CN107619144A - A kind of high slat-containing wastewater divides salt process for reclaiming and system - Google Patents
A kind of high slat-containing wastewater divides salt process for reclaiming and system Download PDFInfo
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Abstract
The invention discloses a kind of technique of zero discharge and its processing system from high slat-containing wastewater recovery crystal salt, processing system includes tubular type microfiltration systems, weak acid resin hard-removal system, NF membrane and divides salt system, nanofiltration concentrated water oxidative system, nanofiltration concentrated water sodium sulphate evaporation and crystallization system, sodium sulphate freezing and crystallizing system etc..In present invention process, pretreated waste water tentatively divides salt using nanofiltration, and the salinity for producing water is mainly sodium chloride, NaCl of the purity not less than 98.5% is obtained through film concentration and evaporative crystallization, using the Na of MVR crystallization production purity more than 99.1% after concentrated water oxidation2SO4；Mother liquor after sodium sulphate evaporative crystallization mixes with the mother liquor after nanofiltration evaporative crystallization obtains saltcake by freezing, and saltcake returns to sodium sulphate evaporative crystallization and is converted into anhydrous sodium sulfate；Under the premise of guaranteed quality, salinity recycled in its entirety rate is more than 90%；Last a small amount of mother liquor is solidified by being spray-dried, while realizes wastewater zero discharge.
Description
Technical field
The present invention relates to a kind of high slat-containing wastewater to divide salt resource technology, in particular it relates to a kind of from high salt
The technique of zero discharge and system for use in carrying of Sewage treatment salt.
Background technology
Shortage of water resources and environmental capacity of water deficiency are to restrict the important bottleneck of certain areas Modern Coal-based Chemical industry development
Problem.Wherein, highly concentrated saline treatment and emission problem are one of significant challenges that industry development faces.By taking the Huanghe valley as an example,
Salt concentration is up to 700~800mg/L in the illiteracy west section area water of the Yellow River, and wherein sulphates content is close to surface water environment quality
Standard limited value, therefore the problem of discharge of wastewater control salt has turned into urgent need to resolve.Waste water zero emission solution is to crack the modern times
Developing Coal Chemical Industry and the important channel of water resource and environment contradiction.However, the crystallization of traditional waste water " zero " discharge by-product
Carnallite is worth without recycling, is easily met water leaching drip and is oozed out, secondary pollution risk be present, and in wastewater treatment process, in water
Micro heavy ion and residual organic matter constantly concentrate, may eventually enter into crystallization salt slurry in so that crystal salt may
Hazard property with hazardous waste, therefore crystallize the disposal of carnallite Environmental Safety and be faced with formidable challenges, it is Modern Coal-based Chemical production
Industry develops one of the problem of urgent need to resolve.
Chinese patent application 201610072782.9 discloses a kind of high saliferous Industry Waste moisture salt Zero discharging system, by height
Salt waste water tentatively divides salt by nanofiltration, and Re Fa or freezing production sodium chloride and sodium sulphate is respectively adopted in the concentrated water and production water to nanofiltration
Or nitrate.
But the rate of recovery of crystal salt is relatively low in the patent application.See, protecting according to existing actual project and pilot scale situation
Under the premise of the quality for demonstrate,proving salt, the rate of recovery is typically in 50-60%, that is, the salt for about still having 40-50% can only be used as outside carnallite
Row, not only limit the recovery of salt, while the outer impurities removal salt amount also increased, is unable to reach point salt recovery salt and reduces solid waste
Target.
In order to crack this problem, carry out the exploitation of crystal salt application technology as the second resource, effectively, economical, efficiently recovery is high
Sodium chloride and sodium sulphate in strong brine, recycling recycling is carried out as product, to realize《Modern Coal-based Chemical is built
If project environment entry criteria (tentative)》Environmental protection demonstration requirement certainly will turn into one of current hot subject.
The content of the invention：
Present invention aim to address the rate of recovery of crystal salt in existing high salt industrial wastewater " zero-emission " technology it is relatively low,
Outer impurities removal salt amount is larger, is unable to reach the problem of point salt reclaims salt and reduces solid waste target.
In order to realize the purpose of the invention described above, on the one hand, the invention provides a kind of from the zero of high-salt wastewater recovery salt
Discharge technology, the technique comprise the following steps：
(1) hardness, basicity, silicon, fluorine ion and the suspension of high-salt wastewater are reduced by pretreatment system；
(2) divide salt by the preliminary of nanofiltration, pretreated high-salt wastewater be divided into two strands, that is, produce water side and concentrated water side,
Wherein, the salinity for producing water side is mainly sodium chloride, and the salinity of concentrated water side is mainly sodium sulphate and partial oxidation sodium；Production water passes through film
Concentration and the first sodium chloride evaporation and crystallization system, obtain the NaCl of purity higher (as being not less than 98.5%)；
(3) tentatively divide the concentrated water obtained by salt through nanofiltration, after removing most of organic matter by oxidative system, steamed by MVR
Hair crystallization obtains sodium sulphate, wherein, sodium sulphate contains the saltcake of freezing and crystallizing unit return；
(4) nanofiltration concentrated water is mixed through sodium peroxydisulfate evaporative crystallization and nanofiltration production water by the mother liquor of sodium chloride evaporative crystallization
Close, into sodium sulphate freezing and crystallizing, obtain saltcake, saltcake, which is returned after sulfate crystal device is dehydrated, is changed into anhydrous sodium sulfate；
(5) mother liquor after sodium peroxydisulfate freezing and crystallizing is made by evaporative crystallization in the second sodium chloride evaporation and crystallization system
Sodium chloride is crystallized, and after dehydration separation, sodium chloride is dissolved into the first sodium chloride evaporation and crystallization system, to improve returning for sodium chloride
Yield and purity；
(6) mother liquor last after the second sodium chloride evaporation and crystallization system is solidified by being spray-dried, and forms carnallite, real
Existing wastewater zero discharge.
The technique of the invention described above is a kind of two fraction salt treatment process for high saliferous industrial wastewater, and it passes through setting
The first fraction salt is carried out in the continuous nanofiltration system in membrane separation concentration unit, and by being arranged in crystallization recycling unit
Evaporative crystallization and (or) freezing and crystallizing system carry out the second fraction salt, to realize sodium chloride and sulfuric acid in high saliferous industrial wastewater
Being completely separated, crystallize and purifying for sodium, is truly realized " dividing salt zero-emission " target of high saliferous industrial wastewater.
The present invention process method the step of in (1) (pretreatment), waste water is reduced or removed by pretreatment system system
Hardness, basicity, silicon, fluorine ion and suspension, so as to ensure the stable operation of nanofiltration system, while improve follow-up system
The crystallization purity salt produced.Preferably, the pretreatment system in present invention process includes tubular type microfiltration systems and weak acid resin removes
Hard system, and tubular type microfiltration systems then further comprise reaction tank, concentration basin, microfiltration membranes and other corollary equipments.
Pretreating process uses tube type filter membrance TMF techniques, to remove the easily knot such as the calcium of the easy fouling in water removal, magnesium, silicon
Dirty material, reduce the fouling and pollution problem of follow-up membranous system and evaporative crystallization technique.Micro-filtration is using the film of micropore in waste water
Sediment separate.It does not need that precipitate particle sizes are sufficiently large and proportion is sufficiently large, thus when material from dissolved state
After being converted into insoluble state, it is a kind of more effective separation method.
In pretreatment, the calcium and magnesium hardness of waste water can be removed completely using weak acid resin hard-removal system.Weak acid resin
Operational mode is preferably sodium form, so it is possible to prevente effectively from the high salinity of waste water removes hard performance impact to resin.Weak acid resin can
First with after 5% HCl regeneration, continue the NaOH transition with 5%；Weak acid resin goes out the water hardness in control in below 5mg/L.
The present invention process method the step of in (2), preliminary by nanofiltration divides salt, and production water side is mainly sodium chloride, is led to
Cross film concentration and evaporative crystallization obtains the NaCl that purity is not less than 98.5%.Preferably, tentatively divide in salt step in nanofiltration, intake
Control is TDS in more than 20000mg/L.If it can be concentrated less than 20000mg/L by embrane method.
Preliminary by nanofiltration divides salt, and nanofiltration, without rejection, is more than 98% to sulfate radical rejection to chlorion.
The present invention process method the step of in (3), after the concentrated water of nanofiltration removes most of organic matter by oxidative system,
Sodium sulphate (wherein sodium sulphate contains the saltcake that freezing and crystallizing unit returns) is obtained by MVR evaporative crystallizations, is evaporated by MVR
The anhydrous sodium sulfate of crystallization available more than 99.1%.Preferably, the oxidative system of nanofiltration concentrated water include catalytic ozonation and
Charcoal absorption.
The present invention process method the step of in (4), it is preferred to use two-stage process for freezing and crystallizing, wherein, second level freezing
The temperature of crystallization is less than the temperature of first order freezing and crystallizing.For example, first order freezing and crystallizing temperature is 5 degrees Celsius, the first order is cold
It is -5 degrees Celsius to freeze crystallization temperature.
In the technique of the invention described above, the saltcake of freezing and crystallizing needs to return to dehydration in sulfate crystal device and is converted into nothing
Aqueous sodium persulfate, and the mother liquor after sodium peroxydisulfate freezing and crystallizing is made by evaporative crystallization in the second sodium chloride evaporation and crystallization system
Sodium chloride crystallizes, and mother liquor last after the second sodium chloride evaporation and crystallization system, then is solidified by being spray-dried, it may be difficult to
Organic matter and the carnallite discharge of crystallization, ensure the purity of product salinity, reach wastewater zero discharge.
In the technique of the present invention, sodium sulphate evaporative crystallization mother liquor and the mixing of sodium chloride evaporative crystallization mother liquor, then by freezing
Recovery section sodium sulphate after crystallization, mother liquor by evaporative crystallization recovery section sodium chloride, realize that carnallite rate is less than 10% again.
On the other hand, in order to realize the purpose of the present invention, present invention also offers a kind of for the invention described above technique
Waste Water Treatment, the system include：
Tubular type microfiltration systems, its be used to remove in high-salt wastewater most of calcium ions and magnesium ions, silicon, heavy metal and suspension and
Partial organic substances；
Weak acid resin hard-removal system, it is used for the hardness, the basicity that further reduce high-salt wastewater；
NF membrane divides salt system, and it is used for the preliminary of high-salt wastewater and divides salt, and high-salt wastewater is divided into two strands, that is, produce water side and
Concentrated water side, wherein, the salinity of production water side is mainly sodium chloride and minimal amount of sodium sulphate, and the salinity of concentrated water side is mainly sodium sulphate
And partial oxidation sodium；
Nanofiltration concentrated water oxidative system, it is used for the waste water removal after the processing of NF membrane point salt system is most of organic
Thing；
Nanofiltration concentrated water sodium sulphate evaporation and crystallization system；
Sodium sulphate freezing and crystallizing system；
Water high-pressure membrane concentration systems are produced in nanofiltration；
The first sodium chloride evaporation and crystallization system for nanofiltration production water；
For mixing the second sodium chloride evaporation and crystallization system of mother liquor；And
Spray drying system.
Preferably, in the system of the present invention, sodium sulphate freezing and crystallizing system uses two-stage freezing and crystallizing device.For example, adopt
With OSLO crystallizers, two Outer Coolers are set, using ethylene glycol as refrigerant.
In the system of the present invention, tubular type microfiltration systems may include reaction tank, concentration basin, microfiltration membranes and other corollary equipments
Deng；Nanofiltration concentrated water oxidative system may include catalytic ozonation and charcoal absorption etc..
With similar technique of zero discharge in the prior art, process of the invention and processing system at least have following
Beneficial effect：
A, in the present invention, sodium sulphate freezing and crystallizing uses two level freezing and crystallizing, if first order cryogenic temperature is 5 Celsius
Degree, second level cryogenic temperature are -5 degrees Celsius, can greatly solve the problems, such as that sodium sulphate scabs and plugging, is freezed by the first order
More than 80% sulfate crystal is come out, the second level continues to cool, and continues by the processing of 10% sulfate crystal, while using two
Level freezing, the energy consumption of freezing and crystallizing reduce by 30%；
B, the present invention uses three fraction salt, i.e. first step nanofiltration divides salt, two level nanofiltration production water evaporation crystallization production sodium chloride, sodium
Concentrated water evaporative crystallization production sodium sulphate is filtered, three fraction salt are to divide the mother liquor of salt to mix in sodium chloride and sodium sulphate to return by freezing and crystallizing
Receive sodium sulphate, hot method evaporative crystallization reclaims sodium chloride, recycling part of sulfuric acid sodium and sodium chloride, and by sodium chloride back dissolving to two
In the water inlet of the evaporative crystallization of grade sodium chloride, ensure that crystal salt purity in turn ensure that the rate of recovery of salt ensure 90% with
On；
C, pre-treatment step of the invention can use tube type filter membrance TMF techniques, to go the calcium of the easy fouling in removing water,
The easy scale forming matter such as magnesium, silicon, the fouling and pollution problem of follow-up membranous system and evaporative crystallization technique are reduced, solves traditional handicraft
The outlet effect difference occurred in softening precipitation process the shortcomings that, including water outlet ss suspended solid concentration is high, and hardness is high, floor space
The shortcomings that big, by TMF tube type filter membrances, calcium and magnesium hardness can be reduced to 50mg/L, and haze reduction eliminates in 1NUT simultaneously
Ultrafiltration system, system flow simplify.
Below, the present invention is described in detail with reference to the drawings and specific embodiments, but this explanation is not
Limiting the scope of the invention.One of ordinary skill in the art should be understood that certain in the specific embodiment of the invention
A little processing steps and device therefor, the implementation for suitably adjusting or replacing without influenceing the present invention can be carried out completely.
Brief description of the drawings
Fig. 1 is the process chart that sodium sulphate and sodium chloride are reclaimed from high-salt wastewater of the present invention.
Embodiment
Accompanying drawing 1 is referred to, which show the main technological steps of the present invention and device systems used.
In the embodiment of the present invention, by pretreatment system system, (including tubular type microfiltration systems, weak acid resin remove
Hard system) hardness of waste water, basicity, silicon, fluorine ion and suspension are reduced or removed, it ensure that the stable fortune of nanofiltration system
OK, while the crystallization purity salt that follow-up system is produced is improved.Preliminary by nanofiltration divides salt, and production water side is mainly sodium chloride, is led to
Cross film concentration and evaporative crystallization obtains the NaCl that purity is not less than 98.5%.Preliminary by nanofiltration divides salt, and the concentrated water of nanofiltration is led to
After crossing the most of organic matter of advanced oxidative system removal, through overheating method evaporative crystallization production sodium sulphate, its mother liquor evaporates with sodium chloride
The mother liquor mixing of crystallization, saltcake is produced using process for freezing and crystallizing, and saltcake is returned in sodium sulphate evaporation and crystallization system, evaporation knot
Crystalline substance obtains more than 99.1% anhydrous sodium sulfate.Mother liquor after freezing and crystallizing is by double evaporation-cooling crystallization recycling partial oxidation
Sodium, returned to by separation of solid and liquid afterchlorinate sodium in the evaporation and crystallization system of sodium chloride, ensure the overall salt rate of recovery of system
More than 90%, last mother liquor is solidified by being spray-dried, while reaches wastewater zero discharge.
In conjunction with high saliferous Industry Waste moisture salt zero-emission project (the treating capacity 195m3/ of certain industrial park coal chemical industry enterprises
T exemplified by), the high saliferous Industry Waste moisture salt Zero discharging system to the present invention and the technique using its two fraction salt treatment of progress
Describe in detail.
The mean concentration of high each pollutant of saliferous industrial wastewater is as follows：
Table 1
By pretreatment system (including tubular type microfiltration systems, weak acid resin hard-removal system) by the hardness of waste water, basicity,
Silicon, fluorine ion and suspension are reduced or removed, wherein, the water quality of high-salt wastewater is as follows after pretreatment system：
Table 2
By the salt treatment of dividing of nanofiltration, the salinity of production water side is mainly sodium chloride, and the salinity of concentrated water side is mainly sodium chloride
And sodium sulphate, water quality are as follows：
Table 3
| Project | Nanofiltration concentrated water | Water is produced in nanofiltration |
| Na2SO4(mg/L) | 63409.68 | 292.81 |
| NaCl(mg/L) | 11567.67 | 11567.67 |
| CODcr(mg/L) | 223.125 | 10.625 |
| SiO2(mg/L) | 15 | 15 |
| TDS(mg/L) | 75238.13 | 11918.07 |
| Flow (m3/h) | 29.25 | 165.75 |
It is mainly sodium chloride by the production water side salinity divided after salt of nanofiltration, is crystallized by multiple-effect evaporation, is steamed by controlling
Hair amount, avoid sodium chloride and sodium sulphate eutectoid, may finally obtain 3312.54Kg/h, the NaCl solids of more than 97% purity and
Partial mother liquid, mother liquor composition are as follows：
Table 4
Divide salt concentrated water side salinity to be mainly sodium sulphate by nanofiltration, by oxidative system (including catalytic ozonation and
Charcoal absorption), the clearance of organic matter is 60%, i.e. COD is reduced to 93.25mg/l by 223.125mg/l.
Nanofiltration concentrated water after matter-water-organic matter purification unit uses evaporative crystallization, and control evaporation capacity avoids sodium chloride and sulfuric acid
Sodium is eutectoid out, evaporation capacity 8.02T/H, produces 3.45T/H anhydrous sodium sulfate, and wherein freezing and crystallizing part returns to 1.2T/H awns
Nitre, the specific water quality of mother liquor after sulfate crystal are as follows：
Table 5
The mother liquor crystallized by sulfate crystal and sodium chloride, first pass through flash distillation and cool to 60 DEG C in advance, then changed by board-like
Hot device cools to 30 DEG C, and sodium sulphate refrigerating process uses two level freezing and crystallizing, and first order cryogenic temperature is 5 degrees Celsius, the second level
Cryogenic temperature is -5 degrees Celsius, is freezed by the first order and comes out more than 80% sulfate crystal, and the second level continues to cool, after
Continuous that the processing of 10% sulfate crystal, two-stage freezing are obtained into 1.2T/h saltcake, saltcake returns to sodium sulphate evaporation and crystallization system
Anhydrous sodium sulfate is converted into after dehydration.Mother liquor after freezing, mother liquor composition are as follows：
Table 6
It is sodium chloride and a small amount of sodium sulphate that freezing mother liquor, which contains main component, and 1.2t/ is obtained by sodium chloride evaporative crystallization 2
H sodium chloride crystal salts, but purity does not reach 98.5% purity requirement, by the evaporation knot of sodium chloride crystal salt back dissolving to sodium chloride
In crystallographic system system, purity is further improved, and the composition of raffinate includes：NaCl0.2t/h, Na2SO40.08t/h, other carnallites and
Organic matter 0.1Kg/h, remnants realize zero-emission by being spray-dried solidification.
Claims (10)
1. a kind of technique of zero discharge from high-salt wastewater recovery salt, the technique comprises the following steps：
(1) hardness, basicity, silicon, fluorine ion and the suspension of high-salt wastewater are reduced by pretreatment system；
(2) divide salt by the preliminary of nanofiltration, pretreated high-salt wastewater is divided into two strands, that is, produce water side and concentrated water side, wherein,
The salinity for producing water side is mainly sodium chloride, and the salinity of concentrated water side is mainly sodium sulphate and partial oxidation sodium；Production water is concentrated by film
And the first sodium chloride evaporation and crystallization system, obtain the higher NaCl of purity；
(3) tentatively divide the concentrated water obtained by salt through nanofiltration, after removing most of organic matter by oxidative system, evaporate and tie by MVR
Crystalline substance obtains sodium sulphate, wherein, sodium sulphate contains the saltcake of freezing and crystallizing unit return；
(4) nanofiltration concentrated water is mixed through sodium peroxydisulfate evaporative crystallization and nanofiltration production water by the mother liquor of sodium chloride evaporative crystallization, entered
Enter sodium sulphate freezing and crystallizing, obtain saltcake, saltcake, which is returned after sulfate crystal device is dehydrated, is changed into anhydrous sodium sulfate；
(5) mother liquor after sodium peroxydisulfate freezing and crystallizing makes chlorination by evaporative crystallization in the second sodium chloride evaporation and crystallization system
Sodium crystallizes, and after dehydration separation, sodium chloride is dissolved into the first sodium chloride evaporation and crystallization system, to improve the rate of recovery of sodium chloride
And purity；
(6) mother liquor last after the second sodium chloride evaporation and crystallization system is solidified by being spray-dried, and forms carnallite, is realized useless
Water zero discharge.
2. technique as claimed in claim 1, wherein, described pretreatment system includes tubular type microfiltration systems and weak acid resin removes
Hard system；Described tubular type microfiltration systems include reaction tank, concentration basin, microfiltration membranes and other corollary equipments.
3. technique as claimed in claim 2, wherein, in described weak acid resin hard-removal system, the operation mould of weak acid resin
Formula is sodium form, and the water hardness that goes out of weak acid resin is controlled in below 5mg/L.
4. technique as claimed in claim 1, wherein, tentatively divide in salt step in nanofiltration, it is TDS in 20000mg/ to enter water management
More than L.
5. technique as claimed in claim 1, wherein, the oxidative system of nanofiltration concentrated water includes catalytic ozonation and activated carbon is inhaled
It is attached.
6. technique as claimed in claim 1, wherein, using two-stage process for freezing and crystallizing, wherein, the temperature of second level freezing and crystallizing
Temperature of the degree less than first order freezing and crystallizing.
7. a kind of Waste Water Treatment for being used for the technique as described in one of claim 1-6, the system include：
Tubular type microfiltration systems, it is used to remove most of calcium ions and magnesium ions, silicon, heavy metal and suspension and part in high-salt wastewater
Organic matter；
Weak acid resin hard-removal system, it is used for the hardness, the basicity that further reduce high-salt wastewater；
NF membrane divides salt system, and it is used for the preliminary of high-salt wastewater and divides salt, and high-salt wastewater is divided into two strands, that is, produces water side and concentrated water
Side, wherein, the salinity of production water side is mainly sodium chloride and minimal amount of sodium sulphate, and the salinity of concentrated water side is mainly sodium sulphate and portion
Divide sodium chloride；
Nanofiltration concentrated water oxidative system, it is used to the waste water after the processing of NF membrane point salt system removing most of organic matter；
Nanofiltration concentrated water sodium sulphate evaporation and crystallization system；
Sodium sulphate freezing and crystallizing system；
Water high-pressure membrane concentration systems are produced in nanofiltration；
The first sodium chloride evaporation and crystallization system for nanofiltration production water；
For mixing the second sodium chloride evaporation and crystallization system of mother liquor；And
Spray drying system.
8. system as claimed in claim 7, wherein, described sodium sulphate freezing and crystallizing system uses two-stage freezing and crystallizing device.
9. system as claimed in claim 7, wherein, described tubular type microfiltration systems include reaction tank, concentration basin, microfiltration membranes and
Other corollary equipments.
10. the system as claimed in claim 1, wherein, described nanofiltration concentrated water oxidative system includes catalytic ozonation and work
Property charcoal absorption.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591464A (en) * | 2015-02-03 | 2015-05-06 | 石家庄工大化工设备有限公司 | Recycling method of high-salinity wastewater |
| CN104961285A (en) * | 2015-06-30 | 2015-10-07 | 石家庄工大化工设备有限公司 | Method for recycling high-salt waste water containing sodium chloride and sodium sulfate |
| CN104973726A (en) * | 2015-06-30 | 2015-10-14 | 石家庄工大化工设备有限公司 | Recovery processing method of high salinity wastewater containing sodium chloride and sodium sulfate |
| CN105036222A (en) * | 2015-08-19 | 2015-11-11 | 石家庄工大化工设备有限公司 | High-salinity wastewater recovery treatment method |
| CN105152443A (en) * | 2015-09-22 | 2015-12-16 | 江苏中圣高科技产业有限公司 | Method and system for recycling crystallized salt resources in high-salt-content wastewater zero discharge |
-
2017
- 2017-10-20 CN CN201710985878.9A patent/CN107619144A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591464A (en) * | 2015-02-03 | 2015-05-06 | 石家庄工大化工设备有限公司 | Recycling method of high-salinity wastewater |
| CN104961285A (en) * | 2015-06-30 | 2015-10-07 | 石家庄工大化工设备有限公司 | Method for recycling high-salt waste water containing sodium chloride and sodium sulfate |
| CN104973726A (en) * | 2015-06-30 | 2015-10-14 | 石家庄工大化工设备有限公司 | Recovery processing method of high salinity wastewater containing sodium chloride and sodium sulfate |
| CN105036222A (en) * | 2015-08-19 | 2015-11-11 | 石家庄工大化工设备有限公司 | High-salinity wastewater recovery treatment method |
| CN105152443A (en) * | 2015-09-22 | 2015-12-16 | 江苏中圣高科技产业有限公司 | Method and system for recycling crystallized salt resources in high-salt-content wastewater zero discharge |
Non-Patent Citations (1)
| Title |
|---|
| 金明柏: "《水处理***设计实务》", 31 December 2010, 中国电力出版社 * |
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