CN102600710B - Treatment method of high-concentration ammonia nitrogen wastewater - Google Patents
Treatment method of high-concentration ammonia nitrogen wastewater Download PDFInfo
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- CN102600710B CN102600710B CN201110458069.5A CN201110458069A CN102600710B CN 102600710 B CN102600710 B CN 102600710B CN 201110458069 A CN201110458069 A CN 201110458069A CN 102600710 B CN102600710 B CN 102600710B
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Abstract
The invention belongs to the technical field of recycling and comprehensively utilizing industrial wastewater and waste gas, and in particular relates to a treatment method of high-concentration ammonia nitrogen wastewater. Particularly, the invention provides a method for comprehensively utilizing two wastes (the ammonia nitrogen wastewater and boiler smoke) and recycling ammonium sulfate. The high-concentration ammonia nitrogen wastewater generated in a production process of a chemical enterprise is collected to serve as a desulfurizing agent which is conveyed into a desulfurizing tower to react with SO2 in the dust-removed smoke of a boiler so as to obtain an ammonium sulfite intermediate product; and the ammonium sulfite is further oxidized to generate the stable ammonium sulfate.
Description
Technical field
The invention belongs to the technical field of industrial wastewater, exhaust-gas resource comprehensive utilization, be specially a kind of processing method of high-concentration ammonia nitrogenous wastewater.
Background technology
In recent years, develop growth rapidly, most petroleum chemical enterprise forming section deposed ammonia or high-concentration ammonia nitrogenous wastewater aborning along with industries such as chemical fertilizer, Coal Chemical Industry, petrochemical industries, the high ammonia-nitrogen wastewater produced therefrom also becomes one of industry development restraining factors.Ammonia nitrogen in waste water is generally exist with ammonium salt or free ammonia form, wherein NH
3-N content, usually between 1000-160000mg/L, to the ammonia nitrogen waste water of high-load, adopts traditional " three wastes " processing mode distillation process or discharge, which not only adds production cost and create environmental pollution.At present, bioanalysis also can only process the ammonia nitrogen waste water of 300 mg/below L.And chemical oxidization method deamination, expense is very expensive, also wastes resource simultaneously.Use chemical precipitation method deamination, not only cost is high, and by-product volume is large, and byproduct does not have commodity market.There is low, the consuming time length of efficiency in blow-off method, ammonia is collected difficulty and caused the shortcomings such as air pollution greatly, easily, and processing method is all undesirable.Therefore, cost-effective technical controlling high-concentration ammonia nitrogenous wastewater is adopted to pollute extremely urgent.
Summary of the invention
The high investment that the object of the invention is to for waste water and waste gas is administered, and provides a kind of processing method of high-concentration ammonia nitrogenous wastewater, is specially and provides two kinds of refuses (ammonia nitrogen waste water and boiler smoke) to fully utilize, a kind of method of reclaim sulfuric acid ammonium.SO in the flue gas after desulfurizing tower and boiler dusting is entered containing after high ammonia-nitrogen wastewater collection as desulfurizing agent using what produce in Production in Chemical Plant process
2react, obtain ammonium sulfite intermediate products, ammonium sulfite is oxidized further and generates stable ammonium sulfate.
Technical scheme of the present invention is: after being collected by high concentration (2%-3%) ammonia nitrogen waste water produced in technical process, be piped to Ammonia vessel, with liquefied ammonia be deployed into molar concentration be the ammoniacal liquor of 10% as desulfurizing agent, be delivered to the SO in the flue gas after desulfurizing tower and boiler dusting by aqua ammonia pump
2react, obtain ammonium sulfite intermediate products, ammonium sulfite is oxidized further and generates stable ammonium sulfate.
Described concentration is molar concentration.
The high-concentration ammonia nitrogenous wastewater produced in described technical process refers to the ammonia nitrogen waste water produced in chemical enterprise coal gas preparation process, process gas purification process technique, and its molar concentration is 2-3%.
Detailed step of the present invention is:
By the high temperature flue-gas from boiler after sack cleaner dedusting, temperature is 130 ~ 160 DEG C, through heat exchanger with to be disposed through desulfurizing tower go out after tower tail gas carries out heat exchange cooling to enter desulfurizing tower, 10% ammonia absorption be deployed into high-concentration ammonia nitrogenous wastewater and liquefied ammonia generates ammonium sulfite, absorb the ammonium sulfite of formation after absorption tower bottom oxide becomes ammonium sulfate, again ammonium sulfate is pumped into filter, flue dust in removing solution sends into crystallizing evaporator, must finished product sulfuric acid ammonium after evaporative crystallization, centrifugal, dry, packaging; Flue gas after absorption purifies through demist and is warmed up to more than dew-point temperature into heat exchanger and enters smoke stack emission.
technological principle of the present invention:
Pass in desulfurizing tower by what produce in the technical process such as chemical enterprise coal gas preparation process, process gas purification process containing high-concentration ammonia nitrogenous wastewater, make it and contain SO
2exhaust gas contact, occur as follows react:
SO
2＋H
2O＋xNH
3= (NH
4)xH
2－XSO
3 （1）
Due in its absorption process of existence of oxygen, (NH
4)
2sO
3-NH
4hSO
3system is by partially oxidized formation (NH
4)
2sO
4, in absorbing liquid, mainly contain (NH
4)
2sO
3, NH
4hSO
3, (NH
4)
2sO
4deng composition.
NH
4)XH
2-XSO
3+1/2O
2+(2-x)NH
3=(NH
4)
2SO
4 (2)
This process is that the sulfite oxidation absorbing intermediate product instability is become stable ammonium sulfate.
Beneficial effect of the present invention is: adopt into the former flue gas of desulfurizing tower and the technology going out the heat exchange of desulfurizing tower flue gas, its advantage has: 1. adopt gas-gas heat exchange cooling, decrease shower water consumption, the internal circulating load of absorbing liquid is little, and energy consumption is low.2. carrying out gas-gas heat exchange heating to going out desulfurizing tower flue gas, improve flue-gas temperature, making the flue-gas temperature entering chimney higher than dew-point temperature, both having decreased the energy consumption that flue gas heats up, and turn avoid the corrosion of flue gas to chimney, reducing chimney anticorrosion disposal cost.
Can be summed up as following some:
1) complete resource---turn waste into wealth, turn harm into good:
Sulfur dioxide, recovery ammonia can be the chemical fertilizer such as ammonium sulfate, phosphorus ammonium, ammonium nitrate by the ammonia process of desulfurization, do not produce secondary pollution, whole resource.
2) desulphurization cost is low:
The ammonia process of desulfurization is absorption method, and the attached value of byproduct is high, and ammonia can be made to rise in value, and operating cost is low.
3) unique advantage that chemical field has " treatment of wastes with processes of wastes against one another " is applied in:
Be desulfurizing agent with high-concentration ammonia nitrogenous wastewater, not only solve the pollution problem of chemical industry and electric power enterprise sulfur dioxide, the high ammonia-nitrogen wastewater discharged again " is eaten up and is used up " in sweetening process, has eliminated two large pollution sources simultaneously.
Adopt the ammonia process of desulfurization directly using deposed ammonia or high-concentration ammonia nitrogenous wastewater for the production of ammonium sulfate directly as agrochemical or the raw material as factory of composite fertilizer; the comprehensive utilization of refuse can be realized; the treatment of wastes with processes of wastes against one another, to turn waste into wealth; not only desulfurization but also pollution treatment water; kill two birds with one stone, realize the target of environmental protection and resource regeneration doulbe-sides' victory.This is the effective way that current minimizing " three wastes " is discharged, and embodies recycling economy resource and innoxious principle.
Flue gas SO after process
2concentration is less than 200mg/Nm
3, desulfuration efficiency is greater than 90%; High ammonia-nitrogen wastewater is all for reaction simultaneously, reduces fresh water (FW) consumption, reduces ammonia nitrogen and discharges 7.5 tons/year.
Therefore, waste water treatment and waste gas pollution control and treatment combine by the present invention, efficiently solve high ammonia-nitrogen wastewater intractability large, costly, there is secondary pollution problems, decrease ammonia nitrogen discharge capacity simultaneously, operating cost is low, without waste water, without waste residue, meet recycling economy rule, zero consumption of sweetening process can be realized.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme of the present invention is described in detail.
From high concentration (2%-3%) ammonia nitrogen waste water of shift conversion step, cleaning procedure in embodiment 1 methanol production process, be piped to flue gas desulphurization system Ammonia vessel, be deployed into 10% ammoniacal liquor with liquefied ammonia, be delivered to SO in desulfurizing tower and boiler smoke by aqua ammonia pump
2react, produce ammonium sulfate.
Effectiveness comparison:
The factory effluent produced in methanol production process is about 150m
3/ h, wherein high-concentration ammonia nitrogenous wastewater 15m
3/ h, high-concentration ammonia nitrogenous wastewater enters Sewage Disposal after mixing with other factory effluents and processes, and sewage plant Buffer Pool ammonia-nitrogen content is about 700-900 mg/l, and regulating reservoir ammonia-nitrogen content is about 350-400mg/l, cost of sewage disposal 3.6 yuan.After high ammonia-nitrogen wastewater enters desulphurization system, sewage plant regulating reservoir ammonia-nitrogen content is about 100-150mg/l, and ton processing cost reduces 1-1.5 unit, and year saves sewage disposal operating cost 150-225 ten thousand yuan, reduces ammonia nitrogen simultaneously and discharges 7.5 tons.
Claims (1)
1. the processing method of a high-concentration ammonia nitrogenous wastewater, after the high-concentration ammonia nitrogenous wastewater produced in technical process is collected, be piped to Ammonia vessel, with liquefied ammonia be deployed into molar concentration be the ammoniacal liquor of 10% as desulfurizing agent, be delivered to the SO in the flue gas after desulfurizing tower and boiler dusting by aqua ammonia pump
2react, obtain ammonium sulfite intermediate products, ammonium sulfite is oxidized further and generates stable ammonium sulfate; The high-concentration ammonia nitrogenous wastewater produced in described technical process refers to the ammonia nitrogen waste water produced in chemical enterprise coal gas preparation process, process gas purification process technique, and its molar concentration is 2-3%;
Its detailed step is: by the high temperature flue-gas from boiler after sack cleaner dedusting, temperature is 130 ~ 160 DEG C, through heat exchanger with to be disposed through desulfurizing tower go out after tower tail gas carries out heat exchange cooling to enter desulfurizing tower, 10% ammonia absorption be deployed into high-concentration ammonia nitrogenous wastewater and liquefied ammonia generates ammonium sulfite, absorb the ammonium sulfite of formation after absorption tower bottom oxide becomes ammonium sulfate, again ammonium sulfate is pumped into filter, flue dust in removing solution sends into crystallizing evaporator, must finished product sulfuric acid ammonium after evaporative crystallization, centrifugal, dry, packaging; Flue gas after absorption purifies through demist and is warmed up to more than dew-point temperature into heat exchanger and enters smoke stack emission.
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|---|---|---|---|
| CN201110458069.5A CN102600710B (en) | 2011-12-31 | 2011-12-31 | Treatment method of high-concentration ammonia nitrogen wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110458069.5A CN102600710B (en) | 2011-12-31 | 2011-12-31 | Treatment method of high-concentration ammonia nitrogen wastewater |
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| CN102600710B true CN102600710B (en) | 2015-02-11 |
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| CN104028098A (en) * | 2014-06-23 | 2014-09-10 | 菱花集团有限公司 | Method and device for applying high-ammonia-nitrogen wastewater to ammonia desulfurization in monosodium glutamate industry |
| CN105800648B (en) * | 2016-03-07 | 2018-02-02 | 攀钢集团攀枝花钢钒有限公司 | The Application way for the ammonium sulfate that flue gas during smelting is produced |
| CN105833678A (en) * | 2016-04-26 | 2016-08-10 | 安阳化学工业集团有限责任公司 | Method for desulfurization of coal-fired boiler flue gas with assistance of desorption waste liquid |
| CN107445231A (en) * | 2017-08-25 | 2017-12-08 | 金川集团股份有限公司 | A kind of device of acid waste water concentrate emission reduction |
| CN107698008A (en) * | 2017-11-25 | 2018-02-16 | 山西师范大学 | New application of the solid-state ammonium sulfate calcium carbonate reaction in water body NH_3-N treating |
| CN111573695A (en) * | 2020-04-09 | 2020-08-25 | 浙江省天正设计工程有限公司 | Recycling treatment process for high-concentration organic wastewater containing phosphorus and sulfur |
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Non-Patent Citations (1)
| Title |
|---|
| 氨氮废水用于烟气脱硫的循环经济产业模式研究;杨继贤等;《中国煤炭》;20101231(第11期);109-110,113 * |
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Inventor after: Chu Hongchun Inventor after: Wang Wei Inventor after: Sun Xiuying Inventor after: Wang Dong Inventor after: Xu Xianbao Inventor after: Zhao Zhongping Inventor after: Ma Xunhua Inventor after: Song Shuqun Inventor after: Shi Jintian Inventor after: Wang Hongji Inventor after: Qin Sheng Inventor before: Wang Xin Inventor before: Wang Wei Inventor before: Chu Hongchun Inventor before: Wang Dong Inventor before: Xu Xianbao Inventor before: Zhao Zhongping Inventor before: Shi Jintian Inventor before: Wang Hongji Inventor before: Song Shuqun Inventor before: Qin Sheng |
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