CN110040886A - A kind of utilization method of sodium sulfate wastewater - Google Patents
A kind of utilization method of sodium sulfate wastewater Download PDFInfo
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- CN110040886A CN110040886A CN201910384940.8A CN201910384940A CN110040886A CN 110040886 A CN110040886 A CN 110040886A CN 201910384940 A CN201910384940 A CN 201910384940A CN 110040886 A CN110040886 A CN 110040886A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/20—Total organic carbon [TOC]
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a kind of utilization methods of sodium sulfate wastewater, calcium chloride is added into sodium sulfate wastewater, however sodium chloride crude brine is obtained by filtration in reaction solution, with the substances such as TOC and ammonia nitrogen in electrocatalytic oxidation method removal crude brine, calcium ion in salt water is removed with sodium carbonate with after sodium hydroxide adjusting PH to 11~12 again, salt water after deliming is acidified with hydrochloric acid adjusts PH to 4~6, resulting salt water is finally entered to the sulfate and sodium chloride in nanofiltration membrane separation device separation salt water, obtain the sodium chloride brine of low sodium sulphate and the aqueous solution rich in sodium sulphate, water distribution of the sodium chloride brine of low sodium sulphate as sodium chloride electrolysis salt water, sodium chloride electrolysis raw material is used as after conventional method refines, aqueous solution rich in sulfate radical, which is back in sodium sulfate wastewater, to be recycled.The invention can efficiently use sodium sulfate wastewater and calcium chloride wastewater, realize the recycling of sodium sulphate.
Description
Technical field
The present invention relates to chemical wastewater treatment and reutilization technology fields, specifically provide a kind of utilization of sodium sulfate wastewater
Method.
Background technique
The waste water of sulfur acid sodium is one of most common high-salt wastewater in industrial wastewater, normally due to its salt content is high, it is difficult
Thoroughly to be handled by wastewater treatment methods such as biochemical degradations.If being directly discharged to nature ring without purified treatment
In border, the salinity that will lead to water body and soil is increased, and is destroyed soil texture, is led to soil hardening, be unfavorable for the growth of animals and plants,
It pollutes the environment.
The common methods of processing sodium sulfate wastewater are to recycle wherein sodium sulphate using multiple-effect evaporation crystallization processes.But multiple-effect is steamed
Hair crystallization investment and operating cost are high, though using mechanical steam recompression evaporator (MVR), investment and operating cost still compared with
Height, simultaneously because sodium sulphate price is low, the sodium sulphate recycled is many times mixed salt, can only without suitable application market
As dangerous waste processing, processing cost is high.Also some other method is recycled to sodium sulfate wastewater.
Publication No. CN106803588 A discloses a kind of method that sodium sulfate wastewater prepares ferrous sulfate sodium.This method
It is that suitable ferrous sulfate by adjusting the concentration of waste sulfate sodium solution, is added using the metabisulfite solution discarded in industry
Afterwards, the precursor that ferrous sulfate sodium can be obtained for a period of time and after evaporating water is stirred in certain temperature.Precursor exists
Sodium-ion battery positive material ferrous sulfate sodium can be obtained in sintering under certain sintering temperature.Publication number CN103880209 B
It provides a kind of sodium sulfate wastewater and prepares sodium-zinc-phosphate method.This method are as follows: chemical precipitation agent is added into sodium sulfate wastewater, so
Reaction solution is filtered afterwards, obtains sulfate precipitation and sodium dihydrogen phosphate；Zinc-containing substance is added to sodium dihydrogen phosphate
In, reaction 2~for 24 hours, then reaction solution is filtered, obtains sodium-zinc-phosphate sediment.Sodium-zinc-phosphate can be used as a kind of novel big
Pore catalyst.The product added value with higher that above two method obtains, but its market demand is small, can not answer on a large scale
With the sodium sulfate wastewater that not can solve big yield handles problem.
Publication number CN102241448 B discloses a kind of method of sodium sulfate wastewater comprehensive utilization, is exchanged using cation
Film electrolytic sulfite, electrolysis generate sulfuric acid and sodium hydroxide.The following steps are included: step 1: using organic or inorganic flocculant
The substances such as the middle suspended matter of waste water, pigment are pre-processed, so that water quality is reached electrolysis and requires；Step 2: it sets in a cell
Enter cationic membrane, electrolytic cell is isolated into several independent tank houses；Step 3: into anode chamber after merging purification, processing
Sodium sulfate wastewater；Tap water or the tap water containing electrolyte are added in cathode chamber, to increase the electric conductivity of electrolyte；Or
The sodium sulfate wastewater after dilution is directly added in the cathodic compartment；Step 4: it opens power supply and is electrolysed, hydroxide is made in cathode chamber
The sulfuric acid solution containing part of sulfuric acid sodium is made in sodium solution, anode chamber.The sodium hydroxide and sulfuric acid concentration that this method obtains are low, need
Concentration, which reaches, just to be met market demands, especially dilute sulfuric acid after higher concentration concentrate is needed just to have market application value to the concentrated sulfuric acid,
Equipment material requires high in concentration process, and energy consumption is high, thus recycles at high cost.
Sodium chloride is the primary raw material of chlorine industry, and dosage is big, meets what electrolysis required if converting sodium sulfate wastewater to
Sodium chloride brine can effectively solve sodium sulfate wastewater processing problem.
Summary of the invention
The present invention provides a kind of method of sodium sulfate wastewater sodium chloride brine, this method is low with processing cost, saves
Can be environmentally friendly the advantages that, obtained product market dosage is big, solves the deficiency of background technique.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme:
A kind of utilization method of sodium sulfate wastewater, it is characterised in that the following steps are included:
(1) calcium chloride is added into sodium sulfate wastewater, is stirred to react after 30-300min and sodium chloride is obtained by filtration in reaction solution
Crude brine；
(2) TOC and ammonia nitrogen substance in crude brine are removed with electrocatalytic oxidation method, then adjusts PH to 10 with sodium hydroxide
Calcium ion in salt water is removed with sodium carbonate after~12, the salt water after deliming is acidified with hydrochloric acid and adjusts PH to 4~6；
(3) above-mentioned resulting salt water is entered into sulfate and sodium chloride in nanofiltration membrane separation device separation salt water, obtained
The sodium chloride brine of low sodium sulphate and aqueous solution rich in sodium sulphate, wherein the sodium chloride brine of low sodium sulphate is as sodium chloride electricity
The water distribution of salt water is solved, and is used as sodium chloride electrolysis raw material after conventional method refines, the aqueous solution rich in sulfate radical is back to sulphur
It is recycled in sour sodium waste water.
The reaction that step (1) is related to are as follows: Na2SO4+CaCl2=CaSO4↓+2NaCl
The reaction realizes that sodium sulfate wastewater is converted into sodium chloride brine, but since calcium sulfate is microsolubility substance, electrolytic salt
Calcium content is required in water high, it is necessary to it removes, sulfate radical content is of less demanding, but can recycle and accumulate in system, thus
It should separate；There are the organic matter and ammonia nitrogen substance of certain content in waste water simultaneously, electrolytic brine also answers such material requirement height
Reach brine quality requirement after removal, wherein TOC is less than 10mg/L, ammonia nitrogen is less than 1mg/L.
Calcium chloride used in step 1 can be calcium chloride wastewater, as epoxychloropropane production in generate calcium chloride wastewater, with stone
Ash is calcium chloride wastewater in the VDC production of raw material, can reduce processing cost.
Subsequent removal of impurities process separates sulfate using chemical method deliming, nano filtering process.It compares, impurity contains when chemical method cleans
Amount is more sensitive on removal of impurities cost influence, therefore to reduce subsequent chemistry method deliming cost, this method step 1 calcium chloride additional amount is
Its 0.8-1 times with sodium sulphate reactive chemistry stoichiometric number is advisable, and to reduce the content of calcium, reduces subsequent sodium carbonate additional amount.
Electrocatalytic oxidation is a kind of wastewater processing technology that cost is relatively low, applicability is good, and can remove in waste water simultaneously has
Machine object and ammonia nitrogen, for this method step 2 using TOC and ammonia nitrogen in electrocatalytic oxidation removal sodium chloride crude brine, TOC removal rate is reachable
60-90%, ammonia nitrogen can be down to and be not detected.
Sodium carbonate can effectively remove calcium ion in salt water, and deliming effect is more preferable under alkaline condition, be imitated according to same ion
It should suitably help after excess and further decrease calcium ion content, therefore sodium carbonate additional amount is itself and calcium in this method step (2)
1.05-1.2 times of ionic reaction stoichiometric number, the salt water calcium content after can making decalcification are down to 10mg/L or less.
Sulfate radical can be removed with barium chloride, but higher cost, improper to high concentration sulfate separation, and nanofiltration UF membrane
Method can preferably realize the separation of monovalent ion and divalent and the above ion, at low cost, therefore this method is made using nano filtering process
The divalent salts such as sodium chloride and sulfate separate in crude brine, sulfuric acid salt rejection rate up to 95%, sodium chloride essentially by.This method
It is acidified with hydrochloric acid into the salt water before nanofiltration, to prevent the salt water after chemical method deliming in nanofiltration process because calcium carbonate occurs in concentration difference
It is deposited in film, salt water pH control is in 4-6 after acidification.Certainly cation exchange resin can also be used, and further to remove chemical method de-
Calcium ion after calcium in salt water makes concentration product of the concentration of its carbonate and calcium ion far from calcium carbonate, to avoid nanofiltration point
From when make tosca in film because of concentration difference.
Nanofiltration membrane separating method can not only make the separation of monovalent salt and divalent salts, and remaining TOC in salt water can also obtained
To certain separation, TOC in the sodium chloride brine after further decreasing nanofiltration.
Water distribution of the sodium chloride brine of the low sodium sulphate obtained through nanofiltration as sodium chloride electrolysis salt water, then through conventional method
Sodium chloride electrolysis raw material is used as after purification.It is back in sodium sulfate wastewater and recycles through the aqueous solution rich in sulfate radical that nanofiltration obtains
It utilizes.
Due to the adoption of the above technical scheme, the invention has the following advantages:
1, sodium sulfate wastewater and calcium chloride wastewater recycling can be achieved, accomplish the treatment of wastes with processes of wastes against one another, calcium sulfate obtained and chlorination
Sodium salt market for water dosage is big.
2, using the synchronous removal TOC of electrocatalytic oxidation and ammonia nitrogen, using nanofiltration separation friend's sulfate, while further separation
TOC, impurity removal process is at low cost, operating flexibility is big, and obtained sodium chloride salt water impurity is few, can be used as matching for sodium chloride electrolysis salt water
Water, it is with good economic efficiency.
3, react simple and easy to control, equipment is simple, has extensive industrialized prospect.
Detailed description of the invention
Fig. 1 is that sodium sulfate wastewater of the present invention utilizes method flow schematic diagram.
Specific embodiment
Embodiment 1
(1) by content be 6.02wt% sodium sulfate wastewater and content be 14.6wt% calcium chloride wastewater stoichiometrically
Than 1: 0.8 mixing, it is stirred to react 30min, filters to obtain calcium sulfate byproduct and sodium chloride crude brine, sulfate radical content in crude brine
0.886wt%, calcium content 0.081wt%, TOC 44.3mg/L, ammonia nitrogen 10.3mg/L；
(2) the sodium chloride crude brine for obtaining step (1), using Electrocatalytic Oxidation except substances such as TOC and ammonia nitrogens, then
It is itself and calcium ion reactive chemistry stoichiometric number by sodium carbonate additional amount with 30wt% sodium hydroxide solution by after salt water tune pH to 11
1.05 times, sodium carbonate solid is added, is filtered after being stirred to react 30min, obtains after decalcification that calcium content is in salt water
0.00092wt%, TOC 7.6mg/L, ammonia nitrogen are not detected；
(3) decalcification salt water in step (2) is added in nanofiltration membrane separation device separation salt water with hydrochloric acid tune pH to 4.0
Sulfate and sodium chloride, obtain the sodium chloride brine of low sodium sulphate and the aqueous solution rich in sodium sulphate, wherein be rich in sulfate radical
Aqueous solution be back in sodium sulfate wastewater and recycle；
The sodium chloride salt water quality of low sodium sulphate is made through above-mentioned steps: sodium chloride content 3.48wt%, sulfate radical contain
0.041wt%, TOC 4.6mg/L are measured, ammonia nitrogen is not detected, and can be used as the water distribution of sodium chloride electrolysis salt water, and through conventional method essence
Sodium chloride electrolysis raw material is used as after system.
Embodiment 2
(1) by content be 7.83wt% sodium sulfate wastewater and content be 14.02wt% calcium chloride wastewater based on chemistry
Amount is stirred to react 60min, filters to obtain calcium sulfate byproduct and sodium chloride crude brine, measure sulfate anion in brine system than 1: 0.9 mixing
Content is 0.606wt%, calcium content 0.112wt%, TOC 46.4mg/L；
(2) the sodium chloride crude brine for obtaining step (1), using Electrocatalytic Oxidation except substances such as TOC and ammonia nitrogens, then
It is itself and calcium ion reactive chemistry stoichiometric number by sodium carbonate additional amount with sodium hydroxide solution by after salt water tune pH to 10.02
1.1 times, sodium carbonate solid being added, is filtered after being stirred to react 30min, salt water calcium content is 0.00062wt% after measuring deliming,
TOC is 9.1mg/L；
(3) decalcification salt water in step (2) is added to nanofiltration membrane separation device separation salt water with hydrochloric acid tune pH to 5.22
In sulfate and sodium chloride, obtain the sodium chloride brine of low sodium sulphate and the aqueous solution rich in sodium sulphate, wherein be rich in sulfuric acid
The aqueous solution of root, which is back in sodium sulfate wastewater, to be recycled；
The sodium chloride salt water quality of low sodium sulphate is made through above-mentioned steps: sodium chloride content 4.65wt%, sodium sulphate contain
Measuring is 0.032wt%, TOC 4.8mg/L, and ammonia nitrogen is not detected, and can be used as the water distribution of sodium chloride electrolysis salt water, and through conventional method
Sodium chloride electrolysis raw material is used as after purification.
Embodiment 3
(1) by content be 8.63wt% sodium sulfate wastewater and content be 14.02wt% calcium chloride wastewater based on chemistry
Amount is stirred to react 300min, filters to obtain calcium sulfate byproduct and sodium chloride crude brine, measure sulfate anion in brine system than 1: 1 mixing
Content is 0.376wt%, calcium content 0.192wt%, TOC 37.8mg/L；
(2) the sodium chloride crude brine for obtaining step (1), using Electrocatalytic Oxidation except substances such as TOC and ammonia nitrogens, then
It is itself and calcium ion reactive chemistry stoichiometric number by sodium carbonate additional amount with sodium hydroxide solution by after salt water tune pH to 12.03
1.2 times, sodium carbonate solid is added, is filtered after being stirred to react 60min, measures after deliming that calcium content is 0.00034wt% in salt water,
TOC is 7.6mg/L；
(3) decalcification salt water in step (2) is added to nanofiltration membrane separation device separation salt water with hydrochloric acid tune pH to 6.03
In sulfate and sodium chloride, obtain the sodium chloride brine of low sodium sulphate and the aqueous solution rich in sodium sulphate, wherein be rich in sulfuric acid
The aqueous solution of root, which is back in sodium sulfate wastewater, to be recycled；
The sodium chloride salt water quality of low sodium sulphate is made through above-mentioned steps: sodium chloride content 5.40wt%, sulfate radical contain
0.028wt%, TOC 4.1mg/L are measured, ammonia nitrogen is not detected, and can be used as the water distribution of sodium chloride electrolysis salt water, and through conventional method essence
Sodium chloride electrolysis raw material is used as after system.
Embodiment 4
(1) by content be 7.83wt% sodium sulfate wastewater and content be 15.48wt% calcium chloride wastewater based on chemistry
Amount is stirred to react 60min, filters to obtain calcium sulfate byproduct and sodium chloride crude brine, measure sulfuric acid in salt water than 1: 0.95 mixing
Radical content is 0.460wt%, calcium content 0.153wt%, TOC 47.3mg/L；
(2) the sodium chloride crude brine for obtaining step (1), using Electrocatalytic Oxidation except substances such as TOC and ammonia nitrogens, then
It is itself and calcium ion reactive chemistry stoichiometric number by sodium carbonate additional amount with sodium hydroxide solution by after salt water tune pH to 11.94
1.2 times, sodium carbonate solid is added, is filtered after being stirred to react 60min, salt water calcium content is 0.00031wt% after measuring deliming,
TOC is 7.1mg/L；；
(3) decalcification salt water in step (2) is added in nanofiltration membrane separation device separation salt water with hydrochloric acid tune pH to 6
Sulfate and sodium chloride obtain the sodium chloride brine of low sodium sulphate and the aqueous solution rich in sodium sulphate, wherein rich in sulfate radical
Aqueous solution is back in sodium sulfate wastewater and recycles；
The sodium chloride salt water quality of low sodium sulphate is made through above-mentioned steps: sodium chloride content 5.01wt%, sulfate radical contain
0.028wt%, TOC 3.6mg/L are measured, ammonia nitrogen is not detected, and can be used as the water distribution of sodium chloride electrolysis salt water, and through conventional method essence
Sodium chloride electrolysis raw material is used as after system.
Embodiment 5
(1) by content be 8.63wt% sodium sulfate wastewater and content be 15.45wt% calcium chloride wastewater based on chemistry
Amount is stirred to react 90min, filters to obtain calcium sulfate byproduct and sodium chloride crude brine, measure sulfate anion in brine system and contain than 1: 1 mixing
Amount is 0.371wt%, calcium content 0.193wt%, TOC 25.88mg/L；
(2) the sodium chloride crude brine for obtaining step (1), using Electrocatalytic Oxidation except substances such as TOC and ammonia nitrogens, then
It is itself and calcium ion reactive chemistry stoichiometric number by sodium carbonate additional amount with sodium hydroxide solution by after salt water tune pH to 11.54
1.2 times, sodium carbonate solid being added, is filtered after being stirred to react 30min, salt water calcium content is 0.00034wt% after measuring deliming,
TOC is 7.3mg/L；；
(3) decalcification salt water in step (2) is added in nanofiltration membrane separation device separation salt water with hydrochloric acid tune pH to 6
Sulfate and sodium chloride obtain the sodium chloride brine of low sodium sulphate and the aqueous solution rich in sodium sulphate, wherein rich in sulfate radical
Aqueous solution is back in sodium sulfate wastewater and recycles；
The sodium chloride salt water quality of low sodium sulphate: sodium chloride content 5.59%, sodium sulphate content is made through above-mentioned steps
0.035wt%, TOC 4.6mg/L, ammonia nitrogen are not detected, and can be used as the water distribution of sodium chloride electrolysis salt water, and refine through conventional method
It is used as sodium chloride electrolysis raw material afterwards.
The above is only specific embodiments of the present invention, but technical characteristic of the invention is not limited thereto.It is any with this hair
Based on bright, to solve essentially identical technical problem, essentially identical technical effect is realized, made ground simple change, etc.
With replacement or modification etc., all it is covered by among protection scope of the present invention.
Claims (4)
1. a kind of utilization method of sodium sulfate wastewater, it is characterised in that the following steps are included:
(1) calcium chloride is added into sodium sulfate wastewater, is stirred to react after 30-300min and sodium chloride crude salt is obtained by filtration in reaction solution
Water.
(2) TOC and ammonia nitrogen substance in crude brine are removed with electrocatalytic oxidation method, then adjusts pH to 10~12 with sodium hydroxide
Calcium ion in salt water is removed with sodium carbonate afterwards, the salt water after deliming is acidified with hydrochloric acid and adjusts pH to 4~6；
(3) above-mentioned resulting salt water is entered into sulfate and sodium chloride in nanofiltration membrane separation device separation salt water, obtains low-sulfur
The sodium chloride brine of sour sodium and aqueous solution rich in sodium sulphate, wherein the sodium chloride brine of low sodium sulphate is as sodium chloride electrolysis salt
The water distribution of water, and sodium chloride electrolysis raw material is used as after conventional method refines, the aqueous solution rich in sulfate radical is back to sodium sulphate
It is recycled in waste water.
2. a kind of utilization method of sodium sulfate wastewater according to claim 1, it is characterised in that: calcium chloride in step (1)
Additional amount is its 0.8-1 times with sodium sulphate reactive chemistry stoichiometric number.
3. a kind of utilization method of sodium sulfate wastewater according to claim 1, it is characterised in that: sodium carbonate in step (2)
Additional amount is its 1.05-1.2 times with calcium ion reactive chemistry stoichiometric number.
4. a kind of utilization method of sodium sulfate wastewater according to claim 1, it is characterised in that: the chlorine of the low sodium sulphate
Change natrium brine TOC be less than 5mg/L, ammonia nitrogen is not detected, sulfate radical is less than 0.05%.
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| CN111635055A (en) * | 2020-05-26 | 2020-09-08 | 南京大学盐城环保技术与工程研究院 | Industrial waste salt refining and purifying coupling process and device |
| CN112429882A (en) * | 2020-12-03 | 2021-03-02 | 南宁市泽威尔饲料有限责任公司 | Method and device for treating ferrous fumarate wastewater |
| CN112794868A (en) * | 2020-12-15 | 2021-05-14 | 洪湖市一泰科技有限公司 | Method for treating sodium tetrachloroaluminate generated in methyl dichlorophosphine production process |
| CN114524545A (en) * | 2022-03-03 | 2022-05-24 | 盛隆资源再生（无锡）有限公司 | Method for recycling wastewater containing sodium sulfate |
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| CN112429882A (en) * | 2020-12-03 | 2021-03-02 | 南宁市泽威尔饲料有限责任公司 | Method and device for treating ferrous fumarate wastewater |
| CN112429882B (en) * | 2020-12-03 | 2023-01-20 | 南宁市泽威尔饲料有限责任公司 | Method and device for treating ferrous fumarate wastewater |
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Application publication date: 20190723 |