CN100450945C - Treatment processes of coke oven gas desulfurization and decyanation waste water - Google Patents
Treatment processes of coke oven gas desulfurization and decyanation waste water Download PDFInfo
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- CN100450945C CN100450945C CNB2005100955916A CN200510095591A CN100450945C CN 100450945 C CN100450945 C CN 100450945C CN B2005100955916 A CNB2005100955916 A CN B2005100955916A CN 200510095591 A CN200510095591 A CN 200510095591A CN 100450945 C CN100450945 C CN 100450945C
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- waste water
- decyanation
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- coke oven
- gas desulfurization
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- ZXMHLGMTFDVKQX-UHFFFAOYSA-N C(C1)CC1C1=CC=CC1 Chemical compound C(C1)CC1C1=CC=CC1 ZXMHLGMTFDVKQX-UHFFFAOYSA-N 0.000 description 1
- RNXHHSGATAAMDH-UHFFFAOYSA-N C(CC1)CC1C1=CC=C1 Chemical compound C(CC1)CC1C1=CC=C1 RNXHHSGATAAMDH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a subsequent disposing method of waste water through HPF method, which comprises the following steps: adding activated charcoal in the waste water to decolor; filtering to obtain supernatant and waste activated charcoal; returning waste activated charcoal to coal field into coke oven; evaporating supernatant under decompressing condition; condensing; cooling condensate to indoor temperature to obtain the solid of multi-amino composite salt; returning steam in the evaporating course into desulfurizing decyanating device to recycle after condensing.
Description
Technical field
The present invention relates to processes of coke oven gas desulfurization and decyanation and handle the waste water that the back forms, relate in particular to and adopt the ammoniacal liquor liquid catalytic that coke(oven)gas is carried out the method for subsequent processing that desulfuration and decyanation is handled the waste water that the back forms, belong to trade effluent and separate and the recovery technology field.
Background technology
In the coking industry, it is a very important process that the desulfuration and decyanation of coke(oven)gas is handled.Desulfurization and decyanation technology has multiple, and wherein the investment of AS method is minimum, but desulfuration and decyanation efficient is relatively poor; Efficient is higher ADA method and HPF method (ammoniacal liquor liquid catalytic).Comparatively speaking, ADA method raw material consumption is big, and production cost is higher; And the ammoniacal liquor liquid catalytic only needs to consume little amount of catalyst because of utilizing self alkali source (ammoniacal liquor) in the process of coking, and production cost is lower, so adopt the enterprise of this method more and more in the coking industry at present.When adopting the HPF method, coke(oven)gas produces multiple ammonium salt in the desulfuration and decyanation process, mainly contain: ammonium thiocyanate, ammonium thiosulfate, ammonium sulfate and a small amount of ammonium sulfide.These many ammonium salts are dissolved in the middle of the circulation fluid, and the constantly accumulation along with the increase of cycling time makes that the concentration of many ammonium salts is more and more higher in the circulation fluid.After many ammonium salts concentration acquires a certain degree, can not recycle, otherwise can influence the efficient of desulfuration and decyanation.At this moment, circulation fluid originally just becomes waste water, and this waste water needs through subsequent disposal if directly the words of discharging are polluted composing environment.
Treatment process for HPF method wastewater for desulfurization and decyanation in the prior art mainly contains three kinds: first kind is to adopt High Temperature High Pressure and under the effect of special catalyst, the many ammonium salts in the waste water all are converted into ammonium sulfate, thereby are recycled.Shanghai Baosteel just adopts this waste water treatment process, but this method equipment requirements height, production cost are big, and general medium and small sized enterprises can't utilize.Second method is the recovery ammonium thiocyanate technology that Shanghai Chemical Research Inst puts forward, Suzhou Steel Plant, Tianjin second producer gas plant all adopt this method, the shortcoming of this method be can only be from waste water the recovery part ammonium thiocyanate, remaining solid thing (main sulfur acid ammonium, ammonium thiosulfate, ammonium thiocyanate and impurity) can not be handled, they are caused secondary pollution by bulk deposition and loss; And the kind of employed catalyzer is bigger for the influence of this method in the desulfuration and decyanation process, and this has further limited promoting the use of of this method.The third method is that pit kiln is returned in the waste water coal blending, and this not only can cause equipment corrosion, and the accumulation problem of sulphur will be more and more serious.
Just because of there being above technical problem, cause some enterprises---particularly medium and small sized enterprises do not pass a test to the processing of processes of coke oven gas desulfurization and decyanation waste water, and these waste water just are not discharged under having through situation about effectively handling, and cause partial area environmental pollution serious.
Summary of the invention
The objective of the invention is deficiency, a kind of treatment process of processes of coke oven gas desulfurization and decyanation waste water is provided at the prior art existence.
For realizing purpose of the present invention, the treatment process of processes of coke oven gas desulfurization and decyanation waste water, described waste water is the waste water of coke(oven)gas through forming after the decyanation of ammoniacal liquor liquid catalytic desulfurizing, the main treating processes of this method is: add the gac processing of decolouring in described waste water, filter then, get clear liquid and waste active carbon, waste active carbon returns coal yard and advances pit kiln, the clear liquid evaporation under reduced pressure concentrates, concentrated solution is cooled to room temperature and promptly gets the multi-ammonium compound salt solid, this multi-ammonium compound salt is through Separation and Recovery, obtain various ammonium salt compounds, and the water vapour in the evaporative process forms water of condensation through condenser cooling back, and this water of condensation returns the desulfuration and decyanation systemic circulation and uses.
Further, in the treatment process of above-mentioned processes of coke oven gas desulfurization and decyanation waste water, in the described decolouring treating processes, activated carbon dosage is 1 of wastewater treatment capacity～5 ‰, and the temperature of keeping treatment solution is at 60～90 ℃, and to drive away wherein volatizable material, volatile matter enters the condenser cooling and reclaims.
Again further, in the treatment process of above-mentioned processes of coke oven gas desulfurization and decyanation waste water, decolouring disposes, and material is warming up to 100～110 ℃ and keep 1～3hr, and then filters, and this process vapor evaporated also enters the condenser cooling and reclaims.
Again further, in the treatment process of above-mentioned processes of coke oven gas desulfurization and decyanation waste water, described clear liquid evaporating concentration process, as controlling index, temperature is controlled at below 100 ℃ with water content＜15%, and at 16 hours with the interior evaporation concentration whole process of finishing.
Further, in the treatment process of above-mentioned processes of coke oven gas desulfurization and decyanation waste water, described clear liquid evaporating concentration process is to carry out under vacuum tightness 〉=750 mmhg, liquidus temperature＜75 ℃ condition.
Effect of the present invention is to make the waste water of coke(oven)gas after the decyanation of ammoniacal liquor liquid catalytic desulfurizing is handled not discharge, and has eliminated the pollution problem to environment; Resulting multi-ammonium compound salt can be recycled, and turns waste into wealth.And technological process of the present invention is simple, technological line is feasible, operating method is reliable, and many ammonium salts side reaction can not take place in the treating processes, purifies for the further separation of many ammonium salt solids thing and lays a good foundation.This technical scheme is applicable to the wastewater treatment of various coke(oven)gas HPF method desulfuration and decyanation devices, is particularly useful for the middle and small scale device, and its economic benefit and social benefit are very remarkable.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
The present invention starts with from the deficiency of analyzing prior art situation and existence thereof, by groping test, seek a more satisfactory treatment process, coke(oven)gas is handled the waste water separated into two parts that the back forms through HPF method desulfuration and decyanation, wherein a part is a water, another part is with ammonium thiocyanate, ammonium thiosulfate, materials such as ammonium sulfate are many ammonium salt solids thing of main component, both are recycled respectively, wherein water turns back to the desulfuration and decyanation treatment system and recycles, many ammonium salt solids thing is then kept its original composition proportion as far as possible, can obtain corresponding compounds after separating purification.
As Fig. 1, the main treating processes of this method is, adds the gac processing of decolouring in waste water, filters then, get clear liquid and waste active carbon, waste active carbon returns coal yard and advances pit kiln, and the clear liquid evaporation under reduced pressure concentrates, and concentrated solution is cooled to room temperature and promptly gets the multi-ammonium compound salt solid, this multi-ammonium compound salt is through Separation and Recovery, can get various ammonium salt compounds, and the water vapour in the evaporative process forms water of condensation through condenser cooling back, this water of condensation returns the desulfuration and decyanation systemic circulation and uses.
Wherein, activated carbon dosage is generally 1 of wastewater treatment capacity～5 ‰, and in the decolouring treating processes, the temperature of keeping treatment solution is at 60～90 ℃, and to drive away wherein volatizable material, volatile matter also enters the condenser cooling and reclaims.Decolouring disposes, and can also earlier material be warming up to 100～110 ℃ and keep 1～3hr, and then filter, and this process vapor evaporated also enters the condenser cooling and reclaims.Such as, 17600 milliliters of this waste water, record and wherein contain NH
4CNS:8.60%, (NH
4)
2S
2O
3: 7.65%, (NH
4)
2SO
4: 3.30%, H
2O:80.55% to this, can add gac 325 and restrain, and removes about 6710 milliliters water while decolouring 80 ℃ of left and right sides, and material kept 2 hours down at 105 ℃, through filtering, got 10560 milliliters of left and right sides clear liquids then, recorded wherein to contain NH
4CNS:13.26%, (NH
4)
2S
2O
3: 12.47%, (NH
4)
2SO
4: 5.44%, H
2O:69.23%.
During the clear liquid evaporation concentration, generally be the controlling index that finishes as evaporative process with water content＜15%, temperature is controlled at below 100 ℃, and at 16 hours with the interior evaporation concentration whole process of finishing.For avoiding the decomposition of ammonium salt in the waste water, more satisfactory concentrated condition is: vacuum tightness 〉=750 mmhg, liquidus temperature＜75 ℃.As, the clear liquid after 7500 milliliters of decolourings contains NH
4CNS:10.35%, (NH
4)
2S
2O
3: 9.15%, (NH
4)
2SO
4: 1.03%, H
2O:79.47% anhydrates 6150 milliliters through concentrating under reduced pressure, can get multi-ammonium compound salt 1810 grams, wherein contains NH
4CNS:43.97%, (NH
4)
2S
2O
3: 38.55%, (NH
4)
2SO
4: 3.40%, H
2O:14.28%.As seen, adopt these processing condition to carry out concentration, compare before handling with after handling, the content ratio of ammonium salt is consistent basically.
In addition, in the evaporating concentration process, water vapour forms water of condensation through condenser cooling back, this water of condensation reaches in the Control Circulation amount and can return the desulfuration and decyanation device under the EQUILIBRIUM CONDITION and recycle, so neither influence the technological effect of desulfuration and decyanation device, can reduce the running cost of device again greatly.
In a word, the invention provides the method for subsequent processing of a kind of coke(oven)gas waste water of formation after the decyanation of ammoniacal liquor liquid catalytic desulfurizing is handled, use this method and can guarantee that this type of waste water does not discharge, effectively eliminate pollution problem environment.Technology of the present invention is simple, technology is reliable, has good popularizing application prospect in this area.
Claims (6)
1. the treatment process of processes of coke oven gas desulfurization and decyanation waste water, described waste water is the waste water of coke(oven)gas through forming after the decyanation of ammoniacal liquor liquid catalytic desulfurizing, it is characterized in that: the main treating processes of this method is, in described waste water, add the gac processing of decolouring, filter then, get clear liquid and waste active carbon, waste active carbon returns coal yard and advances pit kiln, the clear liquid evaporation under reduced pressure concentrates, concentrated solution is cooled to room temperature and promptly gets the multi-ammonium compound salt solid, and this multi-ammonium compound salt obtains various ammonium salt compounds through Separation and Recovery, and the water vapour in the evaporative process forms water of condensation through condenser cooling back, and this water of condensation returns the desulfuration and decyanation systemic circulation and uses.
2. the treatment process of processes of coke oven gas desulfurization and decyanation waste water according to claim 1, it is characterized in that: in the described decolouring treating processes, activated carbon dosage is 1 of wastewater treatment capacity～5 ‰, and the temperature of keeping treatment solution is at 60～90 ℃, to drive away wherein volatizable material, volatile matter enters the condenser cooling and reclaims.
3. the treatment process of processes of coke oven gas desulfurization and decyanation waste water according to claim 1 and 2, it is characterized in that: decolouring disposes, material is warming up to 100～110 ℃ and keep 1～3hr, and then filters, and this process vapor evaporated also enters the condenser cooling and reclaims.
4. the treatment process of processes of coke oven gas desulfurization and decyanation waste water according to claim 1 is characterized in that: described clear liquid evaporating concentration process, with water content＜15% as controlling index.
5. the treatment process of processes of coke oven gas desulfurization and decyanation waste water according to claim 4, it is characterized in that: described clear liquid is in the reduction vaporization concentration process, and temperature is controlled at below 100 ℃, and at 16 hours with the interior evaporation concentration whole process of finishing.
6. the treatment process of processes of coke oven gas desulfurization and decyanation waste water according to claim 4, it is characterized in that: described clear liquid evaporating concentration process is to carry out under vacuum tightness 〉=750 mmhg, liquidus temperature＜75 ℃ condition.
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| CNB2005100955916A CN100450945C (en) | 2005-11-24 | 2005-11-24 | Treatment processes of coke oven gas desulfurization and decyanation waste water |
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|---|---|---|---|
| CNB2005100955916A CN100450945C (en) | 2005-11-24 | 2005-11-24 | Treatment processes of coke oven gas desulfurization and decyanation waste water |
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| CN100450945C true CN100450945C (en) | 2009-01-14 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267778B (en) * | 2010-06-04 | 2013-05-01 | 中国科学院过程工程研究所 | Resource method of waste liquid from coke oven gas desulphurization and decyanation |
| CN102336417B (en) * | 2010-07-21 | 2014-05-21 | 苏州久王多铵盐科技有限公司 | Method for recovering sodium sulfocyanate from desulfurized and decyanated wastewater of coke-oven gas |
| CN102295379B (en) * | 2011-06-30 | 2012-09-05 | 首钢总公司 | Method for treating desulfurization waste liquid of wet oxidation method |
| CN102765778A (en) * | 2012-08-17 | 2012-11-07 | 新疆化工设计研究院 | Method for treating coking waste water |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4104131A (en) * | 1976-07-08 | 1978-08-01 | United States Steel Corporation | Process for separating ammonia and acid gases from waste waters containing fixed ammonia salts |
| RU2084404C1 (en) * | 1994-10-31 | 1997-07-20 | Лариса Ивановна Бельчинская | Method for treating waste water |
-
2005
- 2005-11-24 CN CNB2005100955916A patent/CN100450945C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4104131A (en) * | 1976-07-08 | 1978-08-01 | United States Steel Corporation | Process for separating ammonia and acid gases from waste waters containing fixed ammonia salts |
| RU2084404C1 (en) * | 1994-10-31 | 1997-07-20 | Лариса Ивановна Бельчинская | Method for treating waste water |
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| CN1970458A (en) | 2007-05-30 |
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Address after: 215159 Jiangsu city of Suzhou province Wuzhong District Guangfu Town Industrial Park Suzhou king long circuit light environmental protection science and technology limited company Patentee after: Suzhou Jiuwang Environmental Protection Science & Technology Co., Ltd. Address before: 215159 Jiangsu city of Suzhou province Wuzhong District Guangfu Town East Industrial Park Patentee before: Suzhou Jiuwang Multiple Ammonium Salt Technology Co., Ltd. |
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Owner name: SUZHOU JIUWANG ENVIRONMENTAL PROTECTION TECHNOLOGY Free format text: FORMER NAME: SUZHOU JIUWANG MULTIPLE AMMONIUM SALT TECHNOLOGY CO., LTD. |
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Address after: Guangfu town Wuzhong District Huaqiao village in Suzhou City, Jiangsu province 215159 Suzhou Long Wang environmental Polytron Technologies Inc Patentee after: Suzhou Jiuwang Environmental Protection Technology Co., Ltd. Address before: 215159 Jiangsu city of Suzhou province Wuzhong District Guangfu Town Industrial Park Suzhou king long circuit light environmental protection science and technology limited company Patentee before: Suzhou Jiuwang Environmental Protection Science & Technology Co., Ltd. |
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Granted publication date: 20090114 Termination date: 20151124 |
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