CN108996785A - A kind of high slat-containing wastewater thoroughly divides salt crystallization processes and its system - Google Patents
A kind of high slat-containing wastewater thoroughly divides salt crystallization processes and its system Download PDFInfo
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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
- C01D3/14—Purification
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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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- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- 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
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- 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
- C02F2301/00—General aspects of water treatment
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Abstract
Thoroughly divide salt crystallization technique the invention discloses a kind of high slat-containing wastewater, wherein enter NF after the preprocessed system of high slat-containing wastewater and divide salt system: NF, which is produced after water is concentrated and purification process, enters evaporation and crystallization system, final output sodium chloride crystal salt；Enter freezing and crystallizing+fusion-crystallization system, final output sulfate crystal salt after the purified processing of NF concentrated water and concentration；The partial mother liquid of freezing and crystallizing enters freezing NF system, further solventing-out, and freezing NF concentrated water is back to freezing and crystallizing unit, and freezing NF production water, which is sent to NF production water, to be mixed.The technology of the present invention can guarantee the stability and high efficiency of system water variation water quality time-division salt, realize being completely separated for sal prunella, and product purity salt is high, and the rate of recovery of product salt is high, can reduce the yield of carnallite to the maximum extent.
Description
Technical field
Thoroughly divide salt resource technology the present invention relates to a kind of high slat-containing wastewater, in particular it relates to a kind of
The thorough of high slat-containing wastewater divides salt process and thoroughly divides salt crystal system.
Background technique
Desulfurization wastewater, mine tail water, the coal chemical industrial waste water etc. that the industries such as electric power, petrochemical industry, coal chemical industry generate generally have
There is the features such as high salt content, hardness height, complicated component, big pollution, such as unreasonable disposition will cause serious environmental pollution.Mirror
Ecologically fragile area is typically in these industries, receiving water body needed for non-pollution discharge, and generally without abundance around factory
Water source need the water treatment facilities of high-recovery to meet production requirement.Therefore, in order to which that preserves the ecological environment external wants
The self-demand for resource utilization of summing, wastewater zero discharge/near-zero release have been increasingly becoming a kind of industrial trend.
" pretreatment-biochemical treatment (can be not provided with)-advanced treating-water process with high salt " generallyd use at present it is " close
Zero-emission " technology path, the crystal salt finally generated contain plurality of inorganic salt and large amount of organic.From the angle for reinforcing environmental protection
Degree sets out, and the carnallite that high slat-containing wastewater generates is fixed tentatively as solid dangerous waste.And the cost of current domestic processing solid dangerous waste
Substantially at 3000 yuan/ton or more, cost is even also than the sum of leading portion pretreatment, film concentration, evaporative crystallization Deng Ge workshop section cost
Want high.Therefore, in the design of entire high slat-containing wastewater treatment process, if product can be regard final solid product as
Sale rather than solid dangerous waste disposition will have very big application value.
Recycling currently is substantially to the disposition thinking of salt, i.e. sub-prime divides salt treatment.Salt in high slat-containing wastewater
Main component is typically all sodium chloride, sodium sulphate, both component sums can account for the 90- of all salt in waste water
95%, so the technique direction of current main-stream is directed to realize the technical grade of sodium sulphate and sodium chloride in evaporation and crystal process
Purification & isolation, so that technical grade product be made and have a possibility that export trade.
There are mainly two types of currently used sub-prime point salt treatment: pure thermal method crystallization divides salt technique, Nanofiltering membrane to divide salt+heat
Method/cold process crystallizes group technology.
Chinese patent application CN201610072782.9 discloses a kind of high saliferous Industry Waste moisture salt Zero discharging system, side
After accurate pretreatment unit, membrane separation concentration unit, crystallization recycling cell processing, producing water can return high slat-containing wastewater in method
With, and obtain sodium chloride, sodium sulphate, sodium nitrate crystal salt and carnallite.
Chinese patent application CN201520251103.5 discloses a kind of low energy consumption coal chemical industry strong brine sub-prime crystallization combination
Device, device include: except hard softening plant, NF separation membrane device, reverse osmosis unit with high salt, produce water ED film condensing device, production water
Evaporated crystallization device, produce jellyfish liquid drier, AOP catalytic oxidizing equipment, active carbon filtering device, concentration ED film condensing device,
Concentrated water evaporated crystallization device, concentrated water mother liquor drier.It realizes that coal chemical industry strong brine all recycles by above-mentioned apparatus, realizes
Zero-emission.
In above technical scheme, the separation of sodium chloride, sulfate crystal salt may be implemented, but the carnallite amount generated is big,
The problems such as salt rate of recovery is relatively low, and the purity of product salt is lower, remains high there are the export trade of product salt difficulty, carnallite dangerous waste disposition amount.
Therefore it provides the technology that a kind of high slat-containing wastewater thoroughly divides salt to crystallize becomes industry urgent problem.
Chinese patent application 201710985878.9 discloses a kind of zero-emission work from high slat-containing wastewater recycling crystal salt
Skill and its processing system, the processing system include tubular type microfiltration systems, weak acid resin hard-removal system, nanofiltration membrane point salt system, receive
Filter concentrated water oxidative system, nanofiltration concentrated water sodium sulphate evaporation and crystallization system, sodium sulphate freezing and crystallizing system etc..However, existing skill
In art, even technique of zero discharge, there is also the higher problems of carnallite amount.Thus it is necessary to further promote the salt rate of recovery and drop
The low carnallite quantum of output as the discharge of solid dangerous waste.
Summary of the invention
The object of the present invention is to provide it is a kind of further promoted the salt rate of recovery and reduce carnallite quantum of output, be directed to high saliferous
Waste water thoroughly divides salt crystallization technique, to meet the self-demand of the external requirement and resource utilization preserved the ecological environment.
To achieve the purpose of the present invention, on the one hand, thoroughly divide salt technique side the present invention provides a kind of high slat-containing wastewater
Method comprising following processing step:
(1) high slat-containing wastewater after homogeneous is pre-processed, pretreated waste water enters NF points of salt system, obtains NF
Film produces water and NF film concentrated water；
(2) the resulting NF film production water of step (1) enters concentration systems I, obtains producing the concentrated water after water and concentration, wherein
The production water of the step is sent to reclaiming system；
(3) concentrated water after step (2) concentration enters purification process system I；
(4) concentrated water after step (3) purification process enters evaporation and crystallization system, and the production water of evaporation and crystallization system is sent to returning
Use system；
(5) the NF film concentrated water that NF points of salt system of step (1) generates enters purification process system II；
(6) concentrated water after step (5) purification process carries out concentration systems I I；
(7) concentrated water after step (6) concentration first carries out precooling treatment before entering freezing and crystallizing；
(8) concentrated water after step (7) precooling treatment enters freezing and crystallizing system；
(9) saltcake through step (8) freezing and crystallizing output is sent into fusion-crystallization system；The production water of fusion-crystallization is sent to reuse
System；
(10) a small amount of mother liquor is discharged in step (4), step (8) and step (9), it is entered carnallite crystal system；Carnallite
The production water of crystallization is sent to reclaiming system, and the carnallite of output need to be disposed separately.
Since the process of aforementioned present invention uses freezing and crystallizing+fusion-crystallization technique, crystallization rate is slow, crystallization
Grain partial size is big, sodium sulphate is with high purity, can reach I class Grade A in " GB/T 6009-2014 industrial anhydrous sodium sulfate " standard
Standard requirements.
Preferably, further to promote the salt rate of recovery and reducing carnallite quantum of output, thoroughly divide salt technique side in of the invention
Further comprise following processing step in method:
(11) circulation fluid of partial freeze crystallization is sent into freezing NF system；Wherein, freezing and crystallizing circulation fluid first passes through step
Suddenly (7) and freezing and crystallizing water inlet exchange heat, to improve the solubility of sodium sulphate in circulation fluid；The production water of NF system is freezed with sodium chloride
Based on, it send to step (2) and is concentrated and is crystallized, to recycle sodium chloride；NF concentrated water is freezed based on sodium sulphate, returns to step
(8) freezing and crystallizing is carried out, to recycle sodium sulphate.
In the present invention, before step (1) is pre-processed, the high slat-containing wastewater of plant area initially enters wastewater equalization pond,
Realize runoff investigation and water quality homogeneous.
In aforementioned present invention step (1), pretreatment system may include efficient softening clarification, filter, ultrafiltration apparatus,
Resin softening process is protected with removing most of hardness in waste water, basicity, heavy metal, suspended matter and part silicon and organic matter
Demonstrate,prove subsequent membranous system normal table operation.Preferably, it can control each pollutant catabolic gene concentration of water outlet of pretreatment system are as follows: CODCr
For 50~100mg/l, total hardness is (with CaCO3Meter) it is 2~6mg/l, total alkalinity is (with CaCO3Meter) it is 50~80mg/l.
In aforementioned present invention step (1), NF points of salt system can be by being pressurized between booster pump, cartridge filter, high-pressure pump, section
Pump, nanofiltration membrane group, skid, valve group, in-line meter etc. are constituted.NF film produces water based on sodium chloride, will be fed into step (2) progress
Concentration；NF film concentrated water will be fed into step (5) and carried out purification process based on sodium sulphate, sodium chloride.Preferably, NF is controlled
Dividing salt system is 95%~98% to the rejection of sodium sulphate, and the rejection to sodium chloride is -10%~10%.
In aforementioned present invention step (2), two ways is can be used in concentration systems I: first is that reverse osmosis membrane is concentrated, second is that thermal method
It is concentrated by evaporation.It is such as concentrated using reverse osmosis membrane, process flow, which is pressed, " divides salt (step (1)) → concentration (step (2)) → purifying (step
Suddenly (3)) → evaporative crystallization (step (4)) " it carries out；Such as using thermal method be concentrated by evaporation, process flow by " divide salt (step (1)) →
Purify (step (3)) → concentration (step (2)) → evaporative crystallization (step (4)) " it carries out.The production water of concentration process is sent to reuse system
System.
In aforementioned present invention step (3), purification process system I may include except CODCrDevice removes silicon device, filter, takes off
Carbon device, to remove the COD in concentrated waterCr, silicon, suspended matter, basicity, guarantee subsequent technique crystal salt purity.Preferably, in this hair
Each pollutant catabolic gene concentration of water outlet of bright middle control purification process system I are as follows: CODCrFor 40~60mg/l, total hardness is (with CaCO3
Meter) it is 1~3mg/l, total alkalinity is (with CaCO3Meter) it is 10~30mg/l.
In aforementioned present invention step (4), there are three types of modes for evaporation and crystallization system: first is that multiple-effect evaporation crystallizes, second is that MVR steams
Hair crystallization, third is that TVR evaporative crystallization.The production water of evaporative crystallization is sent to reclaiming system, the sodium chloride crystal salt dry packing of output
Export trade afterwards, a small amount of mother liquor are sent into step (10) and carry out carnallite crystallization.It, can be according to inlet amount, feed component and dense in the step
The balance of degree and Multi-Component Phase Diagram, by control evaporation capacity, residence time and outlet mother liquor amount, to realize the maximum knot of sodium chloride
Partial crystallization output and purity, sodium chloride crystal salt can reach the refining industrial salt level-one in " GB/T 5462-2015 Nacl " standard
Standard requirements.
In aforementioned present invention step (5), purification process system II may include except CODCrDevice removes silicon device, filter, with
Remove the COD in concentrated waterCr, silicon, suspended matter, guarantee subsequent technique crystal salt purity.Preferably, purification process system II is controlled
Each pollutant catabolic gene concentration of water outlet are as follows: CODCrFor 150~250mg/l, silicon is 5~15mg/l.
In aforementioned present invention step (6), reverse osmosis membrane concentration is can be used in concentration systems II, and film produces water and send to reclaiming system,
Film concentrated water enters step (7).
In aforementioned present invention step (7), shell-and-tube heat exchanger is can be used in precooling treatment, and hot side is the concentrated water after concentration, cold
Side is the water inlet for freezing NF.As a kind of specific embodiment of the invention, shell-and-tube heat exchanger, tube side is can be used in heat exchanger
For the concentrated water after concentration, shell side is the water inlet for freezing NF.Tube side inlet temperature is 20~25 DEG C, and tube side outlet temperature is 12~17
℃；Shell side inlet temperature is 0~5 DEG C, and outlet temperature is 4~9 DEG C.
In aforementioned present invention step (8), the sodium chloride crystal salt that freezing and crystallizing is precipitated is sent into fusion-crystallization processing, freezing and crystallizing
A small amount of mother liquor is discharged to carnallite crystallization treatment.Preferably, the temperature for controlling freezing and crystallizing is 0~5 DEG C, and refrigerant is molten using ethylene glycol
Liquid.
In aforementioned present invention step (9), the saltcake of freezing and crystallizing output is sent into fusion-crystallization system, the production water of fusion-crystallization
It send to reclaiming system, export trade after the sulfate crystal salt dry packing of output, a small amount of mother liquor is sent into step (10) and carries out carnallite knot
It is brilliant.In the step, complete molten dehydration by evaporation method is can be used in saltcake thermosol, for example, by using MVR crystallization/TVR crystallization processes, and can basis
Inlet amount, feed component and concentration, by control evaporation capacity, residence time and outlet mother liquor amount, to realize the maximum of sodium sulphate
The accumulation for crystallizing amount of precipitation and purity, and preventing chloride, organic matter, silicon, nitrate etc..
In aforementioned present invention step (10), TVR crystal form is can be used in carnallite crystal system.
In aforementioned present invention step (11), before refrigerating cycle liquid enters freezing NF system, a heat exchanger II need to be increased, with
The solubility of sodium sulphate in circulation fluid is improved, guarantees the normal operation of freezing NF system.Heat exchanger II form can change for shell-and-tube
Hot device, tube side are the water inlet for freezing NF system, and shell side is recirculated cooling water.Tube side inlet temperature is 4~9 DEG C, tube side outlet temperature
Degree is 12~17 DEG C.Recirculated cooling water can be used in refrigerant.
In aforementioned present invention step (11), two-stage the pre-heat treatment is can be used in freezing NF system water inlet, and system, which uses, to be had
The technique of salt action is divided to separate nanofiltration membrane component, and using the form of two-stage nanofiltration, to strengthen the transmitance of membranous system sodium chloride,
One bivalent ions separating effect is provided.Preferably, control NF divides salt system and freezes the two-stage NF system of NF system to sulfuric acid
The rejection of sodium is 97%~98.5%, and the rejection to sodium chloride is -20%~5%.
In above-mentioned process of the invention, due to greatly reducing freezing outlet mother liquor amount using freezing NF system,
And sodium chloride and sodium sulphate salinity are sufficiently recycled, for the total salt rate of recovery of system up to 85%~90%, system carnallite rate is 10%
~15%.
On the other hand, to achieve the purpose of the present invention, the present invention also provides a kind of for the thorough of above-mentioned process
Point salt crystal system, this thoroughly divides the salt crystal system to include:
Pretreatment system；
NF divides salt system, obtains NF film and produces water and NF film concentrated water；
Concentration systems I, the NF film for generating to NF points of salt system produce water and are concentrated；
Purification process system I, concentrated water carries out purification process after the concentration for generating to concentration systems I；
Evaporation and crystallization system, the concentrated water after purification process for generating to purification process system I are evaporated crystallization；
Purification process system II, the NF film concentrated water for dividing salt system to generate NF carry out purification process；
Concentration systems II, the concentrated water after purification process for generating to purification process system II are concentrated；
Chilldown system, concentrated water is first pre-chilled before entering freezing and crystallizing after the concentration for generating to concentration systems II
Processing；
Freezing and crystallizing system, for carrying out freezing and crystallizing to the concentrated water after chilldown system precooling treatment；
Fusion-crystallization system carries out fusion-crystallization processing for the saltcake to freezing and crystallizing system freezing and crystallizing output；
Carnallite crystal system, for evaporation and crystallization system, freezing and crystallizing system and fusion-crystallization system to be discharged on a small quantity
Mother liquor carries out carnallite crystallization.
Preferably, above-mentioned that salt crystal system is thoroughly divided to further comprise freezing NF system, for partial freeze to be crystallized
Circulation fluid be sent into freezing NF system.
In thoroughly dividing in salt crystal system for aforementioned present invention, pretreatment system may include efficient softening clarification, filter tank mistake
Filter, ultrafiltration apparatus, resin softening process, to remove most of hardness, basicity, heavy metal, suspended matter and the part in waste water
Silicon and organic matter.
In thoroughly dividing in salt crystal system for aforementioned present invention, purification process system I may include except CODCrDevice removes silicon dress
It sets, filter, decarbonizer, to remove the COD after concentration caused by concentration systems I in concentrated waterCr, silicon, suspended matter, basicity.
In thoroughly dividing in salt crystal system for aforementioned present invention, purification process system II may include except CODCrDevice removes silicon
Device, filter, the COD in NF film concentrated water to remove the generation of NF points of salt systemCr, silicon, suspended matter.
Compared with prior art, especially compared with Chinese patent application 201710985878.9, technology of the invention has
Many improvement:
1) sulfate crystal mode is different: Chinese patent application 201710985878.9 goes out sodium sulphate technique using thermal method,
The present invention uses freezing and crystallizing+fusion-crystallization technique；
2) salt way of recycling is different: Chinese patent application 201710985878.9 is crystallized using Freeze crystallization sodium chloride
Mother liquor and sulfate crystal mother liquor, to recycle saltcake and sodium chloride；The present invention divides salt using freezing NF system again, to return respectively
Receive sodium chloride and sodium sulphate；
3) pretreatment mode is different, and the present invention is using efficiently softening clarification+filter+ultrafiltration apparatus+resin softening etc.
Technique, to guarantee the quality and grade of product salt；
4) purification process I technique is equipped with before sodium chloride evaporative crystallization, to be further ensured that the quality of product sodium chloride and wait
Grade.
These are different and other different, so that technology of the invention is compared with the existing technology, can guarantee system water
The stability and high efficiency of variation water quality time-division salt realize being completely separated for sal prunella, and product purity salt is high, the rate of recovery of product salt
Height can reduce the yield of carnallite to the maximum extent.
In the following, the present invention is described in detail in conjunction with the drawings and specific embodiments, but this explanation is not
Limiting the scope of the invention.Those skilled in the art should be understood that certain in the specific embodiment of the invention
A little processing steps and device therefor can carry out appropriate adjustment or replacement without influencing implementation of the invention completely.
Detailed description of the invention
Fig. 1 is the process flow chart of the invention for carrying out thoroughly dividing salt to high slat-containing wastewater.
Specific embodiment
It elaborates below in conjunction with drawings and examples to a specific embodiment of the invention:
(1) certain each total quantity control on emission of haline water waste water are as follows: CODCrFor 60mg/l, Ca2+For 150mg/l, Mg2+For
50mg/l, total alkalinity is (with CaCO3Meter) it is 600mg/l, total silicon 35mg/l, TDS 22000mg/l, Cl-For 7000mg/l,
SO4 2-For 6400mg/l, Na+For 7450mg/l.
(2) after efficiently softening clarification, filter, ultrafiltration apparatus, resin softening, pretreatment system is discharged each pollutant
Mean concentration are as follows: CODCrFor 52mg/l, Ca2+For 0.3mg/l, Mg2+For 0.2mg/l, total alkalinity is (with CaCO3Meter) it is 50mg/l,
Total silicon is 20mg/l, TDS 21000mg/l, Cl-For 6750mg/l, SO4 2-For 6500mg/l, Na+For 7500mg/l.
(3) waste water enters NF points of salt system after pre-processing, and NF divides each total quantity control on emission of production water of salt system are as follows: CODCr
For 10mg/l, TDS 11400mg/l, Cl-For 6700mg/l, SO4 2-For 130mg/l, Na+For 4450mg/l.NF divides salt system
Each total quantity control on emission of concentrated water are as follows: CODCrFor 337mg/l, Ca2+For 2.13mg/l, Mg2+For 1.42mg/l, total alkalinity (with
CaCO3Meter) it is 83.93mg/l, total silicon 20mg/l, TDS 86143mg/l, Cl-For 7089.3mg/l, SO4 2-For 49725mg/
L, Na+For 28196.4mg/l.
(4) NF divides the production water of salt mainly based on sodium chloride, concentrated I and I processing of purifying after, into evaporative crystallization system
System, each total quantity control on emission of the water inlet of evaporative crystallization are as follows: CODCrFor 45mg/l, Ca2+For 0.3mg/l, Mg2+For 0.2mg/l,
Total alkalinity is (with CaCO3Meter) it is 100mg/l, total silicon 60mg/l, TDS 107900mg/l, Cl-For 63450mg/l, SO4 2-For
1100mg/l, Na+For 42100mg/l.
(5) evaporation and crystallization system uses MVR evaporation+MVR crystallization processes, and vaporization cycle liquid temperature is 107 DEG C, crystallisation cycle
Liquid temperature is 111 DEG C, and by control evaporation capacity and outlet mother liquor amount, the sodium chloride crystal salt of crystal system passes through dehydration, drying
And packaging, it can reach the refining industrial salt primary standard requirement in " GB/T 5462-2015 Nacl " standard.Outside evaporative crystallization
Arrange each total quantity control on emission of mother liquor are as follows: CODCrFor 1100mg/l, TDS 341000mg/l, Cl-For 158450mg/l, SO4 2-
For 27000mg/l, Na+For 127000mg/l.
(6) NF divides the concentrated water of salt mainly based on sodium sulphate, purified II and II processing of concentration after, into freezing and crystallizing system
System, each total quantity control on emission of the water inlet of freezing and crystallizing are as follows: CODCrFor 294.9mg/l, Ca2+For 3.73mg/l, Mg2+For
2.5mg/l, total alkalinity is (with CaCO3Meter) it is 146.9mg/l, total silicon 35mg/l, TDS 150750mg/l, Cl-For
12406mg/l, SO4 2-For 87019mg/l, Na+For 49344mg/l.
(7) freezing and crystallizing system controlled at 5 DEG C, refrigerant uses ethylene glycol solution, the water inlet of freezing and crystallizing system
Temperature is controlled at 10~12 DEG C, guarantees the purity that saltcake is precipitated by control outlet mother liquor amount.Freezing and crystallizing outlet mother liquor
Each total quantity control on emission are as follows: CODCrFor 3300mg/l, TDS 84000mg/l, Cl-For 15460mg/l, SO4 2-For
37000mg/l, Na+For 27800mg/l.
(8) fusion-crystallization system use MVR crystallization processes, crystallisation cycle liquid temperature be 107 DEG C, by control evaporation capacity,
Residence time and outlet mother liquor amount, sulfate crystal salt can reach " GB/T 6009-2014 work by dehydration, dry and packaging
The standard requirements of I class Grade A in industry anhydrous sodium sulfate " standard.Each total quantity control on emission of fusion-crystallization outlet mother liquor are as follows:
CODCrFor 880mg/l, TDS 345000mg/l, Cl-For 4360mg/l, SO4 2-For 227500mg/l, Na+For 111900mg/l.
(9) freezing and crystallizing circulation fluid part is sent to freezing NF system.Circulation fluid after two-stage preheats, freezing NF system into
Coolant-temperature gage is 15 DEG C, using the form of two-stage nanofiltration, freezes each total quantity control on emission of production water of NF system are as follows: CODCrFor
30mg/l, TDS 23200mg/l, Cl-For 13850mg/l, SO4 2-For 42mg/l, Na+For 9000mg/l.It is main to freeze NF production water
Based on sodium chloride, it is mixed with the production water of NF points of salt system into concentration systems I, to recycle sodium chloride salinity.Freeze NF
Each total quantity control on emission of the concentrated water of system are as follows: CODCrFor 4535mg/l, Ca2+For 48.6mg/l, Mg2+For 29.2mg/l, total silicon
For 45mg/l, TDS 106400mg/l, Cl-For 15500mg/l, SO4 2-For 51300mg/l, Na+For 34600mg/l.Freeze NF
Concentrated water is back to freezing and crystallizing system recycling sodium sulphate, and the impurity such as organic matter, silicon, the chloride of accumulation pass through freezing and crystallizing outlet
Mother liquor discharge system.
(10) the sodium chloride crystal salt of evaporation and crystallization system output purity >=98.5% is 1.98t/h, freezing and crystallizing+melting
The sulfate crystal salt of crystal system output purity >=99.0% is 1.86t/h, and carnallite system output carnallite amount is 0.52t/h,
The system salt rate of recovery is 88.07%, and system carnallite rate is 11.93%.
Although the invention patent is disclosed above in the preferred embodiment, it is not intended to limit the invention the model of patent working
It encloses.Any those skilled in the art improve in the invention scope for not departing from the invention patent when can make a little,
I.e. all same improvement done according to the invention patent, the range that should be the invention patent are covered.
Claims (10)
1. a kind of high slat-containing wastewater thoroughly divides salt process comprising following processing step:
(1) high slat-containing wastewater after homogeneous is pre-processed, pretreated waste water enters NF points of salt system, obtains the production of NF film
Water and NF film concentrated water；
(2) the resulting NF film production water of step (1) enters concentration systems I, obtains producing the concentrated water after water and concentration, wherein the step
Rapid production water is sent to reclaiming system；
(3) concentrated water after step (2) concentration enters purification process system I；
(4) concentrated water after step (3) purification process enters evaporation and crystallization system, and the production water of evaporation and crystallization system is sent to reuse system
System；
(5) the NF film concentrated water that NF points of salt system of step (1) generates enters purification process system II；
(6) concentrated water after step (5) purification process carries out concentration systems II；
(7) concentrated water after step (6) concentration first carries out precooling treatment before entering freezing and crystallizing；
(8) concentrated water after step (7) precooling treatment enters freezing and crystallizing system；
(9) saltcake through step (8) freezing and crystallizing output is sent into fusion-crystallization system；The production water of fusion-crystallization is sent to reuse system
System；
(10) a small amount of mother liquor is discharged in step (4), step (8) and step (9), it is entered carnallite crystal system；Carnallite crystallization
Production water send to reclaiming system, the carnallite of output need to be disposed separately.
Further comprise following processing step 2. thoroughly dividing salt process as described in claim 1:
(11) circulation fluid of partial freeze crystallization is sent into freezing NF system；Wherein, freezing and crystallizing circulation fluid first passes through step (7)
It intakes and exchanges heat with freezing and crystallizing, to improve the solubility of sodium sulphate in circulation fluid；The production water of NF system is freezed based on sodium chloride,
It send to step (2) and is concentrated and is crystallized, to recycle sodium chloride；Freeze NF concentrated water based on sodium sulphate, return to step (8) into
Row freezing and crystallizing, to recycle sodium sulphate.
3. thoroughly dividing salt process as described in claim 1, wherein in the freezing and crystallizing system, control freezing
The temperature of crystallization is 0~5 DEG C, and refrigerant uses ethylene glycol solution.
4. thoroughly dividing salt process as described in claim 1, wherein divide in salt system in NF, control it to sodium sulphate
Rejection is 95%~98%, and the rejection to sodium chloride is -10%~10%.
5. thoroughly dividing salt process as described in claim 1, wherein each pollutant of water outlet of control purification process system I
Controlled concentration are as follows: CODCrFor 40~60mg/l, total hardness is (with CaCO3Meter) it is 1~3mg/l, total alkalinity is (with CaCO3Meter) it is 10
~30mg/l；Control each pollutant catabolic gene concentration of water outlet of purification process system II are as follows: CODCrFor 150~250mg/l, silicon 5
~15mg/l.
6. thoroughly dividing salt process as claimed in claim 2, wherein control NF divides salt system and freezes the two-stage of NF system
NF system is 97%~98.5% to the rejection of sodium sulphate, and the rejection to sodium chloride is -20%~5%.
7. a kind of divide salt crystal system for the thorough of process as described in one of claim 1-6, this thoroughly divides salt to crystallize
System includes:
Pretreatment system；
NF divides salt system, obtains NF film and produces water and NF film concentrated water；
Concentration systems I, the NF film for generating to NF points of salt system produce water and are concentrated；
Purification process system I, concentrated water carries out purification process after the concentration for generating to concentration systems I；
Evaporation and crystallization system, the concentrated water after purification process for generating to purification process system I are evaporated crystallization；
Purification process system II, the NF film concentrated water for dividing salt system to generate NF carry out purification process；
Concentration systems II, the concentrated water after purification process for generating to purification process system II are concentrated；
Chilldown system, concentrated water first carries out precooling treatment before entering freezing and crystallizing after the concentration for generating to concentration systems II；
Freezing and crystallizing system, for carrying out freezing and crystallizing to the concentrated water after chilldown system precooling treatment；
Fusion-crystallization system carries out fusion-crystallization processing for the saltcake to freezing and crystallizing system freezing and crystallizing output；
Carnallite crystal system, for a small amount of mother liquor to be discharged to evaporation and crystallization system, freezing and crystallizing system and fusion-crystallization system
Carry out carnallite crystallization.
8. thoroughly dividing salt crystal system as claimed in claim 7, further comprises freezing NF system, be used for partial freeze
The circulation fluid of crystallization is sent into freezing NF system.
9. thoroughly dividing salt crystal system as claimed in claim 7 or 8, wherein the pretreatment system includes efficiently softening
Clarification, filter, ultrafiltration apparatus, resin softening process, to remove most of hardness in waste water, basicity, heavy metal, suspension
Object and part silicon and organic matter.
10. thoroughly dividing salt crystal system as claimed in claim 7 or 8, wherein the purification process system I includes removing
CODCrDevice removes silicon device, filter, decarbonizer, to remove the COD after concentration caused by concentration systems I in concentrated waterCr、
Silicon, suspended matter, basicity；The purification process system II includes removing CODCrDevice removes silicon device, filter, to remove NF points
The COD in NF film concentrated water that salt system generatesCr, silicon, suspended matter.
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