CN100378012C - Method for treating ammonia nitrogen in charking deposed ammonia - Google Patents
Method for treating ammonia nitrogen in charking deposed ammonia Download PDFInfo
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- CN100378012C CN100378012C CNB2006100193724A CN200610019372A CN100378012C CN 100378012 C CN100378012 C CN 100378012C CN B2006100193724 A CNB2006100193724 A CN B2006100193724A CN 200610019372 A CN200610019372 A CN 200610019372A CN 100378012 C CN100378012 C CN 100378012C
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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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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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Abstract
The present invention relates to a method for treating ammonia nitrogen in charking deposed ammonia. First, 15 to 35 g/L of remover is added into coking deposed ammonia, and the pH value is modulated to 10 to 14. The coking deposed ammonia is sent to a reaction device, and the reacting coking deposed ammonia enters an immersion type blow-off desorption device. Coke oven gas from an ammonium sulfate saturator enters the first and the second segments of gas distributor under the liquid level of the immersion type blow-off desorption device to carry out blow-off desorption. Deposed ammonia after blow-off desorption is sent into an activated sludge processing device by a pump. After cooled, gas containing ammonia after blow-off desorption enters a coke oven gas main pipe. The mixed gas is conveyed into the ammonium sulfate saturator via a blower, and carries out exothermic reaction with sulfate to generate ammonium sulfate. After the gas generates ammonium sulfate, the majority of the gas enters a benzene recovery system and is finally sent to a fuel gas factory or a coke oven factory to use. A small part of the gas enters the immersion type blow-off desorption device to be circularly used. The present invention can enhance ammonia and nitrogen elimination efficiency, save energy, reduce the cost, relieve the loading of ammonia and nitrogen biochemical treatment and protect the environment.
Description
Technical field
The invention belongs to the processing technology field of charking deposed ammonia.Relate in particular to a kind of treatment process that directly applies to ammonia nitrogen in coke-oven plant's remained ammonia or the deposed ammonia.
Background technology
The remained ammonia that in coke-oven plant's production process, is produced, ammonia nitrogen is made of volatilization ammonium salt and solid ammonium-salt, and the volatilization ammonium salt has NH
4OH, (NH
4)
2S, NH
4CN and (NH
4)
2CO
3, solid ammonium-salt has NH
4Cl and (NH
4)
2SO
4Deng.
At present, the coke-oven plant generally adopts the ammonia nitrogen in the vapour method removal remained ammonia both at home and abroad, and promptly the remained ammonia after the oil removing enters ammonia distillation tower top after the ammoniacal liquor interchanger is heated to 90 ℃, and tower bottom feeding water vapor steams the volatilization ammonia in the ammoniacal liquor.Lower the temperature through overhead condenser from the ammonia steam that the ammonia still process cat head is overflowed, the phlegma of generation is done to reflux and is flowed directly in the tower.Ammonia steam after the cooling enters in the neutralizer and reacts with pyridine sulfate, generates crude pyridine; Perhaps gas pipe before saturex and ammoniated coal gas enter saturex in the lump, generate ammonium sulfate with sulfuric acid reaction.And enter coke-oven plant's activated sludge biochemical treatment device after distilled ammonia wastewater of discharging at the bottom of the ammonia still and the raw material ammonia water heat exchange.
Ammonia in the domestic employing coal gas desorption method decoking remained ammonia (Cao Hansheng. remove ammonia in the remained ammonia with the coal gas desorption method. fuel and chemical industry .2000,31 (2): 103～104.), remained ammonia after the oil removing is flowed into sloptank, after adding NaOH in the groove, through the oil-poor interchanger heat exchange of heat, after being heated to 85～90 ℃, steam heater enters three sections flow-through type sieve plate desorption towers, with the coal gas counter current contact that enters at the bottom of the tower, cause temperature reduction in the tower, for making remained ammonia can be maintained to 85～90 ℃, before entering every section tower, earlier remained ammonia is heated with the steam heater outside the tower at flow-through type sieve plate desorption tower.The coal gas that cat head goes out is gone into gas main behind condensate cooler.Remained ammonia behind the deamination send coke-oven plant's activated sludge biochemical treatment device to handle.
In above-mentioned technology, the former is owing to adopt ammonia still equipment big, water vapor desorption service temperature height, and energy consumption is big, the cost height, the total ammonia nitrogen decreasing ratio is low, and the ammonia nitrogen loading that activated sludge biochemical is handled is bigger.Therefore, the processing of Coking Plant Wastewater for a long time is difficult to reach the emission standard of national water quality.The flow-through type sieve-tray tower that the latter adopts, equipment is big, service temperature is higher, also adopts a plurality of steam heater heating for making remained ammonia be maintained to 85～90 ℃ at flow-through type sieve plate desorption tower, energy consumption is bigger, the cost height, the total ammonia nitrogen decreasing ratio is low, and the load that activated sludge biochemical is handled is bigger.Therefore, the processing of Coking Plant Wastewater for a long time is difficult to reach national water quality emission standard.
Summary of the invention
The purpose of this invention is to provide a kind of can save energy, reduce cost, can reduce biochemical ammonia nitrogen loading, can handle the method for the ammonia nitrogen in the charking deposed ammonia effectively.
For achieving the above object, the technical solution adopted for the present invention to solve the technical problems is: add earlier the agent that removes of 15～35g/L in charking deposed ammonia, regulate pH value to 10～14, remove agent or be the Na in the strong base-weak acid salt
2CO
3, or be highly basic.The deposed ammonia that again adding is removed agent is sent into reaction unit by pipeline and is reacted, and reacted deposed ammonia enters immersed type stripping desorption apparatus by pipeline, evenly sprays wherein through the deposed ammonia sparger; Enter the desorb of subsurface one, the two section gas distributor stripping of immersed type stripping desorption apparatus by the small portion coke-oven gas from the ammonium sulfate saturex by pipeline, total ammonia nitrogen is taken off to 100mg/l, decreasing ratio can reach more than 96%.Then with the deposed ammonia after the stripping desorb with being pumped into activated-sludge processing apparatus; The ammonia coke-oven gas that contains after the stripping desorb is overflowed from the top of immersed type stripping desorption apparatus after cooling off, and enters coke-oven gas house steward before the gas blower by pipeline.Coke-oven gas house steward's mixed gas is sent into the ammonium sulfate saturex through gas blower by pipeline, and the sulfuric acid thermopositive reaction in the mixed gas in ammonia and the ammonium sulfate saturex generates ammonium sulfate.Most of coke-oven gas from the ammonium sulfate saturex enters the crude benzol recovery system by pipeline, is sent to combustion gas factory or coke oven at last and uses; Entering immersed type stripping desorption apparatus from the small portion coke-oven gas of ammonium sulfate saturex by pipeline recycles.Wherein:
The chemical ingredients of charking deposed ammonia is that total ammonia is that 2～5g/L, volatilization ammonia are 1～2g/L, CO
2Be that 1～2g/L, sulfide are that 0.2～2g/L, prussiate are that 0.04～0.14g/L, volatile phenol are 1.3～2.5g/L.
Deposed ammonia enters by the liquid inlet of pipeline from reaction unit, the liquid reactions passage that enters separately through the eddy flow plate of installing between each thermal barrier chuck repeatedly reacts again, and reacted liquid is sent into immersed type stripping desorption apparatus from liquid exit by pipeline.Temperature is that 70～100 ℃ thermal barrier enters from the heat-carrier inlet of each thermal barrier chuck, and the heat-carrier passage by separately flows out from heating medium outlet.Thermal barrier is a kind of in water vapor or the thermal conductance oil.
The liquid level of reacted deposed ammonia is higher than one, two section gas distributor in the immersed type stripping desorption apparatus, the medium of stripping desorb ammonia nitrogen is the coke-oven gas from the ammonia content≤30mg/L behind the ammonium sulfate saturex, and coke-oven gas sprays into through the spray orifice of one, two section gas distributor and carries out the stripping desorb in the deposed ammonia.The stripping desorption time is 1～3h, and the stripping desorption temperature is 70～80 ℃, and gas-liquid volume ratio is 500～2000: 1; The ammonia coke-oven gas pneumatic outlet from the top after the prolong cooling that contains after the stripping desorb is overflowed, and the temperature of effusion is 25～40 ℃.
Activated-sludge processing apparatus or be anaerobic-anoxic-aerobic activated sludge biochemical treatment apparatus or be the activated-sludge processing apparatus of other type.Work as Na
2CO
3When removing agent, the deposed ammonia after the stripping desorb send anaerobic-anoxic-aerobic activated sludge biochemical treatment apparatus; When the highly basic conduct removed agent, the deposed ammonia after the stripping desorb gave the activated-sludge processing apparatus of other type.
Adopt technique scheme, the present invention has following characteristics:
1, owing in deposed ammonia, adds Na
2CO
3, make solid ammonium-salt easily be converted into the volatilization ammonium salt, improved the decreasing ratio of ammonia nitrogen.
2, owing to adopt hot coke-oven gas after ammonia and the sulfuric acid thermopositive reaction as stripping desorb medium, without water vapor, as impellent, carry out the desorb of immersed type stripping according to the partial pressure difference of ammonia in the dividing potential drop of coke-oven gas ammonia and the remained ammonia, reduced energy consumption.
3, because the coke-oven gas after the stripping desorb is got back to again in the coke-oven gas manifold system, simultaneously deposed ammonia there is extractive effect, has improved desorption efficiency.
4, since among the coke-oven gas house steward ammonia of coke-oven gas after producing ammonium sulfate, small portion coke-oven gas from the ammonium sulfate saturex enters immersed type stripping desorption apparatus formation closed cycle, do not discharge any pollutent to the external world, the total ammonia nitrogen decreasing ratio can reach more than 96%, can alleviate the load of activated-sludge processing apparatus ammonia nitrogen.
5, owing to utilize the negative pressure cyclic production of coke-oven gas house steward before overbottom pressure behind the ammonium sulfate saturex and the blower fan, do not need additionaling power; Utilize the heat of chemical reaction heat and coke oven remained ammonia to carry out the stripping desorb simultaneously, need not add heat substantially, energy-saving effect is remarkable.
Therefore, the present invention can improve ammonia nitrogen removal efficient, save energy, reduce cost, alleviates the biochemical treatment ammonia nitrogen loading, and has protected environment.
Description of drawings
Fig. 1 is a kind of process flow diagram of the present invention;
Fig. 2 is the structure and the work synoptic diagram of reaction unit among Fig. 1 [9];
Fig. 3 is the structure and the work synoptic diagram of immersed type stripping desorption apparatus [8] among Fig. 1.
Embodiment
Below in conjunction with accompanying drawing the technology of the present invention is further specified.
The chemical ingredients of a kind of charking deposed ammonia [11] is: total ammonia is that 2～5g/L, volatilization ammonia are 1～2g/L, CO
2Be that 1～2g/L, sulfide are that 0.2～2g/L, prussiate are that 0.04～0.14g/L, volatile phenol 1.3～2.5g/L, temperature are 70～80 ℃.The technical process of handling ammonia nitrogen in this deposed ammonia is as shown in Figure 1:
The Na that in above-mentioned charking deposed ammonia [11], adds 15～35g/L earlier
2CO
3As removing agent [10], modulation pH value to 10～12 will add Na again
2CO
3The deposed ammonia [11] that removes agent [10] is sent into as shown in Figure 2 reaction unit by pipeline.Deposed ammonia [11] is by liquid inlet [20] the eddy flow plate [17] through installing between each thermal barrier chuck [19], and the liquid reactions passage [18] that enters separately repeatedly reacts, the solid ammonium-salt in the remained ammonia [11] in whirlwind-type reactor [9] with Na
2CO
3Reaction changes into labile volatilization ammonium salt.Reacted liquid is sent into immersed type stripping desorption apparatus [8] from liquid exit [12] by pipeline.Be guaranteeing the temperature of reaction of whirlwind-type reactor [9], is that 70～100 ℃ thermal barrier enters from the heat-carrier inlet [13] of each thermal barrier chuck [19] with temperature, and the heat-carrier passage [16] by separately flows out from heating medium outlet [14].When supplying to clean or overhaul, opens outage [15].
Reacted deposed ammonia [11] enters immersed type stripping desorption apparatus [8] by pipeline, immersed type stripping desorption apparatus [8] as shown in Figure 3, reacted deposed ammonia [11] enters deposed ammonia sparger [24] by pipeline through deposed ammonia inlet [31], the nozzle of deposed ammonia sparger [24] sprays deposed ammonia [11] wherein equably, the deposed ammonia that is sprayed [11] liquid level is higher than one, two section gas distributor [25], [27], and liquid level immerses height and controlled by liquid level meter [30].The medium of stripping desorb ammonia nitrogen is the 65 ℃ of coke-oven gas [1] from the ammonia content≤30mg/L behind the ammonium sulfate saturex, coke-oven gas [1] enters by gas entry [26] and is immersed in subsurface one, the two section gas distributor of deposed ammonia [11] [25], [27], spray in the deposed ammonia [11] through spray orifice and to carry out the stripping desorb, the stripping desorption time is 2h, the stripping desorption temperature is 70～80 ℃, and gas-liquid volume ratio is 500～1500: 1., as impellent the free ammonia stripping in the remained ammonia is come out according to the partial pressure difference of ammonia in the dividing potential drop of coke-oven gas ammonia and the remained ammonia, total ammonia nitrogen is taken off to 100mg/l, decreasing ratio can reach more than 96%.
Overflow through the ammonia coke-oven gas pneumatic outlet [21] from the top after prolong [22] cooling that contains after the stripping desorb, enter preceding coke-oven gas [1] house steward of gas blower [2] by pipeline.The temperature of overflowing is 25～40 ℃, and the cold water inlet [32] of prolong [22], hot water outlet [23] connect with the cold water pipe and the hot-water line of outside respectively.In addition, the deposed ammonia after the stripping desorb is sent into anaerobic-anoxic-aerobic activated sludge treatment unit [7] by pipeline with pump [6].For guaranteeing the quality of stripping desorb, the upper fixed that exports [29] at deposed ammonia has traverse baffle [28].
The mixed gas of coke-oven gas [1] total pipeline is sent into ammonium sulfate saturex [3] through gas blower [2] by pipeline, and the sulfuric acid thermopositive reaction in the mixed gas in ammonia and the ammonium sulfate saturex [3] generates ammonium sulfate.65 ℃ of hot coke-oven gas major parts from ammonium sulfate saturex [3] enter crude benzol recovery system [4] by pipeline, be sent to combustion gas factory or coke oven [5] heating usefulness at last, enter immersed type stripping desorption apparatus [8] from the small portion coke-oven gas of ammonium sulfate saturex [3] by pipeline and recycle.
Claims (5)
1. method of handling ammonia nitrogen in the charking deposed ammonia, what it is characterized in that adding earlier 15～35g/L in charking deposed ammonia [11] removes agent [10], regulates system pH value to 10～14, removes agent [10] or is Na in the strong base-weak acid salt
2CO
3, or be highly basic, the deposed ammonia [11] that again adding is removed agent [10] is sent into reaction unit [9] by pipeline and is reacted, deposed ammonia [11] enters by the liquid inlet [20] of pipeline from reaction unit [9], pass through between each thermal barrier chuck [19] the liquid reactions passage [18] that the eddy flow plate [17] installed enters separately again and repeatedly react, reacted liquid is sent into immersed type stripping desorption apparatus [8] from liquid exit [12] by pipeline; Temperature is that 70～100 ℃ thermal barrier enters from the heat-carrier inlet [13] of each thermal barrier chuck [19], and the heat-carrier passage [16] by separately flows out from heating medium outlet [14]; Reacted deposed ammonia [11] enters immersed type stripping desorption apparatus [8] by pipeline, evenly spray wherein through deposed ammonia sparger [24], enter immersed type stripping desorption apparatus [8] subsurface by small portion coke-oven gas by pipeline from ammonium sulfate saturex [3], two sections gas distributors [25], [27] stripping desorb, then the deposed ammonia after the stripping desorb is sent into activated-sludge processing apparatus [7] with pump [6], overflowing in the ammonia coke-oven gas top from immersed type stripping desorption apparatus [8] after cooling off that contains after the stripping desorb, enters preceding coke-oven gas [1] house steward of gas blower [2] by pipeline; Coke-oven gas [1] house steward's mixed gas is sent into ammonium sulfate saturex [3] through gas blower [2] by pipeline, sulfuric acid thermopositive reaction in the mixed gas in ammonia and the ammonium sulfate saturex [3] generates ammonium sulfate, most of coke-oven gas from ammonium sulfate saturex [3] enters crude benzol recovery system [4] by pipeline, be sent to combustion gas factory or coke oven [5] at last, enter immersed type stripping desorption apparatus [8] from the small portion coke-oven gas of ammonium sulfate saturex [3] by pipeline and recycle.
2. the method for ammonia nitrogen in the processing charking deposed ammonia according to claim 1 is characterized in that the chemical ingredients of described charking deposed ammonia [11] is, total ammonia is that 2～5g/L, volatilization ammonia are 1～2g/L, CO
2Be that 1～2g/L, sulfide are that 0.2～2g/L, prussiate are that 0.04～0.14g/L, volatile phenol are 1.3～2.5g/L.
3. the method for ammonia nitrogen in the processing charking deposed ammonia according to claim 1 is characterized in that described thermal barrier is a kind of in water vapor or the thermal conductance oil.
4. the method for ammonia nitrogen in the processing charking deposed ammonia according to claim 1, it is characterized in that reacted deposed ammonia [11] liquid level is higher than one in the described immersed type stripping desorption apparatus [8], two sections gas distributors [25], [27], the medium of stripping desorb ammonia nitrogen is the coke-oven gas [1] from the ammonia content≤30mg/L behind the ammonium sulfate saturex, coke-oven gas [1] is through one, two sections gas distributors [25], [27] spray orifice sprays in the deposed ammonia [11] and carries out the stripping desorb, the stripping desorption time is 1～3h, the stripping desorption temperature is 70～80 ℃, and gas-liquid volume ratio is 500～2000: 1; The ammonia coal gas pneumatic outlet [21] from the top after prolong [22] cooling that contains after the stripping desorb is overflowed, and the temperature of effusion is 25～40 ℃.
5. the method for ammonia nitrogen in the processing charking deposed ammonia according to claim 1 is characterized in that described activated-sludge processing apparatus [7] or is anaerobic-anoxic-aerobic activated sludge biochemical treatment apparatus or be the activated-sludge processing apparatus of other type; Work as Na
2CO
3When removing agent [10], the deposed ammonia after the stripping desorb send anaerobic-anoxic-aerobic activated sludge biochemical treatment apparatus, when highly basic when removing agent [10], the deposed ammonia after the stripping desorb gives the activated-sludge processing apparatus of other type.
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| CNB2006100193724A CN100378012C (en) | 2006-06-15 | 2006-06-15 | Method for treating ammonia nitrogen in charking deposed ammonia |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060406B (en) * | 2010-11-19 | 2012-12-19 | 南京工业大学 | Efficient stripping and closed-loop treatment integrated process for recycling ammonia nitrogen wastewater from tail gas |
| CN102989266B (en) * | 2011-09-13 | 2016-12-21 | 杨友发 | The technique of ammonium sulfate crystallization technical finesse ammonia and equipment |
| CN103241788B (en) * | 2013-05-23 | 2014-12-03 | 中唯炼焦技术国家工程研究中心有限责任公司 | Method and device for treating ammonia nitrogen in high-concentration phenolic wastewater |
| CN103408182A (en) * | 2013-08-23 | 2013-11-27 | 济钢集团有限公司 | Process for deoiling residual ammonia water |
| CN105694988A (en) * | 2016-03-03 | 2016-06-22 | 金能科技股份有限公司 | Process for solving coal gas desulfuration liquid expansion in coking industry and system for process |
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|---|---|---|---|---|
| DE2626164A1 (en) * | 1975-06-24 | 1977-01-20 | Centre Rech Metallurgique | Desorption of volatile cpds esp ammonia - from waste liquor from coking plant using a stripping column |
| US4104038A (en) * | 1975-06-24 | 1978-08-01 | Centre De Recherches Metallurgiques-Centrum Voor Research In De Metallurgie | Desorption of volatile compounds dissolved in a liquid phase |
| CN1172070A (en) * | 1997-07-11 | 1998-02-04 | 王天伦 | Method for producing ammonium sulfate by using waste ammonia water |
| CN1207367A (en) * | 1998-04-08 | 1999-02-10 | 冶金工业部建筑研究总院 | Method for treatment of residual coking ammonia water or all coking waste water with flue gas |
| CN1535756A (en) * | 2003-05-23 | 2004-10-13 | 程志久 | Method ofr desulfurization of waste gas and coking waste water treatment and its equipment |
| CN1778911A (en) * | 2005-10-12 | 2006-05-31 | 太原理工大学 | Treatment of coking crude waste water |
-
2006
- 2006-06-15 CN CNB2006100193724A patent/CN100378012C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2626164A1 (en) * | 1975-06-24 | 1977-01-20 | Centre Rech Metallurgique | Desorption of volatile cpds esp ammonia - from waste liquor from coking plant using a stripping column |
| US4104038A (en) * | 1975-06-24 | 1978-08-01 | Centre De Recherches Metallurgiques-Centrum Voor Research In De Metallurgie | Desorption of volatile compounds dissolved in a liquid phase |
| CN1172070A (en) * | 1997-07-11 | 1998-02-04 | 王天伦 | Method for producing ammonium sulfate by using waste ammonia water |
| CN1207367A (en) * | 1998-04-08 | 1999-02-10 | 冶金工业部建筑研究总院 | Method for treatment of residual coking ammonia water or all coking waste water with flue gas |
| CN1535756A (en) * | 2003-05-23 | 2004-10-13 | 程志久 | Method ofr desulfurization of waste gas and coking waste water treatment and its equipment |
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