CN110194552A - A kind of wastewater zero discharge system that realizing salt recycling and method - Google Patents
A kind of wastewater zero discharge system that realizing salt recycling and method Download PDFInfo
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- CN110194552A CN110194552A CN201910485257.3A CN201910485257A CN110194552A CN 110194552 A CN110194552 A CN 110194552A CN 201910485257 A CN201910485257 A CN 201910485257A CN 110194552 A CN110194552 A CN 110194552A
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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
- C02F1/441—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
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
- C02F2301/043—Treatment of partial or bypass streams
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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
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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Abstract
The present invention discloses a kind of wastewater zero discharge system for realizing salt recycling and method, is related to field of waste water treatment；The Zero discharging system includes reverse osmosis membrane system, nanofiltration membrane system and evaporation and crystallization system, and concrete methods of realizing includes waste water being recycled pure water by reverse osmosis membrane system after pretreatment, and carry out concentrate to salinity and form strong brine；Strong brine, which enters nanofiltration membrane system, to carry out point salt and operates, and obtains the concentrated water a containing high price salt ion and is enriched with the production water a of monovalence salt ion；The concentrated water a and production water a carries out concentrate again again by reverse osmosis membrane system respectively, then respectively enters corresponding evaporation and crystallization system and pure salt and mother liquor is prepared；Mother liquor, which enters the product that mother liquor nanofiltration system obtain after point salt operation, can be again introduced into evaporation and crystallization system and/or counter-infiltration system circular treatment, the final zero-emission for realizing waste water.
Description
Technical field
The present invention relates to field of waste water treatment more particularly to a kind of wastewater zero discharge system for realizing salt recycling and sides
Method.
Background technique
Growing tension and economic continuous development along with water resource, industrial enterprise is in environmental protection and discharge of wastewater side
The pressure in face increases increasingly, and wastewater zero discharge is gradually becoming the primary selection of current industrial enterprise.
For general waste water, form it is more complicated, it is inorganic including various organic matters and different ions type
Substance.However, the organic matter scale forming matter related to heavy metal etc. in waste water has been removed after pretreatment, turn
Become the waste water composition based on sodium chloride, sodium sulphate and water.
For general wastewater zero discharge system, principle nothing more than using embrane method or thermal method realize in waste water salinity and
The separation of water, method include reverse osmosis membrane, electrodialytic membranes, flash distillation, multiple-effect evaporation or mechanical compression evaporation etc..However, this
It can only be sodium chloride and the salt-mixture that sodium sulphate component can not determine that a little methods are finally obtained, these solid salts are as waste water zero
The by-product of exhaust system can not be used as the raw material of industry, can only be used as waste treatment, not only bring at higher waste
It is set to this, also brings potential environment hidden danger during waste treatment.
There is partial monopoly (such as CN107619144A, CN206858345U etc.) to refer to be divided using nanofiltration in recent years
Sodium chloride and sodium sulphate are carried out entering back into evaporation and crystallization system after UF membrane, tentatively realize the pure of Zero discharging system by salt
Salt is produced.However, evaporation and crystallization system has to be discharged a certain amount of mother liquor to maintain since the characteristics of UF membrane itself limits
The purity of crystal salt.And these highly concentrated mother liquors can only realize entire industrial wastewater zero-emission by solidifying or mixing the modes such as ash
Place system it is complete.
Summary of the invention
The purpose of the present invention is to provide a kind of wastewater zero discharge systems for realizing salt recycling, to solve the prior art
Present in foregoing problems.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of wastewater zero discharge system for realizing salt recycling, the Zero discharging system include reverse osmosis membrane system, nanofiltration
Membranous system and evaporation and crystallization system, the reverse osmosis membrane system are filtered water using principle of reverse osmosis；The nanofiltration membrane system
System is separated using ion of the nanofiltration principle to different component；The evaporation and crystallization system is using evaporating principle to water and salinity
Isolated evaporation and crystallization system.
Preferably, after the high strong brine in the Zero discharging system carries out point salt treatment by nanofiltration system, finally into
Enter evaporation and crystallization system, the mother liquor of the evaporation and crystallization system discharge in the Zero discharging system is again introduced into nanofiltration system and is divided
Salt treatment, the different component after mother liquor point salt treatment in the Zero discharging system eventually enter into corresponding evaporation and crystallization system
Prepare pure salt.
Preferably, the reverse osmosis membrane system, the nanofiltration membrane system and the evaporation and crystallization system are no less than one.
Preferably, the nanofiltration membrane selects polyamide or poly- piperazine material, the nanofiltration membrane can for wound membrane element,
Flat membrane component, hollow fibre membrane component, processing enter the nanofiltration system of the high strong brine of evaporation and crystallization system, with processing evaporation knot
The nanofiltration system of brilliant the systematic stock solution can be same set of device, or different covering devices.
Preferably, the reverse osmosis membrane selects polyamide or poly- piperazine material；The reverse osmosis membrane can be rolled film
Element, flat membrane component, hollow fibre membrane component.
Preferably, the Zero discharging system further includes pretreatment system and product processing system, and the pretreatment system is set
It sets in the front end of the wastewater zero discharge system, for removing waste water scale forming matter therein；The product systems setting exists
The tail end of the wastewater zero discharge system, for being further processed to product.
Preferably, the pretreatment system includes coagulation, precipitating, biochemistry treatment, advanced oxidation processing, air bearing, mistake
At least one of filter, melded system, the product processing system includes reverse osmosis produced water tank, drying system and mixes in ash system
At least one.
The present invention also provides a kind of wastewater zero discharge system methods for realizing salt recycling, and the method includes following steps
It is rapid:
S1, waste water recycles pure water by reverse osmosis membrane system after pretreatment, and carries out concentrate to salinity and form dense salt
Water；
S2, strong brine, which enters nanofiltration membrane system, to carry out point salt and operates, and obtains the concentrated water a containing high price salt ion and enrichment one
The production water a of valence salt ion；
S3, the concentrated water a and the production water a carry out concentrate again again by reverse osmosis membrane system respectively, then respectively
Pure salt and mother liquor is prepared into corresponding evaporation and crystallization system；
S4, mother liquor, which enters the product that mother liquor nanofiltration system obtain after point salt operation, can be again introduced into evaporation and crystallization system
And/or counter-infiltration system circular treatment.
Preferably, further include between step S3 and S4 by mother liquor obtained in step S3 using pure water or it is different form and
The salt water logistics 352 and 353 of ingredient enter back into the mother liquor nanofiltration system in step S4 after being diluted.
Preferably, the method also includes the processing step of end product, specifically:
Mother liquor nanofiltration system treated concentrated water either can be mixed grey mode by spray drying, roller drying to enter
Drying system is handled.
The beneficial effects of the present invention are:
It is provided by the invention experiment salt recycling wastewater zero discharge system be integrated with reverse osmosis membrane, evaporation and crystallization system with
And nanofiltration membrane system, by different types of preprocessing system, as coagulation, precipitating, biochemistry treatment, advanced oxidation processing,
Air bearing, filtering, softening etc. enter reverse osmosis after eliminating the most suspended substances in water, solid particle and organic matter
System recycles pure water and salt water is concentrated, and strong brine carries out a point salt treatment by nanofiltration system, and isolated purity is higher
Salt water and then be concentrated or be concentrated by evaporation into pure salt crystal system by film and obtain pure salt, and the mother liquor of crystal system
It again passes by nanofiltration membrane system processing and carries out the separation of salt component, the pure component after isolating and purifying imports corresponding evaporative crystallization system
System realizes the technical solution for realizing zero-emission to industry/municipal wastewater, and completes the water resource in waste water and salt resource dual time
It receives, especially to the high yield recycling of sodium chloride and sodium sulphate and recycling, reduces Zero discharging system for solid waste/danger of environment
Useless pollution, realizes circular economy.
Detailed description of the invention
Fig. 1 is the wastewater zero discharge system composition schematic diagram that the present invention realizes salt recycling；
Fig. 2 is the schematic diagram for the wastewater zero discharge system dilution formula of liquid that the present invention realizes salt recycling；
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with attached drawing, to the present invention into
Row is further described.It should be appreciated that the specific embodiments described herein are only used to explain the present invention, it is not used to
Limit the present invention.
Embodiment 1
The present embodiment provides a kind of wastewater zero discharge systems for realizing salt recycling, as shown in Figure 1, in the embodiment of the present invention
In, the major part of wastewater zero discharge system includes reverse osmosis membrane system 201,202,203, nanofiltration membrane system 301,302,303,
Ash system 103 is dried or mixed to evaporation and crystallization system 401,402 and pretreatment system 101, at reverse osmosis produced water tank 102.
Pretreatment system 101 is connected with reverse osmosis membrane system 201, then reverse osmosis membrane system 201 respectively with it is reverse osmosis produced
Water tank 102 is connected with nanofiltration membrane system 301, and nanofiltration membrane system 301 is connected with two sub- processing systems respectively, two sub- processing systems
System is divided into high valence ion processing system and monovalent ion processing system, and high valence ion processing system includes counter-infiltration system 202, steams
Crystal system 401 and nanofiltration membrane system 302 are sent out, and is connected between them using pipeline；Monovalent ion processing system includes reverse osmosis
Permeable system 203, evaporation and crystallization system 402 and nanofiltration membrane system 303, and be connected between them using pipeline.
Wherein, waste water passes through pretreatment system 101, remove the related scale forming matter such as organic matter therein and heavy metal it
Afterwards, waste water composition is changed into based on sodium chloride, sodium sulphate and water.Since waste water salinity is generally lower at this time, so using
Reverse osmosis membrane system 201 recycles the pure water in waste water, and carries out concentrate to salinity, and strong brine subsequently enters nanofiltration membrane system 301
It carries out point salt to operate, obtain concentrated water a and produces water a, enrichment produces rich in water a using sodium sulphate as the high price salt ion of representative in concentrated water a
Integrate the monovalence salt ion using sodium chloride as representative.Optionally, the concentrated water a of nanofiltration membrane system 301 and production water a still can be by corresponding
High valence ion reverse osmosis membrane system 202 and monovalent ion reverse osmosis membrane system 203 carry out concentrate, and recovery section pure water again.
Respectively after high valence ion reverse osmosis membrane system 202 and the processing of monovalent ion reverse osmosis membrane system 203 obtained high price from
Sub- strong brine and monovalent ion strong brine c, high valence ion evaporation and crystallization system 401 and monovalent ion evaporation and crystallization system 402 are made
Standby pure salt, and pass through evaporation and crystallization system 401 and 402 treated that high valence ion mother liquor b and monovalent ion mother liquor c then enters phase
The nanofiltration membrane system 302 and 303 answered carries out point salt and operates, and will finally pass through what nanofiltration membrane system 302 and 303 point salt obtained later
Product a and product b is transported to dry or mixes ash system 103, finally obtains salt product.
Monovalent ion is had in high price strong brine, the presence of high valence ion is had in monovalence strong brine, also in order to guarantee
The salt ion in waste water obtained is able to achieve recycling, to realize that product purity is higher, the higher purpose of product yield.Therefore,
For high valence ion mother liquor b after dividing salt by nanofiltration membrane system 302, obtained production water is transported to monovalent ion reverse osmosis membrane 203
Before or before evaporation and crystallization system 402；Likewise, low price ion mother liquor c is after dividing salt by nanofiltration membrane system 303,
Obtained production water a part is transported to the reverse osmosis concentrated compression system 202 of high valence ion or high valence ion evaporation and crystallization system 401.
In addition, realizing salt recycling as much as possible to realize, high price salt ion and monovalent ion can not be by primary
It is separated from mother liquor completely after processing, therefore obtains production water after the operation of nanofiltration system 302 and 303 point salt and also need
It is again introduced into evaporation and crystallization system and/or counter-infiltration system circular treatment.
It is specifically described as follows, the product transmission direction after the processing of each step is as shown in phantom in Figure 1, evaporation and crystallization system
401 receive the strong brine b based on monovalence salt ion, and then contain a certain amount of high valence ion in its mother liquor, therefore nanofiltration membrane
Concentrated water before importing reverse osmosis membrane 203 or before evaporation and crystallization system 402 after the processing of system 302, into high price from
The reverse osmosis concentrated compression system 202 of son or high valence ion evaporation and crystallization system 401；Meanwhile the production water of mother liquor nanofiltration system 302
It then imports before 202 perhaps before 401 into the reverse osmosis concentrated compression system of monovalent ion or monovalent ion evaporation and crystallization system,
In addition, the production water of mother liquor nanofiltration system 302 due to containing part lead to ebullioscopic monovalence salt ion, also can partially enter with
Minimizing compression, the cost of processing are also accordingly greatly lowered.
Evaporation and crystallization system 402 receives the strong brine based on high price salt ion, and then containing a certain amount of in its mother liquor
Monovalent ion, therefore the production water of its mother liquor nanofiltration system 303 imports before 202 or before 401, it is reverse osmosis into monovalent ion
Concentration systems or monovalent ion evaporation and crystallization system；Meanwhile the concentrated water of mother liquor nanofiltration system 303 then import before 203 or
Before 402, into the reverse osmosis concentrated compression system of high valence ion or high valence ion evaporation and crystallization system, in addition, mother liquor nanofiltration system
303 concentrated water also partially can mix ash into spray drying/roller drying/due to containing the higher organic substance of concentration as model
The drying system 103 of example, compared with direct mother liquor is dry, processing water has obtained minimizing compression, the cost of processing also phase
It should be greatly lowered.
During evaporative crystallization, in order to separate thoroughly monovalent ion and high valence ion solution, higher benefit is realized
Expenditure can reduce ion concentration by diluting the method for mother liquor, therefore before entering mother liquor nanofiltration system 302 and 303, come
Mother liquor from 401 and 402 can be diluted later again by the salt water logistics 352 and 353 of pure water or different compositions and ingredient
Into 302 and 303, this available more detailed narration in Fig. 2.
It is indicated by the dotted line in Fig. 2 it is found that the evaporation and crystallization system mother liquor nanofiltration system 302 and 303 receives respectively comes from
The mother liquor of evaporation and crystallization system 401 and 402, but before entering nanofiltration system 302 and 303, mother liquor can be by from anti-
The pure water of osmosis system water production tank 102 is diluted, can also by from divide concentrated water/production water of salt nanofiltration system 301 into
Row dilution, can also be diluted by the strong brine from counter-infiltration system 401 and 402, can also be by above-mentioned five logistics
Logistics after being mixed in a certain proportion is diluted.
Following experimental examples are tested with the system and method in above-described embodiment, select heterogeneity content waste water and
The nanofiltration membrane of unlike material carries out experimental test:
Experimental example 1
The test film that this experimental example provides is poly- piperazine material rolling nanofiltration membrane, the water quality such as table of the strong brine water inlet of use
Shown in 1, reverse osmosis concentrated salt water water inlet is simulated, operating flux is 15L/ (m2.h), the operation rate of recovery is 75%, and test temperature 20 is taken the photograph
Family name's degree, test result are as shown in table 2.
Table 1. simulates reverse osmosis concentrated salt water influent quality (unit: mg/L)
The test of table 2. divides salt nanofiltration concentrated water and producing water water quality (unit: mg/L)
Experimental example 2
The test film that this experimental example provides is poly- piperazine material rolling nanofiltration membrane, and simulation sodium chloride evaporator mother liquor water quality is such as
Shown in table 3, operating flux is 15L/ (m2.h), the operation rate of recovery is 95%, and wherein nanofiltration membrane is the setting of two-stage UF membrane, second level
Nanofiltration concentrate recirculation enters level-one nanofiltration water inlet, and 20 degrees Celsius of test temperature, test result is as shown in table 4.
Table 3. simulates sodium chloride evaporator mother liquor influent quality (unit: mg/L)
The test of table 4. divides salt nanofiltration concentrated water and producing water water quality (unit: mg/L)
Experimental example 3
Test film is poly- piperazine material rolling nanofiltration membrane, and the nanofiltration concentrated water water quality for simulating embodiment 2 is as shown in table 5, according to
Four times be diluted with water after tested, operating flux be 15L/ (m2.h), the operation rate of recovery is 85%, and test temperature 20 is Celsius
Degree, test result are as shown in table 6.
Water quality (2) (unit: mg/L) after table 5. is simulated the nanofiltration concentrated water water quality (1) of embodiment 2 and diluted
The test of table 6. divides salt nanofiltration concentrated water and producing water water quality (unit: mg/L)
Experimental example 4
Test film is poly- piperazine material rolling nanofiltration membrane, and simulation sodium sulphate refrigerating evaporator mother liquor water quality is as shown in table 7, fortune
Row flux is 15L/ (m2.h), operation the rate of recovery be 75%, 15 degrees Celsius of test temperature.Test result is as shown in table 8.
Table 7. simulates sodium sulphate refrigerating evaporator mother liquor influent quality (unit: mg/L)
The test of table 8. divides salt nanofiltration concentrated water and producing water water quality (unit: mg/L)
By using above-mentioned technical proposal disclosed by the invention, following beneficial effect has been obtained:
This waste water pass through different types of preprocessing system, as coagulation, precipitating, biochemistry treatment, advanced oxidation processing,
Air bearing, filtering, softening etc. enter reverse osmosis after eliminating the most suspended substances in water, solid particle and organic matter
System recycles pure water and salt water is concentrated, and strong brine carries out a point salt treatment by nanofiltration system, and isolated purity is higher
Salt water and then be concentrated or be concentrated by evaporation into pure salt crystal system by film and obtain pure salt, and the mother liquor of crystal system
It again passes by nanofiltration membrane system processing and carries out the separation of salt component, the pure component after isolating and purifying imports corresponding evaporative crystallization system
System, realizes the zero-emission of strong brine.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
Depending on protection scope of the present invention.
Claims (10)
1. a kind of wastewater zero discharge system for realizing salt recycling, which is characterized in that the Zero discharging system includes reverse osmosis membrane
System, nanofiltration membrane system and evaporation and crystallization system, the reverse osmosis membrane system are filtered water using principle of reverse osmosis；It is described
Nanofiltration membrane system is separated using ion of the nanofiltration principle to different component；The evaporation and crystallization system utilizes evaporating principle pair
The evaporation and crystallization system that water and salinity are separated.
2. the wastewater zero discharge system according to claim 1 for realizing salt recycling, which is characterized in that the zero-emission system
After high strong brine in system carries out point salt treatment by nanofiltration system, evaporation and crystallization system, the zero-emission system are eventually entered into
The mother liquor of evaporation and crystallization system discharge in system is again introduced into nanofiltration system and carries out a point salt treatment, the mother in the Zero discharging system
Different component after liquid point salt treatment eventually enters into corresponding evaporation and crystallization system and prepares pure salt.
3. the wastewater zero discharge system according to claim 2 for realizing salt recycling, which is characterized in that the reverse osmosis membrane
System, the nanofiltration membrane system and the evaporation and crystallization system are no less than one.
4. the wastewater zero discharge system according to claim 2 for realizing salt recycling, which is characterized in that the nanofiltration membrane choosing
With polyamide or poly- piperazine material, the nanofiltration membrane can be wound membrane element, flat membrane component, hollow fibre membrane component,
Processing enters the nanofiltration system of the high strong brine of evaporation and crystallization system, the nanofiltration system with processing evaporation and crystallization system mother liquor, can be with
For same covering device, or different covering devices.
5. the wastewater zero discharge system according to claim 2 for realizing salt recycling, which is characterized in that the reverse osmosis membrane
Select polyamide or poly- piperazine material；The reverse osmosis membrane can be wound membrane element, flat membrane component, doughnut membrane element
Part.
6. the wastewater zero discharge system according to claim 1 for realizing salt recycling, which is characterized in that the zero-emission system
System further includes pretreatment system and product processing system, the pretreatment system be arranged in the wastewater zero discharge system most before
End, for removing waste water scale forming matter therein；The tail end of the wastewater zero discharge system is arranged in the product systems, is used for
Product is further processed.
7. the wastewater zero discharge system according to claim 4 for realizing salt recycling, which is characterized in that the pretreatment system
System includes at least one of coagulation, precipitating, biochemistry treatment, advanced oxidation processing, air bearing, filtering, melded system, described
Product processing system includes reverse osmosis produced water tank, drying system and at least one of mixes ash system.
8. a kind of wastewater zero discharge system method for realizing salt recycling, which is characterized in that the described method comprises the following steps:
S1, waste water recycles pure water by reverse osmosis membrane system after pretreatment, and carries out concentrate to salinity and form strong brine；
S2, strong brine, which enters mother liquor nanofiltration membrane system, to carry out point salt and operates, and obtains the concentrated water a containing high price salt ion and enrichment one
The production water a of valence salt ion；
S3, the concentrated water a and the production water a carry out concentrate again again by reverse osmosis membrane system respectively, then respectively enter
Pure salt and mother liquor is prepared in corresponding evaporation and crystallization system；
S4, mother liquor enter the product that mother liquor nanofiltration system obtain after the operation of point salt can be again introduced into evaporation and crystallization system and/
Or counter-infiltration system circular treatment.
9. according to the method described in claim 8, it is characterized in that, further include between step S3 and S4 will be obtained in step S3
Mother liquor is entered back into step S4 after being diluted using the salt water logistics 352 and 353 of pure water or different compositions and ingredient
Mother liquor nanofiltration system.
10. according to the method described in claim 8, it is characterized in that, having the method also includes the processing step of end product
Body are as follows:
By mother liquor nanofiltration system treated concentrated water can either mixing grey mode enters drying by spray drying, roller drying
System is handled.
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| CN111233233A (en) * | 2019-11-21 | 2020-06-05 | 江苏久吾高科技股份有限公司 | Resource utilization method and device for RO concentrated solution |
| CN111547921A (en) * | 2020-05-19 | 2020-08-18 | 厦门嘉戎技术股份有限公司 | System and method for high-salinity concentrated water reduction and purification |
| CN114105349A (en) * | 2020-12-18 | 2022-03-01 | 内蒙古久科康瑞环保科技有限公司 | Zero-emission resource utilization system and process method of fracturing flow-back fluid |
| CN114671554A (en) * | 2020-12-24 | 2022-06-28 | 大连波美科技有限公司 | Zero-discharge sewage system containing guanidine salt and application method |
| CN114772823A (en) * | 2022-03-30 | 2022-07-22 | 烟台金正环保科技有限公司 | Evaporation mother liquor treatment system and process |
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