CN102580498A - Comprehensive treatment method for high-concentration ammonia nitrogen waste water and boiler flue gas - Google Patents
Comprehensive treatment method for high-concentration ammonia nitrogen waste water and boiler flue gas Download PDFInfo
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- CN102580498A CN102580498A CN201110458020XA CN201110458020A CN102580498A CN 102580498 A CN102580498 A CN 102580498A CN 201110458020X A CN201110458020X A CN 201110458020XA CN 201110458020 A CN201110458020 A CN 201110458020A CN 102580498 A CN102580498 A CN 102580498A
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- waste water
- flue gas
- ammonia nitrogen
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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
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- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention belongs to the field of the recycling of waste water and waste gas, and particularly relates to a comprehensive treatment method for high-concentration ammonia nitrogen waste water and boiler flue gas. The method comprises the following steps of: after separating crude synthesis gas formed by the waste water from a gasification process by a gas-liquid separator, conveying the separated gas to a low-temperature methanol washing process, and conveying low-temperature condensate generated by washing the gas and high-pressure flashing gas from a gasification lime water process into a steam stripping tower; conveying steam subjected to gas stripping by the steam stripping tower into a boiler by a pipeline; and performing reduction reaction of NH3 and NOx in the flue gas to generate N2 and water, reacting the NH3 with SO2 in the flue gas to generate (NH4)2SO3, and combining the (NH4)2SO3 with O2 to generate stable (NH4)2SO4. According to the comprehensive treatment method, the high-concentration ammonia nitrogen waste water serving as a denitration agent is used for the desulfuration and denitration of the boiler, so that the problem of the pollution of nitrogen oxides in petrochemical enterprises is solved, the discharged high-concentration ammonia nitrogen waste water is 'eliminated completely' in the desulfuration and denitration processes, two pollution sources are eliminated, and the win-win aims of environmental protection and resource recycling are fulfilled.
Description
Technical field
The invention belongs to waste water and waste gas pollution control and treatment technical field, be specifically related to a kind of high-concentration ammonia nitrogenous wastewater and boiler smoke measure of comprehensive.
Background technology
In recent years, along with the growth that develops rapidly of industries such as chemical fertilizer, petrochemical industry, the high-concentration ammonia nitrogenous wastewater that produces therefrom also becomes one of industry development restraining factors.Most of petroleum chemical enterprises form part deposed ammonia or high-concentration ammonia nitrogenous wastewater aborning.The past deposed ammonia after as discharge of wastewater traditional " three wastes " processing mode handle or discharging, so not only increased production cost but also produced environmental pollution.A large amount of ammonia nitrogen waste waters enter water body; Can cause the reduction even the body eutrophication of water quality, not only aquatic animals such as fish constituted harm, and stimulate water plant undue growth such as algae; Contamination phenomenon such as Chi Hu, red tide appear; Environmental sanitation is polluted, the ecological balance is threatened, more directly consequence is that health to human body exerts an influence.Ammonia-nitrogen content in the industrial wastewater between 1000-160000mg/L, at present, to the ammonia nitrogen waste water of high concentration content, still can't the applying biological method be handled up to standard usually.
Pollute in order to control water; The surface water and phreatic water quality such as protection river, river, lake, sea ensure health, maintaining ecological balance; State Bueau of Environmental Protection's approval has also been implemented " integrated wastewater discharge standard " GB8978-1996; Pollutant load such as ammonia nitrogen, phosphate in the sewage has been done strict restriction, ammonia nitrogen discharging primary standard: the 25mg/L of defined, secondary standard 50mg/L.
Processing for industrial ammonia nitrogen waste water at present mainly contains chemical oxidization method, ammonia blow-off method, chemical precipitation method, break point chlorination method, electroosmose process, electrochemical treatments, catalystic pyrolysis, biological denitrification method etc.Be applied to processing method of industrial waste water, must have convenient in application, waste water quality and economic dispatch advantage are stablized, are adapted to handling property, below various methods commonly used are analyzed one by one.
The most ammonia-nitrogen method of wastewater treatment like nitration denitrification method, break point chlorination method, chemical precipitation method etc., is that the ammonia nitrogen in the waste water is defined as pollutant at present, adopts the method for removing to reduce ammonia nitrogen content in the waste water, does not realize recycling.There is the problem that steam mono-consumption is big, processing cost is high in the stripping deamination technology that the other technology is for example traditional.And in fact, the key that ammonia nitrogen waste water is handled is, realizes that efficient, low energy consumption, recycling three have both.
Chemical oxidization method deamination, expense are very expensive, and by-product volume is big, also waste resource simultaneously, and byproduct do not have commodity market.Blow-off method exists low, the consuming time length of efficient, ammonia to collect difficulty and causes shortcomings such as air pollution greatly, easily.Therefore, adopt cost-effective technology control high-concentration ammonia nitrogenous wastewater to pollute extremely urgent.
The ammonia blow-off method generally adopts stripping pond and stripping tower two kind equipments, but stripping pond floor space is big, and is prone to cause secondary pollution; So the tower equipment of the normal employing of the stripping of ammonia, stripping tower adopts counter-current operation, and the filler of certain altitude is housed in the tower; Thereby help ammonia desorb from waste water to increase the gas-liquid mass transferring area, customary fillers has Raschig ring, polypropylene Pall ring, polypropylene multiaspect hollow ball etc., and waste water is thus lifted to the cat head of packed tower; And be distributed to the whole surface of filler, through filler toward dirty, with the gas reverse flow; The dividing potential drop of airborne ammonia increases with the removal degree of ammonia, increases with gas liquid ratio and reduces.The shortcoming of this method is that power consumption is big.
Chemical precipitation method has simple, the reliable and stable characteristics of technology; It is more commonly used in high-concentration ammonia nitrogenous wastewaters such as percolate, plant's waste water and ammonia industrial discharge waste water are handled; The sediment ammonium magnesium phosphate is a kind of double salt of indissoluble; Solubility product has only 2.510-13, and this product can be used as the additive of compost, garden soil or dewatered sludge, or is used as the fire retardant chemical of structural articles.But because the complicated component in the waste water, the initially influence of factor such as ammonia nitrogen concentration in the pH value of removing kind and proportioning, solution that efficient receives medicament of ammonia nitrogen and the waste water.
Its effect stability of break point chlorination method treatment of high concentration ammonia nitrogen waste water do not receive the influence of coolant-temperature gage, but operating cost is higher, and accessory substance chloramines or chlorinatedorganic also can cause secondary pollution of water.
Ion-exchange is applicable to the advanced treating of the ammonia nitrogen waste water of low concentration; For the ammonia nitrogen waste water of high concentration, can frequently cause operating difficulties because of exchanger regeneration, the exchanger capacity after the regeneration descends; And the ammonia nitrogen in the regenerated liquid still need be handled, and its operating cost is higher.
Biological denitrification method, this method are applicable to the ammonia nitrogen waste water processing of low concentration, and to the waste water of the low concentration of ammonia nitrogen concentration below 300mg/L, general direct employing biological denitrification method is handled; To the intermediate concentration waste water of ammonia nitrogen concentration at 300-1000mg/L, because of its ammonia nitrogen concentration to production by biological toxigenicity and inhibitory action, difficult this method that directly adopts is handled, and therefore generally adopts this method to handle again through dilution waste water.In commercial production, its ammonia nitrogen concentration content of the waste water of generation is higher, so this method is not suitable for the processing that is used for high-concentration ammonia nitrogenous wastewater in the commercial production.
In commercial production particularly in Industrial Stoves, the boiler operatiopn, SO
2Discharge capacity increase severely, make the SO of most city
2Concentration is in higher level of pollution, SO
2The increase of discharge capacity; It is rapidly unusual that acid rain is increased; Serious acid precipitation makes economic loss serious with the fragile ecosystem; Acid rain pollution has caused very large economic loss for forest and crops, and along with expanding economy and the progress of society and the enhancing of people's environmental consciousness, industrial smoke removes SO
2Come into one's own day by day,, flue gas is handled though the producer that has has adopted boiler flue gas desulfurization device.Sulfur method at present relatively more commonly used has lime stone---gypsum wet sulfur removal technology, sodium base wet desulfurizing process, spray drying process sulfur removal technology, circulating fluidized bed desulfurization technique, MgO wet process of FGD technology,
Lime stone---the shortcoming of gypsum wet sulfur removal technology is, system complex, and floor space is big; Cost is higher, and one-time investment is bigger; By-produced gypsum quantity is big, is not easy to handle, and can produce greenhouse gases CO simultaneously
2Discharging, also have discharge of wastewater, easy generation of secondary pollution.
The shortcoming of sodium base wet desulfurizing process is, the cost of desulfurizing agent is higher than the discharging charge far away, and desulfurization is many more, and economy is poor more.
The weak point of spray drying process sulfur removal technology is, this method is very high to the quality requirements of desulfurizing agent, and calcium sulfur ratio is bigger; The requirement production management level is high; Its desulfurization degree is medium, is applicable in using, low-sulfur coal and the medium small boiler not high to desulfuration efficiency, receives the restriction of reaction tower and spraying simultaneously.
Circulating fluidized bed desulfurization technique adopts quick lime or white lime to make absorbent, and cost of material is high, and the lime quality is had higher requirement; Because the flue gas after the desulfurization contains more dust, requires the downstream cleaner to have higher efficiency of dust collection; Desulfurizing byproduct is the mixture of calcium sulfite and calcium sulfate, and comprehensive utilization receives certain restriction.
The shortcoming of MgO wet flue gas desulfurization method is that byproduct reclaims difficulty, because of MgSO
3And MgSO
4Solubility in water is higher; As adopt the way of evaporative crystallization will consume mass energy; As carry out isolated by filtration again after adding flocculating setting agent (polyacrylamide); Flocculating setting agent has influence to downstream unit, but will be under certain pH condition for the soluble salt of ion-type, and adding flocculating setting agent can be with Mg
2+From solution, separate; Desulfurizing agent and magnesia cost are higher; Possibly have side reaction, thus the actual consumption of MgO will than theory estimate many.
Therefore,, not only need appropriate dispose of wastewater and flue gas, make it can not cause environmental pollution, also need reasonably these emission resource consolidations to be used, turn waste into wealth to high-concentration ammonia nitrogenous wastewater that occurs in the industrial and mining enterprises and boiler smoke.
Summary of the invention
In order to solve above-mentioned technical problem, the invention provides a kind of high-concentration ammonia nitrogenous wastewater and boiler smoke measure of comprehensive.The characteristics of this method are, have not only handled the high-concentration ammonia nitrogenous wastewater that produces in the commercial production, have also administered the boiler smoke in the commercial production simultaneously, have alleviated the pollution that waste water and waste gas bring environment.
Main feature of the present invention is, it is a kind of processing method of knockdown high-concentration ammonia nitrogenous wastewater, and it is that high-concentration chemical industry industry ammonia nitrogen waste water is handled the method that combines with the boiler flue gas desulfurization denitration.
The present invention realizes through following technical scheme:
High-concentration ammonia nitrogenous wastewater and boiler smoke measure of comprehensive comprise following step:
A. the crude synthesis gas from gasification process goes out condensate liquid through gas-liquid separator separates, and the synthesis gas of isolating behind the condensate liquid is delivered to the low-temperature rectisol operation, the cryogenic condensation liquid that the washing back produces and get into stripper from gasification ash water operation high pressure flash gas;
B. the steam after stripper gas is carried gets into the process gas pipeline and sends into boiler, and tower bottom divides condensate liquid to send the deoxygenation tank, and deoxygenation tank flashed vapour is incorporated the process gas pipeline into and sent into boiler;
C. the process gas pipeline through being divided into 4 branch road process gas pipelines, gets into boiler from four positions in the burner hearth both sides and the back side at the boiler secondary air open height, is 900～1100 ℃ zone in fire box temperature, NH
3Carry out reduction reaction generation N with the NOx in the flue gas
2And water, its reaction mechanism is following:
4NH
3＋4NO＋O
2?→?4N
2+?6H
2O
2CO(NH
2)
2＋4NO＋O
2?→?4N
2?+?2CO
2+?4H
2O
NH
3With the SO in the flue gas
2Reaction generates (NH
4)
2SO
3, (NH
4)
2SO
3With O
2In conjunction with generating more stable (NH
4)
2SO
4
NH
3＋SO
2?+H
2O?→?（NH
4）
2SO
3
2（NH
4）
2SO
3＋O
2?→?2（NH
4）
2SO
4。
The invention has the beneficial effects as follows:
(1) be that denitrfying agent is used for the boiler desulfurization denitration with the high-concentration ammonia nitrogenous wastewater; Not only solved the pollution problem of petroleum chemical enterprise's nitrogen oxide; Again the high ammonia-nitrogen wastewater of its discharging " is eaten up and used up " in denitrification process; Eliminate two big pollution sources simultaneously, realized the target of environmental protection and resource regeneration doulbe-sides' victory;
(2) the present technique investment is low, and operating cost is low, does not produce secondary pollution, no waste water, and no waste residue meets the recycling economy rule, can realize that zero of denitrification process consumes.
The specific embodiment
Below in conjunction with specific embodiment the present invention is done explanation further,, but therefore do not limit the present invention so that those skilled in the art more understands the present invention.
Embodiment 1
A. the crude synthesis gas from gasification process goes out condensate liquid through gas-liquid separator separates, and the synthesis gas of isolating behind the condensate liquid is delivered to the low-temperature rectisol operation, the cryogenic condensation liquid that the washing back produces and get into stripper from gasification ash water operation high pressure flash gas;
B. the steam after stripper gas is carried gets into DN200 process gas pipeline and sends into boiler, and tower bottom divides condensate liquid to send the deoxygenation tank, and deoxygenation tank flashed vapour is incorporated DN200 process gas pipeline into and sent into boiler;
C. DN200 process gas pipeline through being divided into 4 DN100 pipelines, gets into boiler from four positions in the burner hearth both sides and the back side at the boiler secondary air open height, is 900～1100 ℃ zone in fire box temperature, NH
3Carry out reduction reaction generation N with the NOx in the flue gas
2And water, its reaction mechanism is following:
4NH
3＋4NO＋O
2?→?4N
2+?6H
2O
2CO(NH
2)
2＋4NO＋O
2?→?4N
2?+?2CO
2+?4H
2O
NH
3With the SO in the flue gas
2Reaction generates (NH
4)
2SO
3, (NH
4)
2SO
3With O
2In conjunction with generating more stable (NH
4)
2SO
4
NH
3＋SO
2?+H
2O?→?（NH
4）
2SO
3
2（NH
4）
2SO
3＋O
2?→?2（NH
4）
2SO
4。
Through detecting, in the boiler smoke after the method processing that the present invention adopted, its denitration rate 15%; Sewage plant regulating reservoir ammonia nitrogen is reduced to 100-150mg/l by 350-400mg/l, and cost of sewage disposal per ton reduces 1-1.5 unit, and ten thousand yuan of year saving sewage disposal operating cost 150-225 reduce 7.5 tons of ammonia nitrogen dischargings simultaneously.
Embodiment 2
A. the crude synthesis gas from gasification process goes out condensate liquid through gas-liquid separator separates, and the synthesis gas of isolating behind the condensate liquid is delivered to the low-temperature rectisol operation, the cryogenic condensation liquid that the washing back produces and get into stripper from gasification ash water operation high pressure flash gas;
B. the steam after stripper gas is carried gets into DN200 process gas pipeline and sends into boiler, and tower bottom divides condensate liquid to send the deoxygenation tank, and deoxygenation tank flashed vapour is incorporated DN200 process gas pipeline into and sent into boiler;
C. DN200 process gas pipeline through being divided into 4 DN100 pipelines, gets into boiler from four positions in the burner hearth both sides and the back side at the boiler secondary air open height, is 1100 ℃ zone in fire box temperature, NH
3Carry out reduction reaction generation N with the NOx in the flue gas
2And water; NH
3With the SO in the flue gas
2Reaction generates (NH
4)
2SO
3, (NH
4)
2SO
3With O
2In conjunction with generating more stable (NH
4)
2SO
4
Embodiment 3
A. the crude synthesis gas from gasification process goes out condensate liquid through gas-liquid separator separates, and the synthesis gas of isolating behind the condensate liquid is delivered to the low-temperature rectisol operation, the cryogenic condensation liquid that the washing back produces and get into stripper from gasification ash water operation high pressure flash gas;
B. the steam after stripper gas is carried gets into DN200 process gas pipeline and sends into boiler, and tower bottom divides condensate liquid to send the deoxygenation tank, and deoxygenation tank flashed vapour is incorporated DN200 process gas pipeline into and sent into boiler;
C. DN200 process gas pipeline through being divided into 4 DN100 pipelines, gets into boiler from four positions in the burner hearth both sides and the back side at the boiler secondary air open height, is 1000 ℃ zone in fire box temperature, NH
3Carry out reduction reaction generation N with the NOx in the flue gas
2And water, its reaction mechanism is following:
4NH
3＋4NO＋O
2?→?4N
2+?6H
2O
2CO(NH
2)
2＋4NO＋O
2?→?4N
2?+?2CO
2+?4H
2O
NH
3With the SO in the flue gas
2Reaction generates (NH
4)
2SO
3, (NH
4)
2SO
3With O
2In conjunction with generating more stable (NH
4)
2SO
4
NH
3＋SO
2?+H
2O?→?（NH
4）
2SO
3
2（NH
4）
2SO
3＋O
2?→?2（NH
4）
2SO
4。
Claims (1)
1. high-concentration ammonia nitrogenous wastewater and boiler smoke measure of comprehensive comprise following step:
A. the crude synthesis gas from gasification process goes out condensate liquid through gas-liquid separator separates, and the synthesis gas of isolating behind the condensate liquid is delivered to the low-temperature rectisol operation, the cryogenic condensation liquid that the washing back produces and get into stripper from gasification ash water operation high pressure flash gas;
B. the steam after stripper gas is carried gets into the process gas pipeline and sends into boiler, and tower bottom divides condensate liquid to send the deoxygenation tank, and deoxygenation tank flashed vapour is incorporated the process gas pipeline into and sent into boiler;
C. the process gas pipeline through being divided into 4 branch road process gas pipelines, gets into boiler from four positions in the burner hearth both sides and the back side at the boiler secondary air open height, is 900～1100 ℃ zone in fire box temperature, NH
3Carry out reduction reaction generation N with the NOx in the flue gas
2And water; NH
3With the SO in the flue gas
2Reaction generates (NH
4)
2SO
3, (NH
4)
2SO
3With O
2In conjunction with generating more stable (NH
4)
2SO
4
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107555721A (en) * | 2017-09-30 | 2018-01-09 | 浦湘生物能源股份有限公司 | A kind of high-concentration ammonia nitrogenous wastewater cooperates with the method and system administered with nitrogen oxides |
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Patent Citations (6)
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| JPH0696145A (en) * | 1992-09-14 | 1994-04-08 | Hitachi Ltd | Processing system for character string/graphic |
| JPH06343994A (en) * | 1993-06-07 | 1994-12-20 | Meidensha Corp | Treatment process for digested sludge dehydrated filtrate |
| JPH0975915A (en) * | 1995-09-19 | 1997-03-25 | Hitachi Ltd | Treating system of ammonia nitrogen |
| CN1155521A (en) * | 1995-11-27 | 1997-07-30 | 株式会社荏原制作所 | Method for treating exhaust gases and foul water |
| CN101264948A (en) * | 2008-04-25 | 2008-09-17 | 北京化工大学 | Ammonia nitrogen waste water discharge-reducing and ammonia nitrogen resource utilizing device and method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107555721A (en) * | 2017-09-30 | 2018-01-09 | 浦湘生物能源股份有限公司 | A kind of high-concentration ammonia nitrogenous wastewater cooperates with the method and system administered with nitrogen oxides |
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Inventor after: Chu Hongchun Inventor after: Liu Xiaowei Inventor after: Ma Xunhua Inventor after: Zhao Zhongping Inventor after: Wang Dong Inventor after: Shi Jintian Inventor after: Wang Hongji Inventor after: Song Shuqun Inventor after: Wang Ning Inventor after: Ji Xiuling Inventor after: Tian Liya Inventor before: Wang Xin Inventor before: Tian Liya Inventor before: Liu Xiaowei Inventor before: Chu Hongchun Inventor before: Zhao Zhongping Inventor before: Wang Dong Inventor before: Shi Jintian Inventor before: Wang Hongji Inventor before: Song Shuqun Inventor before: Wang Ning Inventor before: Ji Xiuling |
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Free format text: CORRECT: INVENTOR; FROM: WANG XIN CHU HONGCHUN ZHAO ZHONGPING WANG DONG SHI JINTIAN WANG HONGJI SONG SHUQUN WANG NING JI XIULING TIAN LIYA LIU XIAOWEI TO: CHU HONGCHUN ZHAO ZHONGPING WANG DONG SHI JINTIAN WANG HONGJI SONG SHUQUN WANG NING JI XIULING TIAN LIYA LIU XIAOWEI MA XUNHUA |