CN103785263B - A kind of method that ammonia vent gas treatment reclaims - Google Patents
A kind of method that ammonia vent gas treatment reclaims Download PDFInfo
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- CN103785263B CN103785263B CN201410050253.XA CN201410050253A CN103785263B CN 103785263 B CN103785263 B CN 103785263B CN 201410050253 A CN201410050253 A CN 201410050253A CN 103785263 B CN103785263 B CN 103785263B
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- ammonia
- dust
- spray
- tail gas
- containing exhaust
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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
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Abstract
The present invention relates to ammonium paratungstate in tungsten powder smelting industry and calcine the ammonia tail gas disposal technique produced, in particular, relate to by the recovery realizing tungsten oxide dust and ammonia with the method for sour spray-absorption of gathering dust in ammonia vent gas treatment process, tail gas qualified discharge after process.The present invention includes (1) to gather dust, (2) Water spray gathers dust, (3) condensation, (4) acid absorbs, (5) evaporative crystallization steps, the ammonia-containing exhaust of variable concentrations can be processed, also can process the ammonia-containing exhaust containing other combustible, after treatment, the tungsten oxide dust in tail gas can all reclaim the ammonia tail gas that converter produces, ammonia all can be converted into sulfate of ammoniac (or ammonium chloride, ammonium nitrate) crystal, no longer produces the problem of ammonia pollution and secondary environmental pollution.
Description
Technical field
The present invention relates to ammonium paratungstate in tungsten powder smelting industry and calcine the ammonia tail gas disposal technique produced, in particular, relate to by the recovery realizing tungsten oxide dust and ammonia with the method for sour spray-absorption of gathering dust in ammonia vent gas treatment process, tail gas qualified discharge after process.
Background technology
At home in tungsten powder smelt production, use converter calcining ammonium paratungstate to produce obtained tungsten oxide product, containing the ammonia of 5% in ammonium paratungstate, when calcining and decomposing, produce tail gas, containing 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, the respiratory system of infringement people and skin, it is atmosphere pollution not only, and can body eutrophication be made after formation rainwater, polluted source, cause Heavy environmental pollution.At present, in process converter calcining ammonium paratungstate generation ammonia tail gas, some enterprises adopt Water spray method process ammonia, this method can not absorb ammonia completely, effectively can not reclaim the tungsten powder dirt in converter calcination process, absorbing liquid enters waste water, causes the ammonia-nitrogen content in industrial wastewater to exceed standard, creates new secondary pollution.Along with the progress for the treatment of tail gas technology, the new technologies such as biological filtering tower combined working technology and incineration technology have been had now to the process of ammonia tail gas, biological filtering tower combined working technology is mainly used in the NH_3-N treating in waste water, and incineration technology also only adapts to process containing the high petrochemical industry of ammonia density, 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 and ammonia is placed in high temperature, catalyst, has H
2when 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 its process ammonia tail gas, shortcoming one does not have the ammonia in synthetical recovery ammonia tail gas, but discharged by its Direct Resolution, causes the waste of resource; Two is do not collect tungsten oxide dust in ammonia tail gas, effectively can not improve the rate of recovery of tungsten; Three is need high temperature in catalytic process, creates thermal pollution, and relates to combustion of hydrogen acquisition energy, adds the potential safety hazards 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 be accomplished without harmful tailpipe emissions, effectively can also reclaim converter calcining ammonium paratungstate to produce in tungsten oxide product process with the ammonia of tail gas discharge and tungsten powder dirt, both secondary resource comprehensive utilization had been accomplished, it also avoid the impact that ammonia emission causes atmospheric environment, realize the environmental requirement without ammonia pollution, not only environmental protection but also economic.
Technical solution of the present invention: a kind of method that ammonia vent gas treatment reclaims, comprises the following steps:
(1) gather dust
Produce with converter calcining ammonium paratungstate the ammonia tail gas discharged in tungsten oxide product process to deliver in dust collecting system and carry out cyclone dust collection or gravity gathers dust (cyclone dust collection also can be adopted to add gravity gather dust), effectively to reclaim the tungsten oxide dust in the ammonia-containing exhaust of converter generation, 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 absorbs through Venturi tube or absorption tower Water spray again, after absorbing liquid reaches capacity, crystal structure is allowed to separate out by the method cooled, solution circulation uses, and tail gas enters next step and carries out advanced treating;
(3) condensation
Be passed in condenser by the ammonia tail gas after Water spray gathers dust, control at 30-80 DEG C by its temperature, can collect in condensation chamber and obtain high concentration ammoniacal liquor, the ammoniacal liquor obtained can fully utilize or sell, thus protection of the environment;
(4) acid absorbs
Gather dust with condensed ammonia tail gas by absorption tower through Water spray, be ammonium salt solution with a kind of spray-absorption in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, 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 sulfate solution or ammonium chloride, ammonium nitrate, the ammonium phosphate solution of saturated concentration, by solution evaporative crystallization, the Water circulation that evaporation obtains carries out secondary Water spray in step (2) and gathers dust, the sulfate of ammoniac obtained or ammonium chloride, ammonium nitrate crystals, as byproduct, can be used for the raw materials for production of composite fertilizer, accomplish that resource comprehensive utilization utilizes.
Beneficial effect of the present invention: the ammonia-containing exhaust that can process variable concentrations, also can process the ammonia-containing exhaust containing other combustible, the ammonia tail gas that converter produces after treatment, tungsten oxide dust in tail gas can all reclaim, ammonia all can be converted into sulfate of ammoniac (or ammonium chloride, ammonium nitrate) crystal, no longer produces the problem of ammonia pollution and 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.
Detailed description of the invention
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, sulfuric acid (pH value≤6) spray, evaporative crystallization prepares high-purity sulphuric acid ammonia crystal step, gather dust in step in above-mentioned one-level, first converter high-temperature calcination is decomposed in ammonium paratungstate and produce ammonia-containing exhaust and carry out cyclone dust collection or gravity gathers dust, to be gathered dust by one cyclonic or gravity gathers dust the bulky grain tungsten oxide dust that can fully reclaim in ammonia-containing exhaust, also the effect that next step Water spray gathers dust can be strengthened, secondary Water spray subsequently gathers dust in step, ammonia tail gas after dedusting is carried out secondary gathered dust by the spray tower that gathers dust, remove granule tungsten oxide dust further, ammoniacal liquor is collected again after condensing steps, remaining ammonia tail gas is through persulfuric acid three grades spray, last ammonia tail gas reaches the discharge standard of national regulation, by exhaust blower, gas is entered air, the tungsten oxide dust of the larger particles that one-level is collected after gathering dust and ammonia-containing exhaust being carried out cyclone settling or gravitational settling in step returns converter feeding mouth, terminates 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, ensures that water droplet is by high atomisation, carries out after atomizing spray gathers dust, terminating to enter down one step, ammonia tail gas after being gathered dust by secondary Water spray passes in condenser, controls temperature at 50 DEG C, until condensator outlet is emerged without steam, terminates to enter down one step, condensed ammonia-containing exhaust is passed into three grades of sour spray equipments, acid spray sprays from top to down, and ammonia-containing exhaust is discharged from bottom to top, both reverse abundant haptoreactions, terminates to enter down one step, ammonia-containing exhaust after three grades of acid sprays is entered air 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 by mending after ammonia for the analyzing step in APT production process, described ammonia-containing exhaust carries out spray neutralization reaction by acid, so need to carry out replacing 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 solution that concentration is saturated, by solution evaporative crystallization, evaporate the Water circulation obtained to gather dust in secondary Water spray, the sulfate of ammoniac crystal obtained, as byproduct, can be used for the raw materials for production of composite fertilizer, accomplishes that resource comprehensive utilization utilizes.
Embodiment 2: the present invention includes one-level and gather dust, secondary Water spray gathers dust, condensation, three grades, nitric acid (pH value≤6) spray, evaporative crystallization prepares high pure nitric acid ammonia crystal step, gather dust in step in above-mentioned one-level, first converter high-temperature calcination is decomposed in ammonium paratungstate and produce ammonia-containing exhaust and carry out cyclone dust collection or gravity gathers dust, to be gathered dust by one cyclonic or gravity gathers dust the bulky grain tungsten oxide dust that can fully reclaim in ammonia-containing exhaust, also the effect that next step Water spray gathers dust can be strengthened, secondary Water spray subsequently gathers dust in step, ammonia tail gas after dedusting is carried out secondary gathered dust by the spray tower that gathers dust, remove granule tungsten oxide dust further, ammoniacal liquor is collected again after condensing steps, remaining ammonia tail gas is through pernitric acid three grades spray, last ammonia tail gas reaches the discharge standard of national regulation, by exhaust blower, gas is entered air, the tungsten oxide dust of the larger particles that described ammonia-containing exhaust one-level is collected after gathering dust and ammonia-containing exhaust being carried out cyclone settling or gravitational settling in step returns converter feeding mouth, terminates 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, ensures that water droplet is by high atomisation, carries out after atomizing spray gathers dust, terminating to enter down one step, ammonia tail gas after being gathered dust by secondary Water spray passes in condenser, controls temperature at 40 DEG C, until condensator outlet is emerged without steam, terminates to enter down one step, condensed ammonia-containing exhaust is passed into three grades of sour spray equipments, acid spray sprays from top to down, and ammonia-containing exhaust is discharged from bottom to top, both reverse abundant haptoreactions, terminates to enter down one step, ammonia-containing exhaust after three grades of acid sprays is entered air 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 by mending after ammonia for the analyzing step in APT production process, described ammonia-containing exhaust carries out spray neutralization reaction by acid, so need to carry out replacing 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, evaporate the Water circulation obtained to gather dust in secondary Water spray, the nitric acid ammonia crystal obtained, as byproduct, can be used for the raw materials for production of composite fertilizer, accomplishes that resource comprehensive utilization utilizes.
Claims (1)
1. a method for ammonia vent gas treatment recovery, is characterized in that:
Comprise one-level to gather dust, secondary Water spray gathers dust, condensation, three grades, pH value≤6 sulfuric acid spray, evaporative crystallization prepares high-purity sulphuric acid ammonia crystal step, gather dust in step in above-mentioned one-level, first cyclone dust collection is carried out by producing ammonia-containing exhaust in converter high-temperature calcination decomposition ammonium paratungstate, to be gathered dust the bulky grain tungsten oxide dust that can fully reclaim in ammonia-containing exhaust by one cyclonic, also the effect that next step Water spray gathers dust can be strengthened, secondary Water spray subsequently gathers dust in step, ammonia tail gas after dedusting is carried out secondary gathered dust by the spray tower that gathers dust, remove granule tungsten oxide dust further, ammoniacal liquor is collected again after condensing steps, remaining ammonia tail gas is through persulfuric acid three grades spray, last ammonia tail gas reaches the discharge standard of national regulation, by exhaust blower, gas is entered air, the tungsten oxide dust of the larger particles that one-level is collected after gathering dust and ammonia-containing exhaust being carried out cyclone settling in step returns 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, ensures that water droplet is by high atomisation, carries out after atomizing spray gathers dust, terminating to enter down one step, ammonia tail gas after being gathered dust by secondary Water spray passes in condenser, controls temperature at 50 DEG C, until condensator outlet is emerged without steam, terminates to enter down one step, condensed ammonia-containing exhaust is passed into three grades of sour spray equipments, acid spray sprays from top to down, and ammonia-containing exhaust is discharged from bottom to top, both reverse abundant haptoreactions, terminates to enter down one step, ammonia-containing exhaust after three grades of acid sprays is entered air by exhaust blower, enters the ammonia-containing exhaust≤5mg/m of air
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 by mending after ammonia for the analyzing step in APT production process, described ammonia-containing exhaust carries out spray neutralization reaction by acid, so need to carry out replacing eo-acid according to the pH value of reactant liquor, to maintain the acid degree in spray column, when spray liquid pH value reaches neutrality, obtain the sulfate solution that concentration is saturated, by solution evaporative crystallization, evaporate the Water circulation obtained and gather dust in secondary Water spray, the sulfate of ammoniac crystal obtained is as byproduct.
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| CN103785263B true CN103785263B (en) | 2016-01-20 |
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Cited By (1)
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| CN107543903A (en) * | 2017-08-25 | 2018-01-05 | 北京林业大学 | A kind of method and apparatus for monitoring dewatering technology of mud ammonia and hydrogen sulfide on-line |
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| CN104630490B (en) * | 2015-02-10 | 2017-01-11 | 江西稀有金属钨业控股集团有限公司 | Method for preparing ammonium tungstate |
| CN105236446B (en) * | 2015-11-24 | 2017-12-15 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of recycling method of 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 |
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