CN110950474A - Phenol-cyanogen wastewater resource zero-discharge method and process - Google Patents
Phenol-cyanogen wastewater resource zero-discharge method and process Download PDFInfo
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- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a phenol-cyanogen wastewater biochemical effluent recycling zero-emission method and a novel process technology, which comprises a four-section combined process of deep pretreatment, purification, membrane separation and concentration crystallization systems; wherein, the deep pretreatment removes impurities such as suspended matters, calcium, magnesium and the like, and reduces TOC and total hardness through a coagulating sedimentation/micro-nano advanced oxidation technology; the purification unit removes colloid, suspended matters, germs and the like through UF, and then removes impurities such as calcium, magnesium, aluminum, iron, fluoride ions and the like through resin exchange softening, fluoride removal and other technologies; the membrane separation technology adopts multi-stage NF to separate monovalent salt and multivalent salt, and then realizes the separation of brine through RO; the concentration unit is used for concentrating NF concentrated water and RO concentrated water respectively through ED; and (3) a crystallization process, namely freezing high-concentration sodium sulfate concentrated water by using a heat pump, separating and crystallizing to obtain sodium sulfate decahydrate, and crystallizing and separating to obtain high-purity sodium chloride by using an MVR evaporation technology. MVR adopts intermittent discharge of saturated impurity-containing high-concentration brine for resin regeneration.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a phenol-cyanogen wastewater resource zero-discharge method and a process.
Background
Phenol-cyanogen wastewater is high-concentration organic wastewater generated in the processes of coal coking, coal gas purification, chemical product recovery and chemical product refining, and substances which are difficult to biodegrade are remained in the wastewater after biochemical treatment, wherein the wastewater contains low-concentration toxic and harmful substances such as total cyanide, pyridine, benzo (a) pyrene, polycyclic aromatic hydrocarbon and the like. The traditional treatment technology mainly adopts a biological COD reduction, denitrification and coagulating sedimentation treatment integrated process, the treated water quality is difficult to reach the latest national emission standard or recycling requirement, and the treated water can be only discharged after dilution or used for coke quenching and slag flushing to transfer the pollution in the wastewater into atmospheric pollution.
With the national economic development and the environment of ensuring the environment to reach 'green water in Qingshan', pollution abatement is determined as a restrictive index in the national environmental protection planning. The pollution emission reduction and environmental protection are enhanced, and a greater effect is obtained.
The recycling treatment and zero discharge of the coking wastewater are difficult, and are always a worldwide problem, and the difficulty is that the quality of biochemical effluent of the coking wastewater is complex, the COD is high, and the biochemical effluent is mainly organic matters with polar groups, high in salt content, high in sulfate radical, high in calcium ion and high in fluorine ion. The recycling and zero discharge of the coking wastewater go through three technical stages: a reclaimed water recycling stage; a zero emission stage; and (5) a resource stage.
At present, because environmental protection problems face huge survival pressure, a plurality of coking enterprises are prepared to realize 'zero discharge' of phenol-cyanogen wastewater, and therefore, the treatment process which has better treatment effect, no generation of miscellaneous salt, stronger process stability and low operation cost is sought, and the aim of realizing the zero discharge of wastewater resource is fulfilled. Therefore, the technical personnel in the field provide a phenol-cyanogen wastewater resource zero-discharge method and a process.
Disclosure of Invention
The invention aims to provide a phenol-cyanogen wastewater resource zero-emission method and a process, which aim to solve the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme:
a phenol-cyanogen wastewater recycling zero-discharge method and a process thereof are disclosed, wherein the phenol-cyanogen wastewater biochemical effluent refers to coagulation precipitation effluent after biochemical treatment of phenol-cyanogen wastewater, the recycling zero-discharge method and the process refer to that water, sodium chloride and sodium sulfate in the wastewater are converted into three products after the phenol-cyanogen wastewater biochemical effluent is treated, the three products can be sold, and mixed salt or mixed salt is not generated (needing to be treated again), the process comprises a deep pretreatment unit, a purification unit, a membrane separation unit and a concentration crystallization system, and the process comprises the following steps:
(1) the method comprises the following steps of enabling phenol-cyanogen wastewater subjected to biochemical treatment to enter a deep pretreatment unit, removing partial impurities such as calcium, magnesium, carbonate, suspended matters and colloid in the water through coagulating sedimentation, filtering the precipitated water to remove colloid and fine particles which are difficult to precipitate, wherein the filtering precision is 10-50 mu m;
(2) carrying out micro-nano advanced oxidation reaction on the effluent obtained in the step (1), oxidizing and degrading TOC in the wastewater by using a salt-free oxidant, wherein the TOC is less than 5mg/L, salt is not added, and the residual oxidant is digested by a digester to reduce the oxidation-reduction potential;
(3) enabling the effluent obtained from the deep pretreatment in the step (2) to enter a purification unit, firstly removing substances such as colloids, suspended matters, germs and the like through UF, and independently collecting concentrated water, backwashing water and chemical cleaning water and refluxing to an effluent coagulation reaction tank of a biochemical secondary sedimentation tank;
(4) performing resin cation exchange on UF effluent to remove metal ions such as calcium, magnesium, aluminum, iron and the like; removing fluorine ions through basic resin ion exchange, and purifying the salt of the effluent;
(5) the effluent of the purification unit enters a multistage NF membrane device in a membrane separation unit to separate monovalent salt and multivalent salt, and the produced water contains sodium chloride and trace sodium sulfate and sodium nitrate; the concentrated water contains high-concentration sodium sulfate and a small amount of sodium chloride, and the concentration of the sodium sulfate is 30-50 g/L;
(6) step (5), degrading TOC by catalytic oxidation of secondary NF concentrated water, filtering by ultrafiltration, separating concentrated colloidal substances in the concentrated water, and performing coagulation reaction and retreatment on the ultrafiltration concentrated water;
(7) concentrating the secondary NF concentrated water in the step (6) to 140-150 g/L by ED;
(8) step (7), freezing the high-concentration sodium sulfate by a heat pump, and carrying out crystallization separation to obtain high-purity sodium sulfate decahydrate, wherein a cold source is adopted for 5 ℃;
(9) carrying out salt water separation on the NF produced water in the step (5) through RO, wherein the reverse osmosis concentrated water is 30-50 g/L of sodium chloride; collecting and recycling RO produced water through a pure water tank;
(10) concentrating the RO concentrated water in the step (9) to 120-150 g/L by ED, and concentrating sodium chloride;
(11) evaporating and concentrating the sodium chloride concentrated solution obtained in the step (10) through MVR, crystallizing and separating to obtain high-purity sodium chloride, wherein MVR blowdown salt is used for resin regeneration; MVR evaporation condensate water is collected through the pure water box.
As a further scheme of the invention: the deep pretreatment adopts coagulation/microfiltration, the coagulant includes but is not limited to ferrous sulfate, ferric sulfate, polymeric ferric sulfate, polyaluminium chloride, calcium hydroxide, anion PAM and the like, and the filtration precision of the microfiltration machine is 10-50 um.
As a still further scheme of the invention: the salt-free oxidant includes but is not limited to oxidant such as ozone and hydrogen peroxide, and the catalyst in oxidation reduction includes but is not limited to active carbon and other catalysts.
As a still further scheme of the invention: the purification unit comprises but is not limited to processes and equipment for removing colloids, suspended matters by UF, removing calcium, magnesium, iron and aluminum by cationic resin and removing fluoride ions by alkaline resin.
As a still further scheme of the invention: the membrane separation unit comprises but is not limited to one-stage or multi-stage NF separation and concentration of monovalent salt and multivalent salt, and one-stage or multi-stage RO is adopted to realize the separation of water salt and water produced by NF and the concentration of salt.
As a still further scheme of the invention: and an ED device is adopted for concentration in the concentration and crystallization system.
As a still further scheme of the invention: the evaporative crystallization in the concentration crystallization system is characterized in that sodium chloride concentrated water adopts evaporative crystallization processes including but not limited to MVR, ME and the like, high-concentration sodium sulfate concentrated water adopts a heat pump to provide a cold source for normal-temperature 5-degree freezing crystallization, the purity of produced salt is guaranteed, and impurity-containing concentrated brine is discharged at regular time to be used as resin softened brine.
As a still further scheme of the invention: the sodium sulfate decahydrate in the step (8) and the sodium chloride product in the step (10) meet the requirements of national standard industrial sodium chloride (GB/T5462-.
As a still further scheme of the invention: and (4) collecting the RO produced water in the step (5) and the MVR condensed water in the step (11) by the pure water tank, and reusing the RO produced water and the MVR condensed water in the step (11) for producing circulating cooling water.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, TOC is degraded through micro-nano advanced oxidation reaction and is degraded to below 5 mg/L; impurities such as calcium, magnesium, iron, aluminum, fluorine, colloid, germs, suspended matters and the like are removed through a purification unit; monovalent salt and divalent salt are realized through multi-stage nanofiltration, nanofiltration water is sodium chloride, and concentrated water is sodium sulfate mainly; concentrating and nanofiltration water production through reverse osmosis and ED technologies, and concentrating and nanofiltration concentrated water through multi-stage nanofiltration and ED technologies; obtaining high-purity divalent salt sodium sulfate by freezing and crystallizing sodium filtrate; obtaining high-purity sodium chloride through MVR; reverse osmosis water production and evaporation condensate water can be recycled and produced; the heat pump refrigeration and MVR technology is adopted, the cold end of the heat pump is used for providing a cold source for refrigeration crystallization, and the hot end of the heat pump provides a heat source for the MVR, so that the energy consumption is saved; only a small amount of coagulating sedimentation sludge is generated, so that the generation of miscellaneous salt (hazardous waste) is eliminated, finally, the evaporated crystal salt is sodium sulfate decahydrate and sodium chloride products, and the quality reaches the national standard industrial sodium chloride and sodium sulfate; the method integrates various core technologies, solves the problems of recycling and zero emission of phenol-cyanogen wastewater salt and water, realizes energy conservation, high efficiency, high recycling and zero emission tendency, can reduce the environmental protection pressure of enterprises, can reduce the use of industrial new water, and brings good social and environmental benefits.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, in the embodiment of the present invention, after phenol-cyanogen wastewater after biochemical treatment is precipitated in a secondary sedimentation tank, supernatant enters a process system of the present invention, and first enters a coagulation reaction tank (i) to be fully mixed with an added coagulant, and then enters a reaction tank (ii), the coagulant includes but is not limited to ferrous sulfate, ferric sulfate, polyferric sulfate, polyaluminium chloride, calcium hydroxide, anion PAM, etc., after coagulation reaction for 15min to 30min, the supernatant enters a clear water tank (i), sludge enters a concentration tank, and is dehydrated by pressure filtration, mud cakes are transported to outside, and filtrate flows back to the reaction tank (i);
clear water in a clear water tank (I) is filtered by a filter (I) to remove fine particles, then enters a catalytic oxidation device (I), TOC is efficiently degraded through micro-nano high-grade oxygen, residual oxidants are broken by a digester and then enter the clear water tank (II) after being filtered by the filter (II), salt-free oxidants in the catalytic oxidation device include but are not limited to oxidants such as ozone and hydrogen peroxide, and catalysts in oxidation reduction include but are not limited to active carbon and other catalysts;
and (3) further removing turbidity from clean water in the clean water tank (II) through a UF system, enabling UF concentrated water and backwash water to flow back to the reaction tank (I), removing impurities such as calcium, magnesium, aluminum, iron and the like from UF produced water through a softening device, removing fluorine through a fluorine removal device, and then enabling the UF produced water to enter the UF produced water tank. The softening device and the defluorination device are regenerated by high-salt water discharged by MVR, regenerated concentrated solution is treated by a three-header tank, sludge is dehydrated, and supernatant liquid flows back to the reaction tank (I);
UF product water passes through two stages of NF, NF concentrated water is collected through a concentrated salt water tank (I), the concentrated water enters an ED device (I) for concentration after TOC is degraded through a catalytic oxidation device (II), fresh water flows back to the NF concentrated salt water tank, the concentrated water is cooled to below 5 ℃ through a freezing heat exchanger to form sodium sulfate decahydrate crystals, high-purity sodium sulfate decahydrate crystals are obtained through separation, and low-temperature saturated sulfuric acid solution flows back to a concentrated salt water buffer tank.
NF produced water is collected through a NF produced water pool, and is concentrated through an ED device after being collected through a concentrated salt water pool (II) by two-stage RO, and fresh water of the ED device (II) flows back to the first-stage RO concentrated water pool and enters into the second-stage RO; the concentrated water of the ED device (II) is collected by the high-salt water tank (I), is evaporated and crystallized by the MVR device, and high-purity sodium chloride is obtained after crystallization and separation, and saturated sodium chloride solution enters the high-salt water tank (II). RO produced water and MVR condensed water are collected by a pure water tank and reused in the production process.
Case (2): biochemical treatment effluent 80 m for treating phenol-cyanogen wastewater3/h，CODcr 120 mg/L~150 mg/L，Ca2+60~100 mg/L，Mg2+2~10 mg/L，Fe2+/Fe3+2~8 mg/L，Al3+0.05~0.5 mg/L、F-60~80 mg/L、SO4 2-1500~2000 mg/L、Cl-1000~1500 mg/L、Na+1500~2000 mg/L。
After deep pretreatment such as coagulating sedimentation, filtering, micro-nano catalytic oxidation, digestion and filtering, collecting produced water by using a clean water tank, reducing CODcr to 40-50 mg/L, and achieving the in-line emission standard of pollutants for coking chemical industry (GB 16171-2012).
After deep pretreatment, the turbidity is less than 1 NTU through UF filtration, calcium, magnesium, aluminum, iron and the like are removed through a calcium-magnesium softening device, a fluorine removing device is adopted, the residual hardness is less than 0.05 mmol/L, the residual fluorine ion concentration is less than 2 mg/L, and UF produced water is collected through a production box.
UF produced water passes through two stages of NF, NF concentrated water is collected through a concentrated salt water tank, the concentration of sodium sulfate of nanofiltration concentrated water reaches 30-50 g/L, the concentrated water enters an ED salt concentration device after TOC degradation and ultrafiltration through a catalytic reactor, the outlet water temperature is 35 ℃, fresh water flows back to a first-stage NF concentrated water tank, the TDS of concentrated liquid of the ED device reaches 180 g/L, the sodium sulfate reaches 150g/L, the outlet water temperature after freezing crystallization is 10 ℃, the saturated sodium sulfate is 91 g/L, sodium sulfate crystals are separated, salt generated by separation is sodium sulfate decahydrate, the purity is more than 98%, and 483 kg/h. And refluxing the saturated sulfuric acid solution to an ED concentrated water device for concentration.
And collecting the NF produced water through an NF produced water pool, and passing through two stages of RO, wherein the concentration of sodium chloride in the second stage RO concentrated water reaches 30-50 g/L. The concentrated solution is collected by a strong brine pond and then concentrated by an ED device, and fresh water of the ED device flows back to a first-stage RO concentrated water pond and enters a second-stage RO; the concentrated water of the ED device is 120-150 g/L of sodium chloride, and is collected by a high-salt water tank, and the high-purity sodium chloride is obtained after evaporation, crystallization and separation by an MVR device at 200 kg/h. The saturated sodium chloride solution enters a high-salt water tank. RO produces water, MVR comdenstion water and totals 79 m3And h, collecting the water through a pure water tank, and recycling the water for replenishing the circulating cooling water without generating concentrated water.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. A phenol-cyanogen wastewater recycling zero-discharge method and a process thereof are disclosed, wherein the phenol-cyanogen wastewater biochemical effluent refers to coagulation precipitation effluent after biochemical treatment of phenol-cyanogen wastewater, and the recycling zero-discharge method and the process refer to the conversion of water, sodium chloride and sodium sulfate in the wastewater into three products which can be sold without producing mixed salt or miscellaneous salt (needing to be treated again) after the phenol-cyanogen wastewater biochemical effluent is treated, and the process is characterized by comprising a deep pretreatment unit, a purification unit, a membrane separation unit and a concentration crystallization system, and comprises the following steps:
(1) the method comprises the following steps of enabling phenol-cyanogen wastewater biochemical treatment effluent to enter a deep pretreatment unit, removing partial calcium, magnesium, carbonate, suspended matters and colloidal impurities in the water through coagulating sedimentation, filtering the sedimentation effluent to remove colloid and fine particles which are difficult to precipitate, wherein the filtering precision is 10-50 mu m;
(2) carrying out micro-nano advanced oxidation reaction on the filtered effluent in the step (1), oxidizing and degrading TOC in the wastewater by using a salt-free oxidant, wherein the TOC is less than 5mg/L, salt is not added, and the residual oxidant is digested by a digester to reduce the oxidation-reduction potential;
(3) enabling the effluent obtained from the deep pretreatment in the step (2) to enter a purification unit, firstly removing colloids, suspended matters and germs through UF, and independently collecting concentrated water, backwashing water and chemical cleaning water and refluxing to an effluent coagulation reaction tank of a biochemical secondary sedimentation tank;
(4) performing resin cation exchange on UF effluent to remove metal ions; removing fluorine ions through basic resin ion exchange, and purifying the salt of the effluent;
(5) the effluent of the purification unit enters a multistage NF membrane device in a membrane separation unit to separate monovalent salt and multivalent salt, and the produced water contains sodium chloride and trace sodium sulfate and sodium nitrate;
(6) step (5), degrading TOC by catalytic oxidation of secondary NF concentrated water, filtering by ultrafiltration, separating concentrated colloidal substances in the concentrated water, and performing coagulation reaction and retreatment on the ultrafiltration concentrated water;
(7) concentrating the secondary NF concentrated water in the step (6) to 140-150 g/L by ED;
(8) step (7), freezing the high-concentration sodium sulfate by a heat pump, and carrying out crystallization separation to obtain high-purity sodium sulfate decahydrate, wherein a cold source is adopted for 5 ℃;
(9) carrying out salt water separation on the NF produced water in the step (5) through RO, wherein the reverse osmosis concentrated water is 30-50 g/L of sodium chloride; collecting and recycling RO produced water through a pure water tank;
(10) concentrating the RO concentrated water in the step (9) to 120-150 g/L by ED, and concentrating sodium chloride;
(11) evaporating and concentrating the sodium chloride concentrated solution obtained in the step (10) through MVR, crystallizing and separating to obtain high-purity sodium chloride, wherein MVR blowdown salt is used for resin regeneration; MVR evaporation condensate water is collected through the pure water box.
2. The method and process for realizing zero emission of phenol-cyanogen wastewater resource as claimed in claim 1, wherein the deep pretreatment adopts coagulation/microfiltration, the coagulant includes but is not limited to ferrous sulfate, ferric sulfate, polymeric aluminum chloride, calcium hydroxide and anionic PAM, and the precision filter has a filtration precision of 10-50 um.
3. The method and process for realizing zero emission of phenol-cyanogen wastewater resources as claimed in claim 1, wherein the salt-free oxidant includes but is not limited to ozone and hydrogen peroxide, and the catalyst in oxidation-reduction includes but is not limited to activated carbon.
4. The method and process of claim 1, wherein the purification unit includes but is not limited to UF colloid removal, suspension removal, ca, mg, fe, al removal with cationic resin, and fluoride ion removal with basic resin.
5. The method and process of claim 1, wherein the membrane separation unit includes, but is not limited to, one or more stages of NF separation and concentration of monovalent salt and multivalent salt, and one or more stages of RO are used to realize the separation of salt and water from NF production water and the concentration of salt.
6. The method and process for realizing zero emission of phenol-cyanogen wastewater resources as claimed in claim 1, wherein an ED device is adopted for concentration in the concentration crystallization system.
7. The resource zero-emission method and process of phenol-cyanogen wastewater as claimed in claim 1, wherein the crystallization unit in the concentration crystallization system is a heat pump for providing a cold source for high-concentration sodium sulfate concentrated water to perform normal-temperature 8 ° freezing crystallization.
8. The method and process for realizing zero emission of phenol-cyanogen wastewater resources as claimed in claim 1, wherein the evaporative crystallization unit in the concentration crystallization system is a sodium chloride concentrated water evaporative crystallization process including but not limited to MVR and ME.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112047362A (en) * | 2020-08-28 | 2020-12-08 | 河南倍杰特环保技术有限公司 | Multistage purification equipment and process for high-salt-content wastewater |
| CN112159005A (en) * | 2020-09-28 | 2021-01-01 | 深圳市华加日西林实业有限公司 | Treatment process and treatment system for aluminum processing anode waste liquid |
| CN112390446A (en) * | 2020-11-03 | 2021-02-23 | 宝武水务科技有限公司 | Zero-discharge treatment method for coking wastewater |
| CN112811442A (en) * | 2020-12-21 | 2021-05-18 | 肥城胜利盐业有限公司 | Process and system for refining salt by using high-salinity wastewater |
| CN113860546A (en) * | 2021-09-28 | 2021-12-31 | 四川思达能环保科技有限公司 | Treatment system and treatment method for wastewater generated in production of anhydrous iron phosphate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014089796A1 (en) * | 2012-12-13 | 2014-06-19 | General Electric Company | Method for treating high concentration wastewater such as ro brine |
| CN105502782A (en) * | 2015-12-07 | 2016-04-20 | 湖南湘牛环保实业有限公司 | Technology for recovering water resources and salt from coking wastewater in coal chemical industry |
| CN109607923A (en) * | 2019-01-07 | 2019-04-12 | 揭阳市德克蒸发器有限公司 | A kind of heat pump low temperature divides the wastewater treatment equipment of salt |
-
2019
- 2019-05-22 CN CN201910427438.0A patent/CN110950474A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014089796A1 (en) * | 2012-12-13 | 2014-06-19 | General Electric Company | Method for treating high concentration wastewater such as ro brine |
| CN105502782A (en) * | 2015-12-07 | 2016-04-20 | 湖南湘牛环保实业有限公司 | Technology for recovering water resources and salt from coking wastewater in coal chemical industry |
| CN109607923A (en) * | 2019-01-07 | 2019-04-12 | 揭阳市德克蒸发器有限公司 | A kind of heat pump low temperature divides the wastewater treatment equipment of salt |
Non-Patent Citations (2)
| Title |
|---|
| 汪家权等: "《生态强省 美好安徽》", 31 July 2013 * |
| 王翠萍: "《煤焦化产品回收与加工》", 30 April 2014 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112047362A (en) * | 2020-08-28 | 2020-12-08 | 河南倍杰特环保技术有限公司 | Multistage purification equipment and process for high-salt-content wastewater |
| CN112047362B (en) * | 2020-08-28 | 2023-08-08 | 河南倍杰特环保技术有限公司 | Multistage purification equipment and process for high-salt-content wastewater |
| CN112159005A (en) * | 2020-09-28 | 2021-01-01 | 深圳市华加日西林实业有限公司 | Treatment process and treatment system for aluminum processing anode waste liquid |
| CN112390446A (en) * | 2020-11-03 | 2021-02-23 | 宝武水务科技有限公司 | Zero-discharge treatment method for coking wastewater |
| CN112811442A (en) * | 2020-12-21 | 2021-05-18 | 肥城胜利盐业有限公司 | Process and system for refining salt by using high-salinity wastewater |
| CN113860546A (en) * | 2021-09-28 | 2021-12-31 | 四川思达能环保科技有限公司 | Treatment system and treatment method for wastewater generated in production of anhydrous iron phosphate |
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