CN102580498B - 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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- CN102580498B CN102580498B CN201110458020.XA CN201110458020A CN102580498B CN 102580498 B CN102580498 B CN 102580498B CN 201110458020 A CN201110458020 A CN 201110458020A CN 102580498 B CN102580498 B CN 102580498B
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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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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 method of high-concentration ammonia nitrogenous wastewater and the boiler smoke comprehensive regulation.
Background technology
In recent years, along with the growth that develops rapidly of the industry such as chemical fertilizer, petrochemical industry, the high-concentration ammonia nitrogenous wastewater producing therefrom also becomes one of industry development restraining factors.Most of petroleum chemical enterprises are forming section deposed ammonia or high-concentration ammonia nitrogenous wastewater aborning.Past deposed ammonia after as discharge of wastewater traditional " three wastes " processing mode process or discharge, 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 even body eutrophication of reduction of water quality, not only the aquatic animals such as fish are formed to harm, and stimulate the water plant undue growth such as algae, there is the contamination phenomenon such as Chi Hu, red tide, environmental sanitation is polluted, the ecological balance is threatened, more direct consequence is that the health of human body is exerted an influence.Ammonia-nitrogen content in industrial wastewater conventionally, between 1000-160000mg/L, at present, to the ammonia nitrogen waste water of high concentration content, there is no method applying biological method and processes up to standard.
Pollute in order to control water; the water quality of the surface water such as protection river, river, lake, sea and underground water; ensure health; maintaining ecological balance; State Bueau of Environmental Protection ratifies and has implemented " integrated wastewater discharge standard " GB8978-1996; the pollutant load such as ammonia nitrogen in sewage, phosphate is done to strict restriction, ammonia nitrogen discharge primary standard: the 25mg/L of defined, secondary standard 50mg/L.
At present mainly contain chemical oxidization method, ammonia blow-off method, chemical precipitation method, break point chlorination method, electroosmose process, electrochemical treatments, catalystic pyrolysis, biological denitrification method etc. for the processing of industrial ammonia nitrogen waste water.Be applied to the processing method of industrial wastewater, must have that application is convenient, waste water quality and economic dispatch advantage are stablized, are adapted to handling property, below various conventional methods are analyzed one by one.
Most ammonia-nitrogen method of wastewater treatment, as nitration denitrification method, break point chlorination method, chemical precipitation method etc., is that the ammonia nitrogen in waste water is defined as to pollutant at present, adopts the method for removing to reduce the content of ammonia nitrogen in waste water, does not realize recycling.There is the problem that steam mono-consumption is large, processing cost is high in for example traditional stripping deamination technology of other technology.And in fact, the key of ammonia nitrogen waste water processing is, realize efficient, low energy consumption, recycling three has both.
Chemical oxidization method deamination, expense is very expensive, and by-product volume is large, also waste resource, and byproduct does not have commodity market simultaneously.Blow-off method exists low, the consuming time length of efficiency, ammonia collection difficulty greatly, easily to cause the shortcomings such as air pollution.Therefore, adopt cost-effective technology control high-concentration ammonia nitrogenous wastewater to pollute extremely urgent.
Ammonia blow-off method generally adopts stripping pond and stripping tower two kind equipments, but stripping pond floor space is large, and easily cause secondary pollution, so tower equipment of the normal employing of the stripping of ammonia, stripping tower adopts counter-current operation, the filler of certain altitude is housed in tower, thereby be conducive to ammonia desorb from waste water to increase gas-liquid mass transferring area, customary filler has Raschig ring, polypropylene Pall ring, polypropylene polyhedron empty ball etc., waste water is thus lifted to the tower top of packed tower, and be distributed to the whole surface of filler, by filler toward dirty, with gas reverse flow, the dividing potential drop of airborne ammonia increases with the removal degree of ammonia, increase and reduce with gas liquid ratio.The shortcoming of the method is that power consumption is large.
Chemical precipitation method has simple, the reliable and stable feature of technique, it is more conventional in the high-concentration ammonia nitrogenous wastewaters such as percolate, plant's waste water and ammonia industrial discharge waste water are processed, sediment ammonium magnesium phosphate is a kind of double salt of indissoluble, solubility product only has 2.510-13, 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 due to the complicated component in waste water, the impact of removing efficiency and be subject to the factors such as initial ammonia nitrogen concentration in the pH value of the kind of medicament and proportioning, solution and waste water of ammonia nitrogen.
Break point chlorination method is processed its effect stability of high-concentration ammonia nitrogenous wastewater, be not subject to the impact 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, the exchanger capacity loss after regeneration because of exchanger regeneration, and ammonia nitrogen in regenerated liquid still needs to process, its operating cost is higher.
Biological denitrification method, the method is applicable to the ammonia nitrogen waste water processing of low concentration, the waste water of the low concentration to ammonia nitrogen concentration below 300mg/L, general direct employing biological denitrification method is processed; Intermediate concentration waste water to ammonia nitrogen concentration at 300-1000mg/L, because its ammonia nitrogen concentration is to production by biological toxigenicity and inhibitory action, more difficult direct employing the method is processed, and therefore generally waste water is adopted to the method processing again through dilution.In industrial production, its ammonia nitrogen concentration content of the waste water of generation is higher, and therefore the method is not suitable for the processing for high-concentration ammonia nitrogenous wastewater in industrial production.
In industrial production particularly in Industrial Stoves, boiler operatiopn, SO
2discharge capacity increase severely, make the SO of most cities
2concentration is in higher level of pollution, SO
2the increase of discharge capacity, acid rain is increased rapidly abnormal, serious acid precipitation and the fragile ecosystem make economic loss serious, Acid Rain Pollution has caused very large economic loss to forest and crops, along with expanding economy and social progress and the enhancing of people's environmental consciousness, industrial smoke removes SO
2day by day come into one's own, although some producers have adopted boiler flue gas desulfurization device, flue gas is processed.At present more conventional sulfur method 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 Flue Gas Desulfurization Technology,
Lime stone---the shortcoming of gypsum wet sulfur removal technology is, system complex, and floor space is large; Cost is higher, and one-time investment is larger; By-produced gypsum quantity is large, is not easy to process, and can produce greenhouse gases CO simultaneously
2discharge, also have discharge of wastewater, easily produce secondary pollution.
The shortcoming of sodium base wet desulfurizing process is, the cost of desulfurizing agent is far away higher than discharge charge, and desulfurization is more, and economy is poorer.
The weak point of spray drying process sulfur removal technology is, the method is very high to the quality requirements of desulfurizing agent, and calcium sulfur ratio is larger, 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, is subject to 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 lime quality is had to higher requirement; Because the flue gas after desulfurization contains more dust, require downstream cleaner to there is higher efficiency of dust collection; Desulfurizing byproduct is the mixture of calcium sulfite and calcium sulfate, and comprehensive utilization is subject to certain restrictions.
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 again isolated by filtration after adding flocculating setting agent (polyacrylamide), flocculating setting agent may have impact to downstream unit, but will be under certain pH condition for the soluble salt of ionic, add the flocculating setting agent can be by Mg
2+from solution, separate; Desulfurizing agent and magnesia cost are higher; May there is side reaction, so the actual consumption of MgO is many by what estimate than theory.
Therefore, for the high-concentration ammonia nitrogenous wastewater occurring in industrial and mining enterprises and boiler smoke, not only need appropriate dispose of wastewater and flue gas, make it can not cause environmental pollution, also needing reasonably, by these emission resources integrations, turns waste into wealth.
Summary of the invention
In order to solve above-mentioned technical problem, the invention provides a kind of method of high-concentration ammonia nitrogenous wastewater and the boiler smoke comprehensive regulation.The feature of the method is, not only processed the high-concentration ammonia nitrogenous wastewater producing in industrial production, also administered the boiler smoke in industrial production simultaneously, alleviated the pollution that waste water and waste gas bring environment.
Main feature of the present invention is, the processing method that it is a kind of knockdown high-concentration ammonia nitrogenous wastewater, and it is that high-concentration chemical industry industry ammonia nitrogen waste water is processed to the method combining with boiler flue gas desulfurization denitration.
The present invention realizes by following technical scheme:
The method of high-concentration ammonia nitrogenous wastewater and the boiler smoke comprehensive regulation, comprises following step:
A. go out condensate liquid from the crude synthesis gas of gasification process through gas-liquid separator separates, the synthesis gas of isolating after condensate liquid is delivered to low-temperature rectisol operation, washs the rear low temperature cold lime set producing and enters stripper from gasification ash water operation high pressure flash gas;
B. the steam after stripper air lift enters process gas pipeline and sends into boiler, and tower bottom divides condensate liquid to send deoxygenation tank, and deoxygenation tank flashed vapour is incorporated to process gas pipeline and sends into boiler;
C. process gas pipeline, at boiler secondary air open height by being divided into 4 branch road process gas pipelines, enters boiler from burner hearth both sides and Si Ge position, the back side, is the region of 900～1100 DEG C in fire box temperature, NH
3carry out reduction reaction with the NOx in flue gas and generate N
2and water, its reaction mechanism is as follows:
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 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) taking high-concentration ammonia nitrogenous wastewater as denitrfying agent for boiler desulfurization denitration, not only solve the pollution problem of petroleum chemical enterprise's nitrogen oxide, again the high ammonia-nitrogen wastewater of its discharge " is eaten up and used up " in denitrification process, eliminate two large pollution sources simultaneously, realized the target of environmental protection and resource regeneration doulbe-sides' victory;
(2) this technological investment is low, and operating cost is low, does not produce secondary pollution, without waste water, without waste residue, meets recycling economy rule, can realize zero consumption of denitrification process.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described, so that those skilled in the art more understands the present invention, but does not therefore limit the present invention.
Embodiment 1
A. go out condensate liquid from the crude synthesis gas of gasification process through gas-liquid separator separates, the synthesis gas of isolating after condensate liquid is delivered to low-temperature rectisol operation, washs the rear low temperature cold lime set producing and enters stripper from gasification ash water operation high pressure flash gas;
B. the steam after stripper air lift enters DN200 process gas pipeline and sends into boiler, and tower bottom divides condensate liquid to send deoxygenation tank, and deoxygenation tank flashed vapour is incorporated to DN200 process gas pipeline and sends into boiler;
C. DN200 process gas pipeline, at boiler secondary air open height by being divided into 4 DN100 pipelines, enters boiler from burner hearth both sides and Si Ge position, the back side, is the region of 900～1100 DEG C in fire box temperature, NH
3carry out reduction reaction with the NOx in flue gas and generate N
2and water, its reaction mechanism is as follows:
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 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。
After testing, in the method applied in the present invention boiler smoke after treatment, its denitration rate 15%; Sewage plant regulating reservoir ammonia nitrogen is down 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 discharges simultaneously.
Embodiment 2
A. go out condensate liquid from the crude synthesis gas of gasification process through gas-liquid separator separates, the synthesis gas of isolating after condensate liquid is delivered to low-temperature rectisol operation, washs the rear low temperature cold lime set producing and enters stripper from gasification ash water operation high pressure flash gas;
B. the steam after stripper air lift enters DN200 process gas pipeline and sends into boiler, and tower bottom divides condensate liquid to send deoxygenation tank, and deoxygenation tank flashed vapour is incorporated to DN200 process gas pipeline and sends into boiler;
C. DN200 process gas pipeline, at boiler secondary air open height by being divided into 4 DN100 pipelines, enters boiler from burner hearth both sides and Si Ge position, the back side, is the region of 1100 DEG C in fire box temperature, NH
3carry out reduction reaction with the NOx in flue gas and generate N
2and water; NH
3with the SO in 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. go out condensate liquid from the crude synthesis gas of gasification process through gas-liquid separator separates, the synthesis gas of isolating after condensate liquid is delivered to low-temperature rectisol operation, washs the rear low temperature cold lime set producing and enters stripper from gasification ash water operation high pressure flash gas;
B. the steam after stripper air lift enters DN200 process gas pipeline and sends into boiler, and tower bottom divides condensate liquid to send deoxygenation tank, and deoxygenation tank flashed vapour is incorporated to DN200 process gas pipeline and sends into boiler;
C. DN200 process gas pipeline, at boiler secondary air open height by being divided into 4 DN100 pipelines, enters boiler from burner hearth both sides and Si Ge position, the back side, is the region of 1000 DEG C in fire box temperature, NH
3carry out reduction reaction with the NOx in flue gas and generate N
2and water, its reaction mechanism is as follows:
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 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. the method for high-concentration ammonia nitrogenous wastewater and the boiler smoke comprehensive regulation, comprises following step:
A. go out condensate liquid from the crude synthesis gas of gasification process through gas-liquid separator separates, the synthesis gas of isolating after condensate liquid is delivered to low-temperature rectisol operation, washs the rear low temperature cold lime set producing and enters stripper from gasification ash water operation high pressure flash gas;
B. the steam after stripper air lift enters process gas pipeline and sends into boiler, and tower bottom divides condensate liquid to send deoxygenation tank, and deoxygenation tank flashed vapour is incorporated to process gas pipeline and sends into boiler;
C. process gas pipeline, at boiler secondary air open height by being divided into 4 branch road process gas pipelines, enters boiler from burner hearth both sides and Si Ge position, the back side, is the region of 900～1100 DEG C in fire box temperature, NH
3carry out reduction reaction with the NOx in flue gas and generate N
2and water; NH
3with the SO in 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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| CN102580498B true CN102580498B (en) | 2014-08-13 |
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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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101863523A (en) * | 2010-05-21 | 2010-10-20 | 赛鼎工程有限公司 | Method for treating ammonia-containing waste water from crushed coal pressure gasification |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2011
- 2011-12-31 CN CN201110458020.XA patent/CN102580498B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101863523A (en) * | 2010-05-21 | 2010-10-20 | 赛鼎工程有限公司 | Method for treating ammonia-containing waste water from crushed coal pressure gasification |
Non-Patent Citations (3)
| Title |
|---|
| JP特公平6-96145A 1994.11.30 |
| JP特开平6-343994A 1994.12.20 |
| JP特开平9-75915A 1997.03.25 |
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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 |