CN106630341A - Sodium chloride separating and recycling method for high-salinity wastewater - Google Patents

Sodium chloride separating and recycling method for high-salinity wastewater Download PDF

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Publication number
CN106630341A
CN106630341A CN201610847120.4A CN201610847120A CN106630341A CN 106630341 A CN106630341 A CN 106630341A CN 201610847120 A CN201610847120 A CN 201610847120A CN 106630341 A CN106630341 A CN 106630341A
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China
Prior art keywords
sodium chloride
high pressure
salt
membrane
salt wastewater
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CN201610847120.4A
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Chinese (zh)
Inventor
占坤
朱小波
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JIANGSU XINYU TIANCHENG ENVIRONMENTAL PROTECTION ENGINEERING Co Ltd
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JIANGSU XINYU TIANCHENG ENVIRONMENTAL PROTECTION ENGINEERING Co Ltd
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Priority to CN201610847120.4A priority Critical patent/CN106630341A/en
Publication of CN106630341A publication Critical patent/CN106630341A/en
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00Halides of sodium, potassium or alkali metals in general
    • C01D3/04Chlorides
    • C01D3/06Preparation by working up brines; seawater or spent lyes
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/78Treatment of water, waste water, or sewage by oxidation with ozone

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention relates to a sodium chloride separating and recycling method for high-salinity wastewater. According to the method, divalent salts and organic matters are separated from monovalent salts by using the characteristics of a nano-filtration membrane, a large amount of organic matters are removed from the wastewater, and then, an evaporative concentration and crystallization step is carried out so as to separately obtain sodium chloride solids with fewer impurities. The method has the characteristics of reasonable flow, resource recovery, economical efficiency, high efficiency and stability in operation; and as a deep treatment technology, organic matters and inorganic salt dominated total dissolved solids (TDS) are effectively removed from the high-salinity wastewater, and meanwhile, the sodium chloride solids with fewer impurities are obtained, so that the defects of the existing high-salinity wastewater treatment technologies can be excellently made up, and the treatment of high-salinity concentrated solutions achieves the aim of zero solid and liquid discharge.

Description

A kind of sodium chloride separating and recovering method of high-salt wastewater
Technical field
The present invention relates to a kind of method of wastewater treatment, the sodium chloride separating and recovering method of particularly a kind of high-salt wastewater.
Background technology
Industrial wastewater contains the poisonous and harmful substances such as a large amount of phenol, hydrocarbon, oil, heavy metal, and organic pollution contained by waste water includes Phenols, polycyclc aromatic compound and nitrogenous, oxygen, the heterocyclic compound of sulphur etc., are that one kind typically contains hardly degraded organic substance Industrial wastewater.At present the domestic technology for processing high-salt wastewater is mainly direct evaporative crystallisation process, but produces after evaporative crystallization Solid carnallite complicated component, containing poisonous and harmful substance, can only be processed as danger is useless.So not only easily cause environment secondary Pollution, returns enterprise and causes the useless disposal costs of the danger of great number.The content of the invention
Goal of the invention:It is an object of the invention to provide a kind of flow process is rationally, can resource reclaim, economical and efficient is stable Effective removal high-salt wastewater in organic matter and the total dissolved solid (TDS) based on inorganic salts high-salt wastewater sodium chloride Separating and recovering method.
Technical scheme:The invention discloses a kind of sodium chloride separating and recovering method of high-salt wastewater, comprises the following steps:
1) high-salt wastewater is first passed through into high-voltage operation nanofiltration membrane system, obtains high pressure NF membrane permeate and high pressure NF membrane Concentrate;
2) high pressure NF membrane permeate is obtained into the concentration of sodium chloride high power by the evaporimeter of sodium chloride evaporation and crystallization system Liquid, its concentration reaches 2 × 105Mg/L~2.5 × 105Mg/L, the steam for evaporating to be formed and enter reuse pool conduct after condensed water Recycle-water is utilized;
3) sodium chloride high power concentrate is again by the crystallizer of sodium chloride evaporation and crystallization system by the saturation chlorination in solution Sodium forms crystallization and salts out, and obtains 95%~98.5% sodium chloride salt, and the mother liquor for finally obtaining 0.5%~2% returns to biochemistry System;
4) high pressure NF membrane concentrate is entered into oxidative system carries out oxidation processes, reduces CODcr, in making concentrate CODcr200mg/L~500mg/L.
5) by above-mentioned oxidized reduction CODcrRemaining water and condensed water mixing afterwards enters reuse pool as reuse water conservancy With.
Wherein, the inorganic salts in the high-salt wastewater described in step 1 mainly contain sodium chloride, simultaneously containing a small amount of organic matter.
Wherein, the separation by high pressure nanofiltration membrane system described in step 2, the main sodium chloride-containing of high pressure NF membrane permeate With and a small amount of nitrate, sulfate radical is less than 20~200mg/L, rejection to organics rate 70~90%.
Wherein, high pressure NF membrane permeate described in step 3 obtains sodium chloride crystal salt by evaporation and crystallization system, remaining What about 1%~3% evaporation mother liquor was mainly contained is that nitrate and organic matter are vented back to biochemical system process.
Wherein, the high pressure NF membrane concentrate described in step 4 is produced and add in concentrate oxidant and flocculant, makes CODcr Reduce entering divalent salts evaporative crystallization steps after most 200mg/L~500mg/L.
Wherein, the oxidant is hydrogen peroxide or ozone;Flocculant is iron-magnesium-aluminium inorganic composite flocculant or macromolecule Flocculant.
Wherein, present invention oxidation technology used is selected from, but not limited to, Fenton oxidation, ozone oxidation, electrolytic oxidation technology.
Wherein, total dissolved solid (Totaldissolvedsolids, TDS) refers to the total content that material is dissolved in water, Including calcium ions and magnesium ions, colloid, suspended particulate substance, protein, virus, bacterium, microorganism and corpse, units of measurement is mg/litre (mg/L), it shows in 1 liter of water dissolved with how many milligrams of total dissolved solids.
Wherein, CODcr is referred to using potassium bichromate (K2Cr207) chemical oxygen consumption (COC) that determines as oxidant.
Wherein, nanofiltration membrane of the invention, is selected from, but not limited to, dish tubular nanofiltration membrane, board-like NF membrane, rolling nanofiltration Form membrane.
The processing method of the high-salt wastewater of the present invention, is divided divalent salts and organic matter from monovalent salt using nanofiltration membrane property Separate out and, remove the large amount of organic matter that contains in waste water, be then evaporated concentration and crystallisation step, respectively obtain impurity compared with Few solid sodium chloride solid.
The method has flow process rationally, can resource reclaim, economical and efficient, the characteristics of stable, it is used as a kind of depth Treatment technology, effectively removes organic matter and the total dissolved solid (TDS) based on inorganic salts in high-salt wastewater, while obtaining miscellaneous The less solid sodium chloride solid of matter, can be very good to make up the deficiency in existing high-salt wastewater treatment technology, concentrate high salt Liquid process reaches the target of " solid, liquid zero-emission ".
The processing method of the high-salt wastewater of the present invention has quite varied application prospect, and in future more areas will also be had Its superiority can be embodied, such as printing and dyeing, Coal Chemical Industry, pharmacy industry, using this method to high-concentration salt-containing wastewater at Reason, substantially reduces the useless generation of danger, reduces the high cost that enterprise undertakes to useless process of danger, while waste can also be become into resource, Obtain product sales revenue.
The present invention has just just started development in waste water industry, it is believed that can be widely applied to more necks in this technology in the future Domain, the waste in more water process resource is changed into, and is reduced environmental pollution and is improved resource utilization.
Beneficial effect:
Description of the drawings
Fig. 1 is the process chart of the sodium chloride separating and recovering method of high-salt wastewater;
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment, the present invention is further elucidated.
Embodiment
Certain industrial high-salt wastewater salt content after pretreatment is 6 × 104Mg/L, wherein sodium chloride are 3.5 × 104Mg/L, Other about 0.3 × 104Mg/L (nitrate and ammonium salt), by the high-salt wastewater 1000kg high pressure nanofiltration membrane treatment equipment is first passed through, Obtain the permeate of about 800kg and the concentrate of about 200kg.Permeate enters monovalent salt evaporation and crystallization system, in evaporation process Vapor be changed into after condensed water as recycle-water.The mother liquor of about the 1% of crystallization process generation returns biochemical system reprocessing.Knot Solid salt 47kg of moisture content about 30% is obtained after crystalline substance, after being dried sodium chloride crystal salt 32.7kg is obtained.Concentrate is by senior Oxidation processes organics removal, makes CODcr less than 500mg/l, as recycle-water, about 10% mother after then mixing with condensed water Liquid is back to front end nanofiltration membrane treatment equipment to be continued to separate, and is capable of achieving resource reclaim.
Table 1 evaporates permeate evaporative crystallization composition
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, under the premise without departing from the principles of the invention, some improvement can also be made, these improvement also should be regarded as the present invention's Protection domain.

Claims (6)

1. a kind of sodium chloride separating and recovering method of high-salt wastewater, is characterized in that, comprise the following steps:
1) high-salt wastewater is first passed through into high-voltage operation nanofiltration membrane system, obtains high pressure NF membrane permeate and the concentration of high pressure NF membrane Liquid;
2) high pressure NF membrane permeate is obtained into sodium chloride high power concentrate by the evaporimeter of sodium chloride evaporation and crystallization system, its Concentration reaches 2 × 105Mg/L~2.5 × 105Mg/L, the steam for evaporating to be formed and enter reuse pool as reuse after condensed water Water conservancy is used;
3) sodium chloride high power concentrate is again by the crystallizer of sodium chloride evaporation and crystallization system by the saturated sodium-chloride shape in solution Salt out into crystallization, obtain 95%~98.5% sodium chloride salt, the mother liquor for finally obtaining 0.5%~2% returns to biochemical system;
4) high pressure NF membrane concentrate is entered into oxidative system carries out oxidation processes, reduces CODcr, in making concentrate CODcr200mg/L~500mg/L.
5) by above-mentioned oxidized reduction CODcrRemaining water and condensed water mixing afterwards enters reuse pool and utilizes as recycle-water.
2. a kind of sodium chloride separating and recovering method of high-salt wastewater according to claim 1, is characterized in that, step 1 institute Inorganic salts in the high-salt wastewater stated mainly contain sodium chloride, simultaneously containing a small amount of organic matter.
3. a kind of sodium chloride separating and recovering method of high-salt wastewater according to claim 1, is characterized in that, step 2 institute The separation by high pressure nanofiltration membrane system stated, the main sodium chloride-containing of high pressure NF membrane permeate and and a small amount of nitrate, sulfuric acid 20~200mg/L of root, rejection to organics rate 70~90%.
4. a kind of sodium chloride separating and recovering method of high-salt wastewater according to claim 1, is characterized in that, step 3 institute High pressure NF membrane permeate is stated by evaporation and crystallization system, sodium chloride crystal salt is obtained, remaining about 1%~3% evaporates mother liquor master Contain and have plenty of nitrate and organic matter is vented back to biochemical system process.
5. a kind of sodium chloride separating and recovering method of high-salt wastewater according to claim 1, is characterized in that, step 4 institute The high pressure NF membrane concentrate stated is produced in concentrate and adds oxidant, dosage 1-10mg/L, and flocculant, dosage 5- 30mg/L, makes CODcrReduce entering divalent salts evaporative crystallization steps after most 200~500mg/L.
6. the sodium chloride separating and recovering method of a kind of high-salt wastewater according to claim 1 or 5, is characterized in that, described Oxidant is hydrogen peroxide or ozone;Flocculant is iron-magnesium-aluminium inorganic composite flocculant or high polymer coagulant.
CN201610847120.4A 2016-09-23 2016-09-23 Sodium chloride separating and recycling method for high-salinity wastewater Pending CN106630341A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107473488A (en) * 2017-10-09 2017-12-15 新乡市锦源化工有限公司 Para-ester produces the processing method of waste water
CN107827303A (en) * 2017-09-26 2018-03-23 上海晶宇环境工程股份有限公司 Flying dust washings processing technique and its special equipment
CN110342546A (en) * 2019-01-24 2019-10-18 内蒙古晶泰环境科技有限责任公司 A kind of haline water salt resource recovering system and its technique
CN112225375A (en) * 2020-09-26 2021-01-15 安徽金禾实业股份有限公司 Pretreatment method of sucralose wastewater
CN113698014A (en) * 2020-05-20 2021-11-26 中国石油天然气集团有限公司 Method for recovering refined reverse osmosis concentrated water

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105236650A (en) * 2015-09-29 2016-01-13 北京新源国能科技有限公司 Wastewater processing method
CN105948362A (en) * 2016-06-24 2016-09-21 东华工程科技股份有限公司 Coal chemical RO strong brine treatment process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105236650A (en) * 2015-09-29 2016-01-13 北京新源国能科技有限公司 Wastewater processing method
CN105948362A (en) * 2016-06-24 2016-09-21 东华工程科技股份有限公司 Coal chemical RO strong brine treatment process

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107827303A (en) * 2017-09-26 2018-03-23 上海晶宇环境工程股份有限公司 Flying dust washings processing technique and its special equipment
CN107473488A (en) * 2017-10-09 2017-12-15 新乡市锦源化工有限公司 Para-ester produces the processing method of waste water
CN110342546A (en) * 2019-01-24 2019-10-18 内蒙古晶泰环境科技有限责任公司 A kind of haline water salt resource recovering system and its technique
CN113698014A (en) * 2020-05-20 2021-11-26 中国石油天然气集团有限公司 Method for recovering refined reverse osmosis concentrated water
CN112225375A (en) * 2020-09-26 2021-01-15 安徽金禾实业股份有限公司 Pretreatment method of sucralose wastewater

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Address after: Gaocheng Town, Yixing city environmental protection of 214214 cities in Jiangsu province Wuxi City No. 39 3-4-5

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Address before: Gaocheng Town, Yixing city environmental protection of 214214 cities in Jiangsu province Wuxi City No. 39 3-4-5

Applicant before: JIANGSU XINYU TIANCHENG ENVIRONMENTAL PROTECTION ENGINEERING CO., LTD.

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Application publication date: 20170510