CN105347594A - High-salinity wastewater zero emission and high-purity sodium chloride recovering system - Google Patents
High-salinity wastewater zero emission and high-purity sodium chloride recovering system Download PDFInfo
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- CN105347594A CN105347594A CN201510868674.8A CN201510868674A CN105347594A CN 105347594 A CN105347594 A CN 105347594A CN 201510868674 A CN201510868674 A CN 201510868674A CN 105347594 A CN105347594 A CN 105347594A
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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
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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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
- C02F1/447—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by membrane distillation
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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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
-
- 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
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- 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
- C02F2001/5218—Crystallization
Abstract
The invention discloses a high-salinity wastewater zero emission and high-purity sodium chloride recovering system which comprises a pretreatment system, a membrane separation system and an evaporative crystallization system which are arranged in sequence, wherein the pretreatment system is used for pretreating high-salinity wastewater; the membrane separation system is used for performing membrane separation treatment on the pretreated high-salinity wastewater; the evaporative crystallization system is used for performing evaporative crystallization on the treated high-salinity wastewater from the membrane separation system, so as to obtain high-purity sodium chloride. The waste liquor obtained after sepration of a nanofiltration system is low in sodium chloride concentration, and the operation of directly feeding sodium chloride into an electroosmosis system for concentration is uneconomical, so that sodium chloride is concentrated to 1/6-1/8 of the original sodium chloride and then the sodium chloride is further concentrated till the salt content is 10-15%; fresh water in the electroosmosis system can be returned to the reverse osmosis system for further concentration, and the final concentrate in the electroosmosis system can enter the evaporative crystallization system for evaporative crystallization, so that the content of sodium chloride in the obtained crystal is higher than 92%.
Description
Technical field
The invention belongs to Industrial Waste Water Treatments field, relate to the recovery system of a kind of high-salinity wastewater zero-emission and high purity sodium-chlor.
Background technology
In short supply along with industrial expansion and water resources, the factory effluent that part industry produces contains higher salinity, as Cl
-, SO
4 2-, Na
+, Ca
2+plasma, its pollution concentration and quantity discharged present the trend of rising, therefore, have become one of focus of current wastewater treatment to the pure water reuse of high-salt wastewater process and inorganic salt recovery technology.
Known evaporation technique is the effective technology realizing wastewater zero discharge, but evaporative process belongs to phase transition process, and greatly, working cost is high for consumption quantity of steam or current consumption; Adopt single membrane separating method, there is concentration should not be too high, and fouling membrane fouling is serious, and adopts disc tube reverse osmosis (dt-ro) film cost high; Simple employing electrodialysis is not only invested greatly, application fee is high, and there is reuse water and cannot meet up-to-date discharging standards; Just permeating and belonging to new technology in wastewater application, but complex process, technology are immature and energy consumption is higher.
At present, it is extensive that film combined treatment high salinity waste water realizes zero-discharge technology Application comparison, but the inadequate system of integrated artistic, the rate of recovery is not high, reuse water quality is low, it is low to reclaim inorganic salt purity, system energy consumption is high, such as ZL201110225251.6 introduces a kind of calcium chloride wastewater process and reuse method, pretreated waste water is all entered electrodialysis to concentrate, concentrated solution enters evaporation equipment, fresh water is by common reverse osmosis produced Water circulation, it is large that the electrodialysis that technological process is simple concentrates energy consumption, changes film cost intensive.The high salinity zero discharge of industrial waste water technique separately having ZL201310311089.9 to introduce, electrodialysis process is carried out by filtering the concentrated solution repeatedly, material after electrodialysis concentrates carries out evaporating and crystallization, but the salt that this technique obtains is carnallite does not have use value.
Therefore, from cleaner production, watering balance, resource reclaim angle system analysis combination membrane process feature, the comprehensive treating process of high salinity trade effluent is made to have good social and economic effects.
Summary of the invention
The object of the invention is to, for the above deficiency existed, provide the recovery system of a kind of high-salinity wastewater zero-emission and high purity sodium-chlor.
For this reason, the invention provides following solution:
A recovery system for high-salinity wastewater zero-emission and high purity sodium-chlor, described recovery system comprises pretreatment system, film separating system and evaporation and crystallization system, and described pretreatment system, film separating system and evaporation and crystallization system are arranged successively; Described pretreatment system is used for carrying out pre-treatment to high-salt wastewater; Described film separating system is used for carrying out membrane separation to pretreated high-salt wastewater; Described evaporation and crystallization system is carried out evaporative crystallization for the high-salt wastewater from film separating system and is obtained highly purified sodium-chlor.High-salt wastewater mentioned in context be saltiness higher than 1.5%wt, dissolvability solid amount is higher than the high salinity trade effluent of 15000mg/L.
Further, described film separating system comprises nanofiltration system, reverse osmosis system and electrodialysis system, described nanofiltration system, reverse osmosis system and electrodialysis system are arranged successively, the product water of described nanofiltration system enters reverse osmosis system and carries out reverse-osmosis treated, the dense water of described nanofiltration system enters freezing and crystallizing system, the dense water of described reverse osmosis system enters electrodialysis system and carries out electrodialysis process, the product Water circulation of described reverse osmosis system, the concentrated solution of described electrodialysis system enters evaporation and crystallization system, the fresh water reuse of described electrodialysis system is to the entrance of reverse osmosis system.
Further, described nanofiltration system is the combination of one-level nanofiltration device or multistage nanofiltration device.
Further, in described electrodialysis system, total dissolved solid is greater than 10%.
Further, described electrodialysis system adopts homogeneous membrane or heterogeneous membrane or half homogeneous membrane.
Further, described pretreatment system comprises dosing and softens clarification system, ozone high grade oxidation system, activated carbon filtration system, ultrafiltration system and resin melded system, and described dosing is softened clarification system, ozone high grade oxidation system, activated carbon filtration system, ultrafiltration system and resin melded system and arranged successively.
Further, described dosing softens in clarification system that to add medicament be one or more combination in alkali, soda ash, flocculation agent.
Further, described resin melded system is one or more the combination in cation bed, weak acid bed, degassing tower.
Further, described evaporation and crystallization system is one or more the combination in MVR evaporation and crystallization system, heterogeneous evaporation and crystallization system and membrane distillation system.
Further, the recycling condensing water of described evaporation and crystallization system.
MVR be mechanical steam recompression technology (
mechanical
vapor
recompression) abbreviation, the secondary steam and energy thereof that utilize vapo(u)rization system self to produce, through vapour compressor compressed action, promote the heat content of secondary steam, lead into cooling tower, the cooling water circulation preheating material of cooling tower, so circulation provides heat energy to vapo(u)rization system, thus reduces a power-saving technology of the demand of the energy to external world.
The invention provides the recovery system of a kind of high-salinity wastewater zero-emission and high purity sodium-chlor, comprehensively analyzed by Technological Economy, the concentration that nanofiltration system is separated post chlorization sodium is not high, directly entering electrodialysis system carries out concentrated uneconomical, first carry out being concentrated into original 6 ~ 8 times with reverse osmosis system, enter electrodialysis system again and be concentrated into 10 ~ 15% further, the fresh water reuse of electrodialysis system concentrates further to reverse osmosis system, the concentrated solution of electrodialysis system enters evaporation and crystallization system and carries out evaporative crystallization, to obtain in crystal sodium chloride content higher than 92%, reach technical grade requirement, the product water of reverse osmosis system and the equal reuse of water of condensation of evaporation and crystallization system, the recovery system of described high-salinity wastewater zero-emission and high purity sodium-chlor can be applied in the system of zero-discharge technology, thus realizes the effect of wastewater zero discharge.Therefore, the recovery system of the high-salinity wastewater zero-emission provided and high purity sodium-chlor has good social and economic effects.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the recovery system of a kind of high-salinity wastewater zero-emission provided by the present invention and high purity sodium-chlor;
In figure: clarification system is softened in 101-dosing; 102-ozone high grade oxidation system; 103-activated carbon filtration system; 104-ultrafiltration system; 105-resin melded system; 201-nanofiltration system; 202-reverse osmosis system; 203-electrodialysis system; 301-evaporation and crystallization system.
Embodiment
With reference to the drawings and specific embodiments, the present invention is described in detail further.
A recovery system for high-salinity wastewater zero-emission and high purity sodium-chlor, described recovery system comprises pretreatment system, film separating system and evaporation and crystallization system, and described pretreatment system, film separating system and evaporation and crystallization system are arranged successively; Described pretreatment system is used for carrying out pre-treatment to high-salt wastewater; Described film separating system is used for carrying out membrane separation to pretreated high-salt wastewater; Described evaporation and crystallization system is carried out evaporative crystallization for the high-salt wastewater from film separating system and is obtained highly purified sodium-chlor.
Described film separating system comprises nanofiltration system 201, reverse osmosis system 202 and electrodialysis system 203, described nanofiltration system 201, reverse osmosis system 202 and electrodialysis system 203 are arranged successively, the product water of described nanofiltration system 201 enters reverse osmosis system 202 and carries out reverse-osmosis treated, the dense water of described reverse osmosis system 202 enters electrodialysis system 203 and carries out electrodialysis process, the product Water circulation of described reverse osmosis system 202, the concentrated solution of described electrodialysis system 203 enters evaporation and crystallization system, and the fresh water reuse of described electrodialysis system 203 is to the entrance of reverse osmosis system 202.
Described nanofiltration system 201 is the combination of one-level nanofiltration device or multistage nanofiltration device.
In described electrodialysis system 203, total dissolved solid is greater than 10%.
Described electrodialysis system 203 adopts homogeneous membrane or heterogeneous membrane or half homogeneous membrane.
Described pretreatment system comprises dosing and softens clarification system 101, ozone high grade oxidation system 102, activated carbon filtration system 103, ultrafiltration system 104 and resin melded system 105, and described dosing is softened clarification system 101, ozone high grade oxidation system 102, activated carbon filtration system 103, ultrafiltration system 104 and resin melded system 105 and arranged successively.
Described dosing softens in clarification system 101 that to add medicament be one or more combination in alkali, soda ash, flocculation agent.
Described resin melded system 105 is one or more the combination in cation bed, weak acid bed, degassing tower.
Described evaporation and crystallization system 301 is one or more the combination in MVR evaporation and crystallization system, heterogeneous evaporation and crystallization system and membrane distillation system.
Further, the recycling condensing water of described evaporation and crystallization system 301.
Particularly, following technique can be adopted:
With the treatment capacity of 360 tons per hour to each treatment unit design of whole technique and installation and debugging, finally carry out spot testing, pilot plant test carried out to certain high-salt wastewater:
The saltiness 1%wt of certain factory's high-salt wastewater, COD
cr160mg/L, suspended substance are less than 70mg/L, Ca
2+concentration is 360ppm, Mg
2+concentration is 35ppm, and the concentration of silicon is 50ppm, Cl
-concentration is 1800ppm, SO
4 2-concentration is 2540ppm;
Pretreatment system: the high-salt wastewater of 360m3/h is carried out add the coagulating precipitation sofening treatment such as alkali, soda ash, flocculation agent and remove calcium ions and magnesium ions, water outlet Ca
2+, Mg
2+concentration all lower than 50ppm, the concentration of silicon is lower than 5ppm;
Dosing softens the waste water after clarification through ozone high grade oxidation and activated carbon filter, makes COD lower than 80ppm; Be less than 0.5NTU by ultrafiltration system turbidity again, and pass through cation bed, weak acid bed, degassing tower successively to ensure water outlet Ca
2+, Mg
2+, CO
3 2-be less than 5ppm;
Through the high-salt wastewater of pretreatment system process, enter two-stage nanofiltration device, final water production rate 240m3/h, the Cl of its nanofiltration system
-concentration is 1800ppm, SO
4 2-concentration is 5ppm, and the product water of nanofiltration system is entered reverse osmosis system and be separated concentrated; The product water of reverse osmosis system carries out reuse, and the final concentrated stream amount of reverse osmosis system is 35m3/h, saltiness 1.5%wt;
The dense water of reverse osmosis system enters osmosis system and concentrates, the fresh water of osmosis system is got back to reverse osmosis system and is concentrated, the final concentrated solution aquifer yield of electrodialysis system is 3.5m3/h, saltiness 15%wt, the concentrated solution of electrodialysis system is delivered to MVR evaporation and crystallization system and carries out evaporative crystallization, MVR evaporation and crystallization system adopts sub-prime crystallization to extract sodium-chlor, the recycling condensing water of MVR evaporation and crystallization system.
Above-mentioned embodiment is used for explaining and the present invention is described; be only the preferred embodiments of the present invention; instead of limit the invention; in the protection domain of spirit of the present invention and claim; the any amendment made the present invention, equivalent replacement, improvement etc., all fall into protection scope of the present invention.
Claims (10)
1. a recovery system for high-salinity wastewater zero-emission and high purity sodium-chlor, is characterized in that, described recovery system comprises pretreatment system, film separating system and evaporation and crystallization system, and described pretreatment system, film separating system and evaporation and crystallization system are arranged successively; Described pretreatment system is used for carrying out pre-treatment to high-salt wastewater; Described film separating system is used for carrying out membrane separation to pretreated high-salt wastewater; Described evaporation and crystallization system is carried out evaporative crystallization for the high-salt wastewater from film separating system and is obtained highly purified sodium-chlor.
2. the recovery system of a kind of high-salinity wastewater zero-emission according to claim 1 and high purity sodium-chlor, it is characterized in that, described film separating system comprises nanofiltration system, reverse osmosis system and electrodialysis system, described nanofiltration system, reverse osmosis system and electrodialysis system are arranged successively, the product water of described nanofiltration system enters reverse osmosis system and carries out reverse-osmosis treated, the dense water of described reverse osmosis system enters electrodialysis system and carries out electrodialysis process, the product Water circulation of described reverse osmosis system, the concentrated solution of described electrodialysis system enters evaporation and crystallization system, the fresh water reuse of described electrodialysis system is to the entrance of reverse osmosis system.
3. the recovery system of a kind of high-salinity wastewater zero-emission according to claim 2 and high purity sodium-chlor, is characterized in that, described nanofiltration system is the combination of one-level nanofiltration device or multistage nanofiltration device.
4. the recovery system of a kind of high-salinity wastewater zero-emission according to claim 2 and high purity sodium-chlor, is characterized in that, in described electrodialysis system, total dissolved solid is greater than 10%.
5. the recovery system of a kind of high-salinity wastewater zero-emission according to claim 2 and high purity sodium-chlor, is characterized in that, described electrodialysis system adopts homogeneous membrane or heterogeneous membrane or half homogeneous membrane.
6. the recovery system of a kind of high-salinity wastewater zero-emission according to claim 1 and high purity sodium-chlor, it is characterized in that, described pretreatment system comprises dosing and softens clarification system, ozone high grade oxidation system, activated carbon filtration system, ultrafiltration system and resin melded system, and described dosing is softened clarification system, ozone high grade oxidation system, activated carbon filtration system, ultrafiltration system and resin melded system and arranged successively.
7. the recovery system of a kind of high-salinity wastewater zero-emission according to claim 6 and high purity sodium-chlor, is characterized in that, described dosing softens in clarification system that to add medicament be one or more combination in alkali, soda ash, flocculation agent.
8. the recovery system of a kind of high-salinity wastewater zero-emission according to claim 6 and high purity sodium-chlor, is characterized in that, described resin melded system is one or more the combination in cation bed, weak acid bed, degassing tower.
9. the recovery system of a kind of high-salinity wastewater zero-emission according to claim 1 and high purity sodium-chlor, it is characterized in that, described evaporation and crystallization system is one or more the combination in MVR evaporation and crystallization system, heterogeneous evaporation and crystallization system and membrane distillation system.
10. the recovery system of a kind of high-salinity wastewater zero-emission according to claim 1 and high purity sodium-chlor, is characterized in that, the recycling condensing water of described evaporation and crystallization system.
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