CN106517622A - Separation and reuse method of sodium sulfate from high salinity wastewater - Google Patents
Separation and reuse method of sodium sulfate from high salinity wastewater Download PDFInfo
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- CN106517622A CN106517622A CN201610846599.XA CN201610846599A CN106517622A CN 106517622 A CN106517622 A CN 106517622A CN 201610846599 A CN201610846599 A CN 201610846599A CN 106517622 A CN106517622 A CN 106517622A
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- sodium sulphate
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- salt wastewater
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/16—Purification
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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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
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
- C02F2301/046—Recirculation with an external loop
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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 separation and reuse method of sodium sulfate from high salinity wastewater. Divalent salts and organic matters are separated from monovalent salts by means of nanofiltration membrane characteristics to remove a great amount of organic matters in wastewater, then evaporation concentration and crystallization steps are carried out to obtain a sodium sulfate solid with few impurity. The method has the characteristics of reasonable process, resource recovery, economical efficiency and high efficiency, and stable operation, can be used as an advanced treatment technology to effectively remove organic matter and inorganic salt based total dissolved solids (TDS) from high salinity wastewater, at the same time acquires the sodium sulfate solid with few impurity, can well make up for the shortcomings of existing high salinity wastewater treatment technology, and makes the high salinity concentrated solution treatment reach the purpose of "zero emission of solid and liquid".
Description
Technical field
The present invention relates to a kind of method of wastewater treatment, particularly a kind of separating and recovering method of the sodium sulphate 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.The technology for processing high-salt wastewater domestic at present 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.Environment is not only easily caused so 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 sulphate
Separating and recovering method.
Technical scheme：The invention discloses a kind of separating and recovering method of the sodium sulphate 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 concentrate；
2) high pressure NF membrane concentrate is entered oxidative system carries out oxidation processes, reduces CODcr, in making concentrate
CODcr200mg/L～500mg/L.
3) by above-mentioned oxidized reduction CODcrConcentrate afterwards, obtains sulphur by the evaporimeter of sodium sulphate evaporation and crystallization system
Sour sodium high power concentrate, in the sodium sulphate high power concentrate, the content containing total dissolved solid is 2 × 105Mg/L～2.5
×105Mg/L, the steam for evaporating are utilized as recycle-water after forming condensed water；
4) sodium sulphate high power concentrate is again by the crystallizer of sodium sulphate evaporation and crystallization system by the saturation sulfuric acid in solution
Sodium forms crystallization and salts out, and obtains 95%～99% sodium sulfate salt, and the mother liquor for finally obtaining 1%～12% returns to high pressure nanofiltration
Film front end, proceeds to separate.
Wherein, the inorganic salts in the high-salt wastewater described in step 1 mainly contain sodium sulphate, simultaneously containing a small amount of organic matter.
Wherein, sodium sulphate and organic matter in the high pressure NF membrane concentrate that the high pressure nanofiltration membrane system described in step 2 is produced
Concentrated at double, contained nitrate simultaneously.
Wherein, the high pressure NF membrane concentrate described in step 2 adds oxidant and flocculant in producing concentrate, makes CODcr
Divalent salts evaporative crystallization steps are entered after reducing 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, NF membrane described in step 4 produces concentrate by evaporation and crystallization system, obtains sulfate crystal salt, remaining
About 1%～12% evaporation mother liquor mainly contains the mixing carnallite such as sodium sulphate, sodium nitrate, and the water inlet end for returning nanofiltration membrane system enters again
Row point salt treatment.
Wherein, oxidation technology used by the present invention is selected from, but not limited to, Fenton oxidation, ozone oxidation, electrolytic oxidation technology.
Wherein, total dissolved solid (Totaldissolvedsolids, TDS) dissolves the total content of material in referring to 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.
Divalent salts and organic matter are divided from monovalent salt by the processing method of the high-salt wastewater of the present invention 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 sulfate.The method has flow process rationally, can resource reclaim, economical and efficient, the characteristics of stable, which is used as one
Further treatment technique is planted, organic matter and the total dissolved solid (TDS) based on inorganic salts in high-salt wastewater is effectively removed, while
The less solid sodium sulfate of impurity is obtained, be can be very good to make up the deficiency in existing high-salt wastewater treatment technology, made high salt dense
The process of contracting liquid 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, also has more areas in future
Its superiority can be embodied, such as the industry such as printing and dyeing, Coal Chemical Industry, pharmacy, using this method to high-concentration salt-containing wastewater at
Reason, substantially reduces the useless generation of danger, reduces the high cost that enterprise is undertaken 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, is changed into resource the waste in more water process, reduces environmental pollution and improves resource utilization.
Description of the drawings
Fig. 1 is the process chart of the separating and recovering method of the sodium sulphate of high-salt wastewater；
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment, further elucidate the present invention.
Embodiment
Certain industrial high-salt wastewater sodium sulphate after pretreatment is 2.2 × 104Mg/L, other about 0.3 × 104Mg/L (nitric acid
Salt and ammonium salt), high-salt wastewater 1000kg is first passed through into high pressure nanofiltration membrane treatment equipment, the concentrate of about 200kg is obtained.Concentration
Containing the most organic retained in the inorganic salts and high-salt wastewater based on sodium sulphate in liquid, by advanced oxidation process
Organics removal, makes CODcr less than 500mg/l, and subsequently into divalent salts evaporation and crystallization system, the vapor in evaporation process becomes
For after condensed water, used as recycle-water, about 10% mother liquor reflux continues to separate to front end nanofiltration membrane treatment equipment.Obtain after crystallization
Solid salt 31kg of moisture content about 30%, obtains sulfate crystal salt 21.8kg after being dried.The solid sodium sulfate impurity for obtaining compared with
It is few, it is capable of achieving resource reclaim.
1 COD of table and sulfate radical rejection effect
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 separating and recovering method of the sodium sulphate 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 concentrate；
2) high pressure NF membrane concentrate is entered oxidative system carries out oxidation processes, reduces CODcr, in making concentrate
CODcr200mg/L～500mg/L.
3) by above-mentioned oxidized reduction CODcrConcentrate afterwards, obtains sodium sulphate by the evaporimeter of sodium sulphate evaporation and crystallization system
High power concentrate, in the sodium sulphate high power concentrate, the content containing total dissolved solid is 2 × 105Mg/L～2.5 ×
105Mg/L, the steam for evaporating are utilized as recycle-water after forming condensed water；
4) sodium sulphate high power concentrate is again by the crystallizer of sodium sulphate evaporation and crystallization system by the saturation sodium sulphate shape in solution
Salt out into crystallization, obtain 95%～99% sodium sulfate salt, finally obtain 1%～12% mother liquor return to high pressure NF membrane before
End, proceeds to separate.
2. a kind of separating and recovering method of the sodium sulphate 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 sulphate, simultaneously containing a small amount of organic matter.
3. a kind of separating and recovering method of the sodium sulphate of high-salt wastewater according to claim 1, is characterized in that, step 2 institute
In the high pressure NF membrane concentrate that the high pressure nanofiltration membrane system stated is produced, sodium sulphate and organic matter are concentrated at double, contain nitre simultaneously
Hydrochlorate.
4. a kind of separating and recovering method of the sodium sulphate of high-salt wastewater according to claim 1, is characterized in that, step 2 institute
The high pressure NF membrane concentrate stated adds oxidant, dosage 1-10mg/L, and flocculant, dosage 5- in producing concentrate
30mg/L, makes CODcrDivalent salts evaporative crystallization steps are entered after reducing most 200～500mg/L.
5. a kind of separating and recovering method of the sodium sulphate of the high-salt wastewater according to claim 1 or 4, is characterized in that, described
Oxidant is hydrogen peroxide or ozone；Flocculant is iron-magnesium-aluminium inorganic composite flocculant or high polymer coagulant.
6. a kind of separating and recovering method of the sodium sulphate of high-salt wastewater according to claim 1, is characterized in that, step 4 institute
Stating NF membrane and concentrate being produced by evaporation and crystallization system, obtain sulfate crystal salt, remaining about 1%～12% evaporates mother liquor master
Sodium sulphate to be contained, sodium nitrate etc. mix carnallite, and the water inlet end for returning nanofiltration membrane system carries out a point salt treatment again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610846599.XA CN106517622A (en) | 2016-09-23 | 2016-09-23 | Separation and reuse method of sodium sulfate from high salinity wastewater |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610846599.XA CN106517622A (en) | 2016-09-23 | 2016-09-23 | Separation and reuse method of sodium sulfate from high salinity wastewater |
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| Publication Number | Publication Date |
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| CN106517622A true CN106517622A (en) | 2017-03-22 |
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| CN201610846599.XA Pending CN106517622A (en) | 2016-09-23 | 2016-09-23 | Separation and reuse method of sodium sulfate from high salinity wastewater |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824194A (en) * | 2019-03-04 | 2019-05-31 | 宜兴国际环保城科技发展有限公司 | A kind of processing method of high COD organic wastewater with high salt |
| CN109970265A (en) * | 2019-03-29 | 2019-07-05 | 长春黄金研究院有限公司 | A kind of gold concentrate smelting factory low cyanogen process method for purifying water containing high concentration sodium sulfate |
| CN110937581A (en) * | 2019-12-18 | 2020-03-31 | 江苏南大环保科技有限公司 | Refining method for efficiently removing organic matters in byproduct sulfate |
| CN114956425A (en) * | 2022-05-31 | 2022-08-30 | 昆山三一环保科技有限公司 | Treatment system and treatment method for waste lithium battery recovery wastewater |
Citations (3)
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|---|---|---|---|---|
| CN101928087A (en) * | 2009-06-26 | 2010-12-29 | 中国石油化工股份有限公司 | Method for treating high salinity wastewater |
| CN102491452A (en) * | 2011-11-18 | 2012-06-13 | 吉林吉恩镍业股份有限公司 | Process for treating sodium sulfate wastewater by using nanofiltration-reverse osmosis combined membrane |
| 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 |
-
2016
- 2016-09-23 CN CN201610846599.XA patent/CN106517622A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928087A (en) * | 2009-06-26 | 2010-12-29 | 中国石油化工股份有限公司 | Method for treating high salinity wastewater |
| CN102491452A (en) * | 2011-11-18 | 2012-06-13 | 吉林吉恩镍业股份有限公司 | Process for treating sodium sulfate wastewater by using nanofiltration-reverse osmosis combined membrane |
| 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)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824194A (en) * | 2019-03-04 | 2019-05-31 | 宜兴国际环保城科技发展有限公司 | A kind of processing method of high COD organic wastewater with high salt |
| CN109970265A (en) * | 2019-03-29 | 2019-07-05 | 长春黄金研究院有限公司 | A kind of gold concentrate smelting factory low cyanogen process method for purifying water containing high concentration sodium sulfate |
| CN110937581A (en) * | 2019-12-18 | 2020-03-31 | 江苏南大环保科技有限公司 | Refining method for efficiently removing organic matters in byproduct sulfate |
| CN110937581B (en) * | 2019-12-18 | 2022-08-19 | 江苏南大环保科技有限公司 | Refining method for efficiently removing organic matters in byproduct sulfate |
| CN114956425A (en) * | 2022-05-31 | 2022-08-30 | 昆山三一环保科技有限公司 | Treatment system and treatment method for waste lithium battery recovery 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 Applicant after: Jiangsu Xinyu Tiancheng environmental protection Co. Ltd. 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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