CN101289234A - Process for treating industrial waste water containing hydroxybenzene and ammine by double-tower stripping - Google Patents
Process for treating industrial waste water containing hydroxybenzene and ammine by double-tower stripping Download PDFInfo
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Abstract
A method for treating wastewater with phenol and ammonia coal from chemical industry by double-tower steam stripping is disclosed. The steps of the technical method of the invention are as follows: 1. acidic gases are deacidified; 2. amino is removed; 3. ammonia is concentrated and purified. The invention has the advantages that: 1. by the method of the invention, acidic gases and ammonia can be removed comparatively thoroughly, residual quantity of the acidic gases can be reduced to be below 10mg/L and the total amount of ammonia can be reduced to below 10mg/L, thereby avoiding the resistance function of the ammonia to the follow-up biochemical section; 2. the method of the invention can greatly improve the desorption rate of phenol or decrease the operation cost of the extraction section; 3. the method of the invention can effectively separate volatile phenol from ammonia, and the content of the volatile phenol and the acidic gases can be decreased to below 10mg/L, thus lightening the energy consumption and purifying load in the follow-up ammonia refining process; 4. the concentration of the ammonia can be improved to over 98 percent; 5. the method can effectively remove oil contaminants with low boiling point.
Description
Technical field
The present invention relates to a kind of method of handling coal chemical industrial waste water, relate in particular to a kind of double tower stripping and handle the method that contains phenol, ammonia coal chemical industrial waste water.
Background technology
China is a coal big country, and along with the worsening shortages of petroleum resources, the development of Coal Chemical Industry industries such as coal system oil, gas maked coal is in the ascendant, and the consequent is the serious environmental pollution problem.Produce a large amount of high pollution waste water in gasification, the coking, contained the pollutent such as phenol, ammonia, sour gas of high density.For such waste water, just can enter follow-up biochemical treatment after must taking the chemical separating flow process to isolate most phenol, ammonia, sour gas earlier.
The problem that all has at present following several respects in the technology aspect the coal chemical industrial waste water processing and technology more or less: 1, deacidifying process is unreasonable, make the sour gas such as carbonic acid gas, hydrogen sulfide of dissolved ionic state in the waste water can not be converted into free state cost-effectively, the residual quantity of sour gas is too high; 2, during deamination, the separation of ammonia, phenol is not thorough, causes in the ammonolysis product phenol content and content of acid gas very high, has strengthened the load of the refining section of follow-up ammonia; When 3, the ammonia content in the waste water is high, the fluctuation of service of deammoniation tower.In the part flow process, the complicated tower stripping ammonia that adopts the band side line to extract out, when ammonia concentration was high, because extraction amount, the internal circulating load of ammonia are big, it was unstable often to cause the deamination Tata to be pressed, the ammonia content of purifying waste water fluctuation.4, owing to can not solve the problem that volatile phenol influence the ammonia quality effectively, some technology takes to extract earlier the technology of deamination again, thereby the pH when extracting is higher.When pH＞8, phenol mainly exists with ionic state in water and wetting ability improves greatly, makes the efficient of extracting and dephenolizing reduce significantly.
Because the existence of above problem, the technology of still not having a kind of comparatively mature and reliable, stable operation at present can make most coal chemical industrial waste waters can satisfy the requirement of biochemical treatment continuously and stably after pre-treatment.A large amount of coal chemical industrial waste waters still is in the state of the discharging that exceeds standard.
Summary of the invention
The object of the present invention is to provide a kind of double tower stripping to handle the method that contains phenol, ammonia coal chemical industrial waste water, this invention can remove sour gas and ammonia up hill and dale, can reduce the quantity of solvent that non-condensable gas is carried secretly, reduces solvent loss.
The present invention is achieved like this, and its processing method step is:
(1) acid gas removal body: make to contain phenol, ammonia coal chemical industrial waste water and divide hot and cold two bursts of extracting tower top and middle and upper parts of extracting out to enter in the tower from the band side line, making tower top pressure is 0.2～0.7MPa (a), 40～80 ℃ of temperature, tower bottom pressure are 0.25～0.75Mpa (a), 120～170 ℃ of temperature.Sour gas comes out from the cat head stripping, can enter according to the composition situation that sulfur recovery unit, torch burn or directly emptying, extraction still liquid at the bottom of the tower;
(2) deamination: the waste water that removes sour gas enters in the deammoniation tower from the middle and upper part, and tower top pressure is 0.2～0.7Mpa (a), 40～80 ℃ of temperature, and tower bottom pressure is 0.25～0.75Mpa (a), 120～170 ℃ of temperature.Ammonia-the water vapor that contains ammonia 5-10% comes out from the cat head stripping.Extraction still liquid at the bottom of the tower.Still liquid can enter the extracting and dephenolizing device or directly advances biochemical device and carry out subsequent disposal according to the composition situation;
(3) ammonia concentrates and purifies: contain a large amount of volatile phenols and sour gas from ammonia-water vapor that deammoniation tower top stripping goes out, concentrate and make with extra care by three grades of fractional condensation devices that constitute by interchanger and branch flow container, the temperature of one-level fractional condensation device is 110-150 ℃, and pressure is 0.4-0.65Mpa (a); The temperature of secondary fractional condensation device is 70-90 ℃, and pressure is 0.3-0.5Mpa (a); The temperature of three grades of fractional condensation devices is 30-55 ℃, and pressure is 0.1-0.4Mpa (a).The liquid phase of three grades of fractional condensation devices is divided into the profit two-phase after overcooling, oil phase is as the light oil products extraction; A water part is back to the deamination cat head, and another part is back to the feeding line of extracting tower.Through concentrating with purify after ammonia can sell or further be refined into liquefied ammonia after sell.
The product of the present invention's preparation is realized by this device, it comprises that extracting tower, deammoniation tower, one-level condensate cooler, one-level divide flow container, B-grade condensation water cooler, secondary to divide flow container, three grades of condensate coolers, three fraction flow containers, water-and-oil separator, reflux pump, feed pipe, pump, acid withdrawer, it is characterized in that feed pipe connects extracting tower by pump, the extracting tower cat head connects acid withdrawer, connects deammoniation tower at the bottom of the tower.The deammoniation tower cat head connects the one-level condensate cooler, connects extraction plant or biochemical device at the bottom of the tower.The one-level condensate cooler connects one-level and divides flow container, and one-level divides the flow container tank deck to connect the B-grade condensation water cooler, and jar end connects water-and-oil separator.The B-grade condensation water cooler connects secondary and divides flow container, and secondary divides the flow container tank deck to connect three grades of condensate coolers, and jar end connects water-and-oil separator.Three grades of condensate coolers connect three fraction flow containers, connect water-and-oil separator at the bottom of the three fraction flow container jars, and tank deck connects deammoniation tower and extracting tower respectively.The upper oil phase of water-and-oil separator connects the light oil storage facility of back, the lower layer of water reflux pump that is connected, and reflux pump connects deammoniation tower and feed pipe respectively.
The utility model has the advantages that: 1, utilize the inventive method can remove sour gas and ammonia more up hill and dale, the residual quantity of sour gas can be reduced to below the 10mg/L, total ammonia content is reduced to below the 100mg/L, thereby avoided the resistancing action of ammonia to follow-up biochemical section, and can alleviate the fouling crystalline degree of inorganic salt on equipment, improve equipment operating efficiency; 2, can increase substantially the decreasing ratio of phenol or the process cost of minimizing extraction section; 3, can effectively volatile phenol be separated from ammoniacal liquor, the volatile phenol in the ammoniacal liquor, content of acid gas can be reduced to below the 10mg/L, alleviate follow-up ammonia purified energy consumption and purify load; 4, the concentration of ammoniacal liquor can be increased to more than 98%; 5, can remove the lower boiling oil pollutant effectively.
Description of drawings
Fig. 1 is a structural representation of the present utility model.
In the drawings, 1, extracting tower, 2 deammoniation towers, 3 one-level condensate coolers, 4 one-levels divide flow container, 5 B-grade condensation water coolers, 6 secondarys to divide flow container, 7 three grades of condensate coolers, 8 three fraction flow containers, 9 water-and-oil separators, 10 reflux pumps, 11 feed pipes, 12 pumps, 13, acid withdrawer
Embodiment
Embodiment 1:
(1) make and contain phenol, ammonia coal chemical industrial waste water and divide hot and cold two bursts of extracting tower top and middle and upper parts of extracting out from the band side line to enter in the tower, making tower top pressure is 0.2MPa (a), 40 ℃ of temperature, and tower bottom pressure is 0.255Mpa (a), 120 ℃ of temperature.Sour gas comes out from the cat head stripping, can enter according to the composition situation that sulfur recovery unit, torch burn or directly emptying, extraction still liquid at the bottom of the tower;
(2) waste water that removes sour gas enters in the deammoniation tower from the middle and upper part, and tower top pressure is 0.2～Mpa (a), 40 ℃ of temperature, and tower bottom pressure is 0.25Mpa (a), 120 ℃ of temperature.Ammonia-the water vapor that contains ammonia 5% comes out from the cat head stripping.Extraction still liquid at the bottom of the tower.Still liquid can enter the extracting and dephenolizing device or directly advances biochemical device and carry out subsequent disposal according to the composition situation;
(3) contain a large amount of volatile phenols and sour gas from ammonia-water vapor that deammoniation tower top stripping goes out, concentrate and make with extra care by three grades of fractional condensation devices that are made of interchanger and branch flow container, the temperature of one-level fractional condensation device is 110 ℃, and pressure is 0.4Mpa (a); The temperature of secondary fractional condensation device is 70 ℃, and pressure is 0.3Mpa (a); The temperature of three grades of fractional condensation devices is 30 ℃, and pressure is 0.1Mpa (a).The liquid phase of three grades of fractional condensation devices is divided into the profit two-phase after overcooling, oil phase is as the light oil products extraction; A water part is back to the deamination cat head, and another part is back to the feeding line of extracting tower.Through concentrating with purify after ammonia can sell or further be refined into liquefied ammonia after sell.
The product of the present invention's preparation is realized by this device:
This device comprises that extracting tower 1, deammoniation tower 2, one-level condensate cooler 3, one-level divide flow container 4, B-grade condensation water cooler 5, secondary to divide flow container 6, three grades of condensate coolers 7, three fraction flow containers 8, water-and-oil separator 9, reflux pump 10, feed pipe 11, pump 12, sour gas withdrawer 13, it is characterized in that feed pipe 11 connects extracting tower 1 by pump 12, extracting tower 1 cat head connects acid withdrawer 13, connects deammoniation tower 2 at the bottom of the tower.Deammoniation tower 2 cats head connect one-level condensate cooler 3, connect extraction plant or biochemical device at the bottom of the tower.One-level condensate cooler 3 connects one-level and divides flow container 4, and one-level divides flow container 4 tank decks to connect B-grade condensation water cooler 5, and jar end connects water-and-oil separator 9.B-grade condensation water cooler 5 connects secondary and divides flow container 6, and secondary divides flow container 6 tank decks to connect three grades of condensate coolers 7, and jar end connects water-and-oil separator 9.Three grades of condensate coolers 7 connect water-and-oil separator 9 at the bottom of connecting 8 jars of three fraction flow containers, 8, three fraction flow containers, and tank deck connects deammoniation tower 2 and extracting tower 1 respectively.The upper oil phase of water-and-oil separator 9 connects the light oil storage facility of back, the lower layer of water reflux pump 10 that is connected, and reflux pump 10 connects deammoniation tower 2 and feed pipe 11 respectively.Extracting tower 1 is that theoretical stage is 5～25 grades a stripping tower, and opening for feed is above to be dumped packing, and opening for feed is column plate or dumped packing with the lower section.Deammoniation tower 2 is that theoretical stage is 10～30 grades a stripping tower.
Embodiment 2:
(1) make and contain phenol, ammonia coal chemical industrial waste water and divide hot and cold two bursts of extracting tower top and middle and upper parts of extracting out from the band side line to enter in the tower, making tower top pressure is 0.7MPa (a), 80 ℃ of temperature, and tower bottom pressure is 0.75Mpa (a), 170 ℃ of temperature.Sour gas comes out from the cat head stripping, can enter sulfur recovery unit, torch burning or directly emptying according to the composition situation.Extraction still liquid at the bottom of the tower;
(2) waste water that removes sour gas enters in the deammoniation tower from the middle and upper part, and tower top pressure is 0.7Mpa (a), 80 ℃ of temperature, and tower bottom pressure is 0.75Mpa (a), 170 ℃ of temperature.Ammonia-the water vapor that contains ammonia 10% comes out from the cat head stripping.Extraction still liquid at the bottom of the tower.Still liquid can enter the extracting and dephenolizing device or directly advances biochemical device and carry out subsequent disposal according to the composition situation;
(3) contain a large amount of volatile phenols and sour gas from ammonia-water vapor that deammoniation tower top stripping goes out, concentrate and make with extra care by three grades of fractional condensation devices that are made of interchanger and branch flow container, the temperature of one-level fractional condensation device is 150 ℃, and pressure is 0.65Mpa (a); The temperature of secondary fractional condensation device is 90 ℃, and pressure is 0.5Mpa (a); The temperature of three grades of fractional condensation devices is 55 ℃, and pressure is 0.4Mpa (a).The liquid phase of three grades of fractional condensation devices is divided into the profit two-phase after overcooling, oil phase is as the light oil products extraction; A water part is back to the deamination cat head, and another part is back to the feeding line of extracting tower.Through concentrating with purify after ammonia can sell or further be refined into liquefied ammonia after sell.
Claims (2)
1, a kind of double tower stripping is handled the method that contains phenol, ammonia coal chemical industrial waste water, and its processing method step is:
(1) acid gas removal body: make to contain phenol, ammonia coal chemical industrial waste water and divide hot and cold two bursts of extracting tower top and middle and upper parts of extracting out to enter in the tower from the band side line, making tower top pressure is 0.2～0.7MPa, 40～80 ℃ of temperature, tower bottom pressure is 0.25～0.75Mpa, 120～170 ℃ of temperature, sour gas comes out from the cat head stripping, can enter according to the composition situation that sulfur recovery unit, torch burn or directly emptying, extraction still liquid at the bottom of the tower;
(2) deamination: the waste water that removes sour gas enters in the deammoniation tower from the middle and upper part, tower top pressure is 0.2～0.7Mpa, 40～80 ℃ of temperature, tower bottom pressure is 0.25～0.75Mpa, 120～170 ℃ of temperature, ammonia-the water vapor that contains ammonia 5-10% comes out from the cat head stripping, extraction still liquid at the bottom of the tower, and still liquid can enter the extracting and dephenolizing device or directly advances biochemical device and carry out subsequent disposal according to the composition situation;
(3) ammonia concentrates and purifies: contain a large amount of volatile phenols and sour gas from ammonia-water vapor that deammoniation tower top stripping goes out, concentrate and make with extra care by three grades of fractional condensation devices that constitute by interchanger and branch flow container, the temperature of one-level fractional condensation device is 110-150 ℃, pressure is 0.4-0.65Mpa, the temperature of secondary fractional condensation device is 70-90 ℃, pressure is 0.3-0.5Mpa, the temperature of three grades of fractional condensation devices is 30-55 ℃, pressure is 0.1-0.4Mpa, the liquid phase of three grades of fractional condensation devices is divided into the profit two-phase after overcooling, oil phase is as the light oil products extraction; A water part is back to the deamination cat head, and another part is back to the feeding line of extracting tower.Through concentrating with purify after ammonia can sell or further be refined into liquefied ammonia after sell.
2, the described double tower stripping of a kind of realization claim 1 is handled and is contained phenol, the device of the method for ammonia coal chemical industrial waste water, it comprises extracting tower, deammoniation tower, the one-level condensate cooler, one-level is divided flow container, the B-grade condensation water cooler, secondary divides flow container, three grades of condensate coolers, three fraction flow containers, water-and-oil separator, reflux pump, feed pipe, pump, acid withdrawer, it is characterized in that feed pipe connects extracting tower by pump, the extracting tower cat head connects acid withdrawer, connect deammoniation tower at the bottom of the tower, the deammoniation tower cat head connects the one-level condensate cooler, connect extraction plant or biochemical device at the bottom of the tower, the one-level condensate cooler connects one-level and divides flow container, one-level divides the flow container tank deck to connect the B-grade condensation water cooler, the jar end, connect water-and-oil separator, the B-grade condensation water cooler connects secondary and divides flow container, secondary divides the flow container tank deck to connect three grades of condensate coolers, the jar end, connect water-and-oil separator, three grades of condensate coolers connect three fraction flow containers, connect water-and-oil separator at the bottom of the three fraction flow container jars, tank deck connects deammoniation tower and extracting tower respectively, the upper oil phase of water-and-oil separator connects the light oil storage facility of back, the lower layer of water reflux pump that is connected, reflux pump connects deammoniation tower and feed pipe respectively.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA200810106916XA CN101289234A (en) | 2008-06-16 | 2008-06-16 | Process for treating industrial waste water containing hydroxybenzene and ammine by double-tower stripping |
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| CNA200810106916XA CN101289234A (en) | 2008-06-16 | 2008-06-16 | Process for treating industrial waste water containing hydroxybenzene and ammine by double-tower stripping |
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Cited By (22)
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| CN101857331A (en) * | 2010-06-10 | 2010-10-13 | 哈尔滨瑞格能源环境技术发展有限责任公司 | Coal chemical industry wastewater zero emission treatment method and system |
| CN101503267B (en) * | 2009-03-13 | 2010-12-01 | 哈尔滨工业大学 | Coal chemical industry wastewater treating method |
| CN101985414A (en) * | 2010-09-27 | 2011-03-16 | 高要市华新香料有限公司 | Production method for natural benzaldehyde |
| CN102259943A (en) * | 2011-07-21 | 2011-11-30 | 天津市昊永化工科技有限公司 | Energy-saving method for recycling wastewater containing phenol and ammonia |
| CN102320671A (en) * | 2011-06-17 | 2012-01-18 | 青岛科技大学 | Method for treating waste water containing acid and ammonia |
| CN102954669A (en) * | 2011-08-25 | 2013-03-06 | 中国石油化工股份有限公司 | Liquid ammonia production method |
| CN103073145A (en) * | 2013-02-01 | 2013-05-01 | 济钢集团有限公司 | System for recovering light oil from residual ammonia water |
| CN103449550A (en) * | 2013-09-19 | 2013-12-18 | 青岛科技大学 | Acid-containing ammonia-containing wastewater treatment method capable of saving high-temperature position steam |
| CN103496812A (en) * | 2013-09-29 | 2014-01-08 | 河南龙成煤高效技术应用有限公司 | Method for treating high-concentration phenol-ammonia wastewater |
| CN104003419A (en) * | 2014-06-16 | 2014-08-27 | 武汉钢铁(集团)公司 | Device and method for recycling waste ammonia gas in arsenic coking process |
| CN104030514A (en) * | 2014-06-30 | 2014-09-10 | 北京阳光欣禾科技有限公司 | Dual-effect and energy-saving waste water steam stripping deacidification and deamination technique method |
| CN104860465A (en) * | 2015-05-22 | 2015-08-26 | 江西明兴环境工程有限公司 | Double-tower catalysis thermal-coupling reflux deamination method and deamination device thereof |
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| CN105984886A (en) * | 2015-02-05 | 2016-10-05 | 薛斌 | Process for producing anhydrous ammonia by ammonia distillation and deacidification |
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| CN109111006A (en) * | 2018-09-21 | 2019-01-01 | 河南龙成煤高效技术应用有限公司 | A kind of method and equipment recycling ammonia from pyrolysis of coal waste water |
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| CN114455687A (en) * | 2022-03-17 | 2022-05-10 | 北京中科康仑环境科技研究院有限公司 | Method for recovering oil-free ammonia water from oil-containing ammonia-containing wastewater by deamination |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101503267B (en) * | 2009-03-13 | 2010-12-01 | 哈尔滨工业大学 | Coal chemical industry wastewater treating method |
| CN101857331B (en) * | 2010-06-10 | 2011-12-14 | 哈尔滨瑞格能源环境技术发展有限责任公司 | Coal chemical industry wastewater zero emission treatment method and system |
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| CN101985414B (en) * | 2010-09-27 | 2013-08-07 | 高要市华新香料有限公司 | Production method for natural benzaldehyde |
| CN101985414A (en) * | 2010-09-27 | 2011-03-16 | 高要市华新香料有限公司 | Production method for natural benzaldehyde |
| CN102320671A (en) * | 2011-06-17 | 2012-01-18 | 青岛科技大学 | Method for treating waste water containing acid and ammonia |
| CN102259943A (en) * | 2011-07-21 | 2011-11-30 | 天津市昊永化工科技有限公司 | Energy-saving method for recycling wastewater containing phenol and ammonia |
| CN102259943B (en) * | 2011-07-21 | 2012-08-22 | 天津市昊永化工科技有限公司 | Energy-saving method for recycling wastewater containing phenol and ammonia |
| CN102954669B (en) * | 2011-08-25 | 2014-11-19 | 中国石油化工股份有限公司 | Liquid ammonia production method |
| CN102954669A (en) * | 2011-08-25 | 2013-03-06 | 中国石油化工股份有限公司 | Liquid ammonia production method |
| CN103073145A (en) * | 2013-02-01 | 2013-05-01 | 济钢集团有限公司 | System for recovering light oil from residual ammonia water |
| CN103449550A (en) * | 2013-09-19 | 2013-12-18 | 青岛科技大学 | Acid-containing ammonia-containing wastewater treatment method capable of saving high-temperature position steam |
| CN103496812A (en) * | 2013-09-29 | 2014-01-08 | 河南龙成煤高效技术应用有限公司 | Method for treating high-concentration phenol-ammonia wastewater |
| CN104003419A (en) * | 2014-06-16 | 2014-08-27 | 武汉钢铁(集团)公司 | Device and method for recycling waste ammonia gas in arsenic coking process |
| CN104003419B (en) * | 2014-06-16 | 2016-08-24 | 武汉钢铁(集团)公司 | A kind of device and method reclaiming the ammonia that gives up in coking arsenic flow process |
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| CN105984886B (en) * | 2015-02-05 | 2018-09-11 | 薛斌 | A kind of technique of ammonia still process depickling production anhydrous ammonia |
| CN105984886A (en) * | 2015-02-05 | 2016-10-05 | 薛斌 | Process for producing anhydrous ammonia by ammonia distillation and deacidification |
| CN104860465A (en) * | 2015-05-22 | 2015-08-26 | 江西明兴环境工程有限公司 | Double-tower catalysis thermal-coupling reflux deamination method and deamination device thereof |
| CN105152437A (en) * | 2015-07-14 | 2015-12-16 | 王庆元 | Online extraction and dephenolization method of coal tar wastewater |
| CN107032555A (en) * | 2016-12-07 | 2017-08-11 | 赛鼎工程有限公司 | A kind of method for handling oil-containing coal gasification waste water |
| CN107827315A (en) * | 2017-10-27 | 2018-03-23 | 陕西煤业化工集团神木天元化工有限公司 | Semi-coke wastewater processing method |
| CN108840389A (en) * | 2018-07-25 | 2018-11-20 | 合肥中亚环保科技有限公司 | A kind of novel pre-extracted system |
| CN109111006A (en) * | 2018-09-21 | 2019-01-01 | 河南龙成煤高效技术应用有限公司 | A kind of method and equipment recycling ammonia from pyrolysis of coal waste water |
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| CN109399666A (en) * | 2018-12-14 | 2019-03-01 | 南京新世纪江南环保科技发展有限公司 | A kind of method and device recycling ammonia from acid water |
| CN109879342A (en) * | 2019-04-23 | 2019-06-14 | 宁波马克斯迈环保科技有限公司 | Soul water stripper distillate heat utilization device and method |
| CN109879342B (en) * | 2019-04-23 | 2024-04-26 | 宁波马克斯迈环保科技有限公司 | Sour water stripper distillate heat utilization device and method |
| CN112851048A (en) * | 2021-03-11 | 2021-05-28 | 陕西尚远水务有限公司 | Semi-coke wastewater treatment method |
| CN114455687A (en) * | 2022-03-17 | 2022-05-10 | 北京中科康仑环境科技研究院有限公司 | Method for recovering oil-free ammonia water from oil-containing ammonia-containing wastewater by deamination |
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