CN102863112A - Phenol and ammonia wastewater recycling treatment method by using single tower for performing de-acidification and de-amination simultaneously - Google Patents
Phenol and ammonia wastewater recycling treatment method by using single tower for performing de-acidification and de-amination simultaneously Download PDFInfo
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Abstract
The invention relates to a treatment method for wastewater containing phenol and dissoluble amine salts produced in chemical industry production, and particularly relates to a phenol and ammonia wastewater recycling treatment method by using a single tower for performing de-acidification and de-amination simultaneously. By means of an energy-saving technology which uses a single device for decomposing amine salts and achieving separation and purification, the device investment is reduced; and the energy recycling is achieved by using a differential pressure rectification technology, so that the energy consumption is reduced. Specifically, a de-acidification and de-amination coupling tower is used, and side withdrawing and differential pressure rectification technologies are utilized for achieving a simultaneous de-acidification and de-amination process and recycling ammonia and phenol in coal gasification wastewater, and accordingly, the method is energy saving and emission reducing, the technological process is simplified simultaneously, and the operation difficulty is reduced. According to the phenol and ammonia wastewater recycling treatment method by using the single tower for performing de-acidification and de-amination simultaneously, technical problems of large device investment and high energy consumption in phenol and ammonia wastewater recycling in a coal gasification process are solved, the technological process is simplified through the coupling of devices, and high economic and social values are provided.
Description
Technical field
But the present invention relates to contain in a kind of Coal Chemical Industry the method for wastewater treatment of phenol and cracked ammonium salt, a kind of by depickling denitrification coupling tower specifically, adopt side line extraction, differential pressure distillation technology, realize the process of simultaneously depickling of single tower deamination, ammonia in the gas recovery waste water and phenol, simplification of flowsheet in the time of energy-saving and emission-reduction reduces facility investment.
Background technology
The coal gasification technology is efficiently to utilize the effective ways of coal, is widely used in the industry such as coal preparing natural gas, synthetic ammonia, methyl alcohol and coal power generation.Can produce a large amount of waste water in gasification, the coking, wherein contain a large amount of suspended substances, tar, light oil, lipid acid, carbonic acid gas, hydrogen sulfide, ammonia, phenol etc., must could be recycled after treatment.
Processing the conventional process flow that contains phenol, ammonia waste water in the Coal Chemical Industry is the concentrated and purification-phenol extraction-solvent recuperation of depickling-deamination-ammonia.Depickling, deamination process are carried out separately in extracting tower, deammoniation tower respectively, not only flow process is complicated, use equipment is many, also more single tower is large in the simultaneously consumption of energy, it is not thorough that the defective meeting of depickling causes in the follow-up deamination process phenol ammonia to separate, phenol and content of acid gas are high in the ammonia, strengthened follow-up ammonia concentrated with scavenging process in load, the unstable of simultaneously tower operation also can have influence on follow-up normal running.
The patent No. is that the patent of invention " a kind of energy-conservation phenol ammonia waste water recovery and treatment method " of ZL201110204145.X discloses a kind of energy-conservation phenol ammonia waste water recovery processing technique.This patent of invention is mainly passed through the coupling of equipment between extracting tower, deammoniation tower and the water tower, be that the thick ammonia condenser while of deammoniation tower cat head is as the reboiler of extracting tower and water tower, utilize the differential pressure distillation technology, realize the ladder comprehensive utilization of thermal source, reduce the energy expenditure in the phenol ammonia waste water treating processes, greatly save the consumption of steam and recirculated water, in gas recovery waste water, reach energy-saving and cost-reducing purpose in ammonia and the phenol.This invention has solved the high technical barrier of phenol ammonia waste water recycling energy expenditure in traditional coal gasification course, realized the comprehensive utilization of energy, but do not reduce the investment of equipment, it is thorough not to save energy and reduce the cost, and also has the space of further simplification of flowsheet and operation easier.
Summary of the invention
The object of the invention is to further simplification of flowsheet, reduce facility investment, the also phenol ammonia waste water recovery and treatment method of simultaneously depickling deamination of a kind of single tower cracked ammonium salt is provided when reducing energy consumption, a kind of by depickling denitrification coupling tower specifically, adopt side line extraction, differential pressure distillation technology, realize the process of simultaneously depickling of single tower deamination, ammonia in the gas recovery waste water and phenol, simplification of flowsheet in the time of energy-saving and emission-reduction reduces facility investment, reduces operation easier.
The invention solves the technical barrier that facility investment is large, energy expenditure is high in the recycling of phenol ammonia waste water in the coal gasification course, invented a kind of brand-new single tower cracked ammonium salt and the phenol ammonia waste water New Process for Treatment of simultaneously depickling deamination.This technique adopts the method for side line extraction by depickling denitrification coupling tower, the ammonia in the high efficiente callback waste water and phenol, and simplification of flowsheet in the time of energy-saving and emission-reduction reduces facility investment, reduces operation easier.
The invention provides for achieving the above object following technical scheme:
The phenol ammonia waste water recovery and treatment method of simultaneously depickling of a kind of single tower deamination is characterized in that being undertaken by following step:
(1) waste water depickling deamination
Carry the phenol ammonia waste water of coming to enter oil removing pot from the gas liquor separator, the waste water that oil removing is pumped by raw water is divided into two strands and enters depickling denitrification coupling tower: directly enter depickling deammoniation tower cat head after the stock-traders' know-how water quench under the normal temperature condition; After the heat exchange of waste water preheater, enter in the tower from depickling deammoniation tower middle and upper part at the bottom of another stock-traders' know-how ammonia enriching section condenser, the depickling deammoniation tower, temperature is 80 ~ 150 ℃; Waste water carries out the stripping effect in the depickling deammoniation tower, the sour gas of generation is discharged from cat head, enters claus sulphur recovery units, torch burning or directly emptying; Waste water after processing through the depickling deamination is discharged at the bottom of tower, and temperature reaches 115 ~ 180 ℃, through give the raw water preheating for twice, once temperature is reduced to 20 ~ 50 ℃ after the cooling, enters the recovery of carrying out phenol in the extraction tower; The thick ammonia of tower middle part side line extraction enters the water tower reboiler as the thermal source of water tower reboiler, give its heat supply, take full advantage of on the one hand the heat of thick ammonia, reduce the energy consumption in the phenol ammonia recovering process, the water tower reboiler has been realized the coupling of equipment as the condenser of thick ammonia on the other hand, reduce heat-exchange equipment, simplification of flowsheet reduces investment, solves the technical barrier that the investment of phenol ammonia waste water recycling equipment is large in the coal gasification course, energy expenditure is high thereby reach.Ammonia level is 7 ~ 20% in the thick ammonia of side line extraction, can further carry out the preparation of the concentrated and ammoniacal liquor of ammonia, takes full advantage of resource.Wherein depickling deammoniation tower cat head working pressure is 200 ~ 1000kPa (g), and service temperature is 30 ~ 180 ℃.
Described depickling deammoniation tower refers to tray column, the mixed structure combination tower that composite board type tower or filler combine with tray column.
(2) phenol extraction and solvent recuperation
Contain a large amount of phenol mixtures through the waste water of discharging at the bottom of the tower after the effect of depickling deammoniation tower stripping, enter the extraction that extraction tower carries out phenol after the heat exchange and reclaim, extraction phase advances the phenol tower and carries out separating of phenol and solvent, obtains the crude phenols product; The extracting phase intake tower reclaims solvent, is purified water, thereby has realized the purifying treatment of phenol ammonia waste water.
(3) the concentrated and ammoniacal liquor preparation of ammonia
The thick ammonia of depickling deammoniation tower side line extraction contains a large amount of volatile phenols and sour gas, behind the thermal source as the water tower reboiler, enter minute phase system and carry out the preparation of the concentrated and ammoniacal liquor of ammonia, wherein the waste water after the phase-splitting is back to the recovery that oil removing pot is proceeded phenol ammonia.
The more detailed art treatment of the present invention is as follows:
(1) waste water depickling deamination
Carry the phenol ammonia waste water of coming to enter oil removing pot from the gas liquor separator, phenol ammonia waste water through behind oil removal, tar and the light oil pumps to be divided into two strands through raw water and enters depickling denitrification coupling tower: directly enters depickling deammoniation tower cat head after a stock-traders' know-how feed cooler is cooled to normal temperature; After another stock-traders' know-how ammonia enriching section after-condenser, preheater one, preheater two preheatings (waste water preheating at the bottom of the employing depickling deammoniation tower), temperature reaches 80 ~ 150 ℃, enters in the tower from depickling deammoniation tower middle and upper part; Waste water carries out the stripping effect in the depickling deammoniation tower, the sour gas of generation is discharged from cat head, goes claus sulphur recovery units, torch burning or directly emptying; Waste water after processing through the depickling deamination is discharged at the bottom of tower, and temperature reaches 115 ~ 180 ℃, and temperature is reduced to 20 ~ 50 ℃ after giving raw water preheating, primary water cooling twice, enters the recovery of carrying out phenol in the extraction tower; The thick ammonia of tower middle part side line extraction enters the water tower reboiler as the thermal source of water tower reboiler, give its heat supply, take full advantage of on the one hand the heat of thick ammonia, reduce the energy consumption in the phenol ammonia recovering process, the water tower reboiler has been realized the coupling of equipment as the condenser of thick ammonia on the other hand, reduce heat-exchange equipment, simplification of flowsheet reduces investment, solves the technical barrier that the investment of phenol ammonia waste water recycling equipment is large in the coal gasification course, energy expenditure is high thereby reach.Ammonia level is 7 ~ 20% in the thick ammonia of side line extraction, can further carry out the preparation of the concentrated and ammoniacal liquor of ammonia, takes full advantage of resource;
Depickling deammoniation tower cat head working pressure is 200 ~ 1000kPa (g), and service temperature is controlled at 30 ~ 180 ℃;
Depickling deamination tower bottom reboiler adopts saturation steam to heat;
The depickling deammoniation tower can adopt tray column, the mixed structure combination tower that composite board type tower or filler combine with tray column;
(2) phenol extraction and solvent recuperation
Contain a large amount of phenol mixtures through the waste water of discharging at the bottom of the tower after the effect of depickling deammoniation tower stripping, entering the extraction that extraction tower carries out phenol behind heat exchange to 20 ~ 50 ℃ reclaims, the extraction phase that produces after extraction enters the phenol tower and carries out separating of phenol and solvent, phenol column overhead overhead product advances solvent tank and reclaims solvent, obtains the crude phenols product at the bottom of the tower; The extracting phase intake tower reclaims solvent, and the water tower cat head distillates solvent, is purified water at the bottom of the tower, thereby the rough purification that has realized the phenol ammonia waste water is processed.
The service temperature of extraction process is 20 ~ 50 ℃, and extraction agent is ether solvent, such as isopropyl ether;
The working pressure of water tower is 0 ~ 50kPa (g), and service temperature is 60 ~ 120 ℃, and water tower tower bottom reboiler thermal source is the thick ammonia of depickling deammoniation tower side line extraction;
Phenol tower working pressure is 0 ~ 50kPa (g), and service temperature is 60 ~ 230 ℃;
(3) the concentrated and ammoniacal liquor preparation of ammonia
The thick ammonia of depickling deammoniation tower side line extraction contains a large amount of volatile phenols and sour gas, behind the thermal source as the water tower reboiler, enter a minute phase system, secondary phase-splitting tank deck is discharged the higher ammonia of concentration, enter ammonia upgrading tower bottom, after process water absorbs, be prepared into ammoniacal liquor, wherein one-level phase separation tank and the waste water of secondary phase separation tank after phase-splitting are back to the recovery that oil removing pot is proceeded phenol ammonia.
One-level phase separation tank temperature is 100 ~ 130 ℃, and secondary phase separation tank temperature is controlled to be 50 ~ 60 ℃;
The concentrated cat head working pressure of ammonia is 0 ~ 50kPa (g), and service temperature is 20 ~ 80 ℃.
Wherein said depickling denitrification coupling tower is: tray column, the mixed structure combination tower that composite board type tower or filler combine with tray column.
The present invention compares with existing treatment process, and the advantage that has is:
(1) overcomes the problem that power loss is large in the invention file 1 (ZL 201110204145.X), equipment integrationization is low, simplified technical process, reduced the investment of equipment, reduced operation easier in the time of energy-saving and emission-reduction.
(2) the present invention is coupled as one with extracting tower and deammoniation tower, adopt side line extraction, differential pressure distillation technology, realize the process of simultaneously depickling of single tower deamination, recovery and the recycling of energy have been realized, reduced by a tower, simplify technical process, reduced the energy expenditure of wastewater treatment, greatly saved the consumption of steam and recirculated water.Simultaneously can remove more up hill and dale sour gas and ammonia, 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 has avoided ammonia on the impact of phenol extraction process and the biochemical treatment of follow-up waste water.
Maximum characteristics of the present invention are: realized the coupling of extracting tower and deammoniation tower, utilized side line extraction, differential pressure distillation technology, optimized the comprehensive utilization of energy, further reach energy-saving and cost-reducing purpose, simplify technical process, reduced the investment of equipment, reduced operation easier.
Description of drawings
Fig. 1 is the phenol ammonia waste water recovery and treatment method process flow sheet of simultaneously depickling of a kind of single tower of the present invention deamination;
1-oil removing pot wherein, 2-raw material water pump, 3-feed cooler, 4-depickling deammoniation tower, 5-depickling deamination column bottoms pump, 6-preheater one, 7-preheater two, 8-water cooler one, 9-extraction tower, 10-extracts column bottoms pump, 11-preheater three, 12-water tower, 13-water column bottoms pump, 14-water cooler two, 15-water tower reboiler, 16-water tower top condenser, 17--phenol overhead condenser, 18-solvent tank, 19-solvent pump, 20-phenol tower, 21-phenol column bottoms pump, 22-one-level phase separation tank, 23-after-condenser, 24-secondary phase separation tank, 25-ammonia upgrading tower.
Embodiment
Below in conjunction with embodiment the present invention is described, the scheme of embodiment described here, do not limit the present invention, one of skill in the art can make improvements and change according to spirit of the present invention, described these improvement and variation all should be considered as within the scope of the invention, and scope of the present invention and essence are limited by claim.The used reagent of the present invention (such as isopropyl ether), industrial chemicals all have commercially available.The phenol ammonia waste water derives from the waste water that factory produces.
Embodiment 1
(1) after 120t/h waste water was come from the conveying of gas liquor separator, through oil removal, tar and light oil, temperature was 40 ℃, pressure 1.0 MPa.Concentration is phenol 7g/L, ammonia 9g/L, carbonic acid gas 3.8g/L, hydrogen sulfide 0.2g/L.
(2) contain the phenol ammonia waste water from what the gas liquor separator was come, be divided into two strands: one 35t/h enters cat head after feed cooler (3) is cooled to normal temperature; Another strand is heated to 95 ℃ by secondary complete condenser (23), preheater two (7), preheater one (6), enters depickling deammoniation tower (4) middle and upper part.
(3) the depickling deammoniation tower is tray column.Depickling deammoniation tower working pressure 500kPa (g) (gauge pressure), 85 ℃ of tower top temperatures, at the bottom of the tower 155 ℃, adopt reboiler to heat at the bottom of the tower, thermal source is saturation steam.Sour gas is discharged from cat head, and the still liquid that removes sour gas is discharged at the bottom of tower, and ammonia level is 10% in the thick ammonia of side line extraction, as the thermal source of water tower reboiler.
(4) waste water that removes sour gas is sent through depickling deamination column bottoms pump (5), temperature reaches 35 ℃ after preheater one (6), preheater two (7) and water cooler one (8) heat exchange cooling, enter extraction tower (9) top, the solvent (such as isopropyl ether) of sending here from solvent pump (19) enters from the bottom of extraction tower, the two carries out phenol counter-current extraction process in extraction tower, the solvent that is rich in phenol distillates from the extraction tower top, contain the waste water of solvent and micro-phenol at the bottom of the tower and after the solvent phase-splitting, at the bottom of tower, discharge.
(5) from the solvent that is rich in phenol that distillates of extraction cat head, enter the top of phenol tower (20).Phenol tower bottom reboiler employing 2.5Mpa(gauge pressure) saturation steam is as thermal source.Phenol tower working pressure is 10kPa (g) (gauge pressure), and tower top temperature is 70 ℃, is 205 ℃ at the bottom of the tower.The solvent gas that cat head distillates enters solvent tank (18) after phenol overhead condenser (17) condensation.Obtain the crude phenols product at the bottom of the tower, send through phenol column bottoms pump (21).
The waste water that contains solvent and micro-phenol of (6) discharging at the bottom of the extraction tower is sent into preheater three (11) through extraction column bottoms pump (10), and preheating temperature is 80 ℃ and enters water tower (12) top.Water tower is tray column, and tower bottom reboiler adopts the thick ammonia of depickling deammoniation tower side line extraction as heat source.The solvent gas that cat head is discharged enters solvent tank (18) after water tower top condenser (16) condensation.Be purified water at the bottom of the tower, send through water column bottoms pump (13), through going out device behind preheater three (11) and the water cooler of purifying waste water (14).
(7) the thick ammonia of depickling deammoniation tower side line extraction enters one-level phase separation tank (22) and carries out gas-liquid separation after standpipe reboiler (15) is as thermal source, one-level phase separation tank working pressure is 300kPa (g) (gauge pressure), 115 ℃ of service temperatures, the gas that the phase separation tank top is told goes after-condenser (23) to continue to condense to 80 ℃, enter secondary phase separation tank (24) and carry out gas-liquid separation, secondary phase separation tank working pressure is 100kPa (g) (gauge pressure), 60 ℃ of service temperatures.Liquid after one-level phase separation tank and the phase-splitting of secondary phase separation tank is back to the recovery that oil removing pot is proceeded phenol ammonia.
The ammonia of the higher concentration of (8) telling from secondary phase separation tank (24) top enters ammonia upgrading tower (25) bottom, and tower top adopts 40 ℃ of process waters to absorb, and obtains ammoniacal liquor at the bottom of the tower.Ammonia upgrading tower working pressure is 10kPa (g) (gauge pressure), and tower top temperature is 40 ℃, and column bottom temperature is 70 ℃.
Embodiment 2
The result's following (process sees example 1 for details) who detects:
(1) behind the depickling deamination in the waste water ammonia concentration be 95 the milli g/L.
(2) solvent-oil ratio is 1.25kg/t waste water.
(3) phenol content is 200 milli g/L in the processed waste water.
(4) mass concentration of crude phenols product is 99.4%.
(5) ammoniacal liquor quality concentration is 12% at the bottom of the ammonia upgrading tower, and ammonia concentration is 38 milligrams/cubic metre in the tail gas.
(6) steam consumption of device is 170kg steam/t waste water.
Embodiment 3
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, every foundation technical spirit of the present invention all still belongs in the scope of technical solution of the present invention any simple modification, equivalent variations and modification that above embodiment does.
Claims (2)
1. the phenol ammonia waste water recovery and treatment method of simultaneously depickling of a single tower deamination is characterized in that being undertaken by following step:
(1) waste water depickling deamination
Carry the phenol ammonia waste water of coming to enter oil removing pot from the gas liquor separator, the waste water that oil removing is pumped by raw water is divided into two strands and enters depickling denitrification coupling tower: directly enter depickling deammoniation tower cat head after the stock-traders' know-how water quench under the normal temperature condition; After the heat exchange of waste water preheater, enter in the tower from depickling deammoniation tower middle and upper part at the bottom of another stock-traders' know-how ammonia enriching section condenser, the depickling deammoniation tower, temperature is 80 ~ 150 ℃; Waste water carries out the stripping effect in the depickling deammoniation tower, the sour gas of generation is discharged from cat head, enters claus sulphur recovery units, torch burning or directly emptying; Waste water after processing through the depickling deamination is discharged at the bottom of tower, and temperature reaches 115 ~ 180 ℃, through give the raw water preheating for twice, once temperature is reduced to 20 ~ 50 ℃ after the cooling, enters the recovery of carrying out phenol in the extraction tower; The thick ammonia of tower middle part side line extraction enters the water tower reboiler as the thermal source of water tower reboiler, gives its heat supply; Wherein depickling deammoniation tower cat head working pressure is 200 ~ 1000kPa (g), and service temperature is 30 ~ 180 ℃; Described depickling deammoniation tower refers to tray column, the mixed structure combination tower that composite board type tower or filler combine with tray column;
(2) phenol extraction and solvent recuperation
Contain a large amount of phenol mixtures through the waste water of discharging at the bottom of the tower after the effect of depickling deammoniation tower stripping, entering the extraction that extraction tower carries out phenol behind heat exchange to 20 ~ 50 ℃ reclaims, the extraction phase that produces after extraction enters the phenol tower and carries out separating of phenol and solvent, phenol column overhead overhead product advances solvent tank and reclaims solvent, obtains the crude phenols product at the bottom of the tower; The extracting phase intake tower reclaims solvent, and the water tower cat head distillates solvent, is purified water at the bottom of the tower, thereby the rough purification that has realized the phenol ammonia waste water is processed;
The service temperature of extraction process is 20 ~ 50 ℃, and extraction agent is isopropyl ether; The working pressure of water tower is 0 ~ 50kPa (g), and service temperature is 60 ~ 120 ℃, and water tower tower bottom reboiler thermal source is the thick ammonia of depickling deammoniation tower side line extraction; Phenol tower working pressure is 0 ~ 50kPa (g), and service temperature is 60 ~ 230 ℃;
(3) the concentrated and ammoniacal liquor preparation of ammonia
The thick ammonia of depickling deammoniation tower side line extraction contains a large amount of volatile phenols and sour gas, behind the thermal source as the water tower reboiler, enter a minute phase system, secondary phase-splitting tank deck is discharged the higher ammonia of concentration, enter ammonia upgrading tower bottom, after process water absorbs, be prepared into ammoniacal liquor, wherein one-level phase separation tank and the waste water of secondary phase separation tank after phase-splitting are back to the recovery that oil removing pot is proceeded phenol ammonia;
One-level phase separation tank temperature is 100 ~ 130 ℃, and secondary phase separation tank temperature is controlled to be 50 ~ 60 ℃;
The concentrated cat head working pressure of ammonia is 0 ~ 50kPa (g), and service temperature is 20 ~ 80 ℃.
2. treatment process claimed in claim 1, wherein said depickling denitrification coupling tower is: tray column, the mixed structure combination tower that composite board type tower or filler combine with tray column.
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| CN103553165A (en) * | 2013-11-07 | 2014-02-05 | 东北大学 | Treatment method for high-salinity phenol-containing wastewater |
| CN103570172A (en) * | 2013-10-24 | 2014-02-12 | 天华化工机械及自动化研究设计院有限公司 | Phenol-ammonia coal gasification sewage treatment method |
| CN104058538A (en) * | 2014-06-30 | 2014-09-24 | 北京阳光欣禾科技有限公司 | Technology method for steam stripping deacidification and deamination of waste water |
| CN104787954A (en) * | 2015-04-08 | 2015-07-22 | 天津市创举科技有限公司 | Wastewater pretreatment technology |
| CN105000735A (en) * | 2015-07-03 | 2015-10-28 | 神木富油能源科技有限公司 | Pretreatment method of medium and low temperature coal pyrolysis wastewater and system thereof |
| CN105936562A (en) * | 2016-04-14 | 2016-09-14 | 天津大学 | Energy-saving method and device for treating coal chemical industry phenol ammonia wastewater by thermal coupling |
| CN105984886A (en) * | 2015-02-05 | 2016-10-05 | 薛斌 | Process for producing anhydrous ammonia by ammonia distillation and deacidification |
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| CN113185049A (en) * | 2021-06-07 | 2021-07-30 | 天津同创恒泰科技有限公司 | High-concentration phenol-ammonia wastewater double-tower energy-saving treatment system and method |
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| CN103570172A (en) * | 2013-10-24 | 2014-02-12 | 天华化工机械及自动化研究设计院有限公司 | Phenol-ammonia coal gasification sewage treatment method |
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| CN105000735A (en) * | 2015-07-03 | 2015-10-28 | 神木富油能源科技有限公司 | Pretreatment method of medium and low temperature coal pyrolysis wastewater and system thereof |
| CN105936562A (en) * | 2016-04-14 | 2016-09-14 | 天津大学 | Energy-saving method and device for treating coal chemical industry phenol ammonia wastewater by thermal coupling |
| CN107413194A (en) * | 2016-12-29 | 2017-12-01 | 天津市创举科技股份有限公司 | Preparation method and equipment of concentrated ammonia water for desulfurization and denitrification |
| CN108854165A (en) * | 2017-12-28 | 2018-11-23 | 郑州铂来化研科技有限公司 | Oily separation method in a kind of deammoniation tower ammonia lime set |
| CN108862432A (en) * | 2018-05-31 | 2018-11-23 | 上海化工研究院有限公司 | A kind of preprocess method of high concentrated organic wastewater |
| CN111592168A (en) * | 2020-06-30 | 2020-08-28 | 查都（上海）科技有限公司 | Phenol ammonia recovery unit of long period operation |
| CN113185049A (en) * | 2021-06-07 | 2021-07-30 | 天津同创恒泰科技有限公司 | High-concentration phenol-ammonia wastewater double-tower energy-saving treatment system and method |
| CN113213686A (en) * | 2021-06-07 | 2021-08-06 | 天津同创恒泰科技有限公司 | Single-tower treatment system and method for phenol ammonia sewage |
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