | Ammonium nitrate and xylylenediamine coproduction method and heat exchange network |
| CN113429317A (en) * | 2021-06-22 | 2021-09-24 | 四川金象赛瑞化工股份有限公司 | Non-liquid phase production method of phthalonitrile |
| CN114515499A (en) * | 2022-02-21 | 2022-05-20 | 新泰市日进化工科技有限公司 | Intelligent ammonia-containing tail gas recovery control system and method for acid sprayer |
| CN114515499B (en) * | 2022-02-21 | 2023-04-07 | 新泰市日进化工科技有限公司 | Intelligent ammonia-containing tail gas recovery control system and method for acid sprayer |
| CN114984733A (en) * | 2022-05-10 | 2022-09-02 | 成都虹波钼业有限责任公司 | Method for treating mixed gas containing carbon dioxide and ammonia |
| WO2023222433A1 (en) | 2022-05-17 | 2023-11-23 | Basf Se | Process for preparing ammonium chloride |
| CN115057568A (en) * | 2022-06-08 | 2022-09-16 | 厦门钨业股份有限公司 | Method for treating ammonium paratungstate crystallization mother liquor |
| CN115057568B (en) * | 2022-06-08 | 2023-10-31 | 厦门钨业股份有限公司 | Method for treating ammonium paratungstate crystallization mother liquor |
| CN117326982A (en) * | 2022-09-30 | 2024-01-02 | 四川元理材料科技有限公司 | Industrial process for synthesizing isophorone dicarbamic acid n-butyl ester by urea method |
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