CN108947064A - A kind of the sub-prime crystallization processes and its system of brine waste - Google Patents
A kind of the sub-prime crystallization processes and its system of brine waste 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
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—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
- C02F1/041—Treatment of water, waste water, or sewage by heating by distillation or evaporation by means of vapour compression
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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
- C02F1/22—Treatment of water, waste water, or sewage by freezing
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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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
Abstract
The invention discloses a kind of sub-prime crystallization techniques of brine waste.Enter MVR vapo(u)rization system after the impurity such as the preprocessed removal hardness of brine waste, basicity, the concentrated water after MVR evaporation minimizing enters freezing and crystallizing system through flash distillation cooling and after purifying further removal of impurities processing.The saltcake that freezing and crystallizing generates final output sulfate crystal salt after fusion-crystallization is then sent after freezing mother liquor heat exchange to two-stage nanofiltration system.Nanofiltration concentrated water is back in freezing and crystallizing system, and nanofiltration produces water and enters sodium chloride crystal system, final output sodium chloride crystal salt.Present invention process process relative to nanofiltration divide salt or other divide salt technology, process is simpler, can effectively realize being completely separated for sal prunella, and product purity salt is high, and the salt rate of recovery is high, can reduce the yield of carnallite to the maximum extent.
Description
Technical field
The present invention relates to a kind of sub-prime crystallization techniques of brine waste, in particular it relates to a kind of brine waste
Sub-prime crystallization processes method and sub-prime crystal system.
Background technique
Mine tail water, coal chemical industrial waste water that the industries such as petrochemical industry, coal chemical industry generate etc. is universal after reverse osmosis concentration
Have the characteristics that salt content height, complicated component, pollution are big, it is necessary to which rationally disposition, high-salinity wastewater zero-emission have been increasingly becoming one
The inevitable requirement of kind environmental protection.However, the carnallite that high-salinity wastewater zero-emission generates is identified as solid dangerous waste, at the current country
The cost for managing solid dangerous waste is too high (generally at 3000 yuan/ton or more), causes heavy burden to enterprise, early stage realizes zero-emission
Coal chemical industry enterprises all suffer from original carnallite crystal system be changed to a point salt system, realize the recycling problem of salt.Therefore, containing
In the disposed of in its entirety technological design of salt waste water, how to realize that waste water recycles to the greatest extent, the resource utilization of salt and it is non-solid
Dangerous waste processing, system investments and operating cost rationalize the focus for having become common concern in the industry now.
According to the water analysis of multiple projects, sal prunella accounting in mine tail water/coal chemical industrial waste water (sodium chloride, sodium sulphate this
Two kinds of components account for the ratio of total salt amount) and sal prunella ratio (ratio of sodium chloride component and sodium sulphate component) enumerate it is as follows:
85% or more even 95% or more component is sodium chloride and sodium sulphate in mine tail water/coal chemical industrial waste water.Therefore,
Realize that the technical grade purification & isolation of sodium chloride and sodium sulphate will have so that technical grade product be made and have a possibility that export trade
There is great application value.There are mainly two types of currently used sub-prime crystallization treatments: being crystallized using the thermal method of sal prunella coproduction principle
Salt technique, Nanofiltering membrane is divided to divide salt technique.
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, root may be implemented by thermal method or Nanofiltering membrane
It is seen according to the operating condition of existing actual items, too long, investment that there are technique chains and operating cost carnallite amount that is high, and generating
Greatly, the salt rate of recovery is relatively low, and the purity of product salt is lower, causes zero-emission point salt system can not continuous and steady operation, investment and fortune
The problems such as capable at high cost, product salt difficulty export trade, carnallite dangerous waste disposition amount remain high.Therefore it provides a kind of technically reliable, economy
Feasible brine waste sub-prime crystallization technique becomes industry urgent problem.
Summary of the invention
The object of the present invention is to provide the low sub-prime knots for brine waste of a kind of product purity salt height, carnallite quantum of output
Crystal technique, especially for mine tail water, coal chemical industry be useless etc., high-salt wastewaters realize sub-prime crystallization, are preserved the ecological environment with meeting
The self-demand of external requirement and resource utilization.
Foregoing invention purpose to realize the present invention, the present invention provides a kind of sub-prime crystallization processes sides of brine waste
Method, the process include following processing step:
(1) brine waste after homogeneous enters efficiently softening clarification unit, to remove most of hardness in waste water, alkali
Degree, heavy metal and part silicon and organic matter；
(2) waste water after step (1) softening, into filter unit, to remove the suspended matter in waste water；
(3) through step (2) filtered waste water, into resin pliable cell, further to remove the total hardness in waste water；
(4) through step (3) treated waste water, into decarburization unit, further to remove the total alkalinity in waste water；
(5) waste water TDS is concentrated into 20%~23% into MVR vapo(u)rization system through step (4) treated waste water；It steams
The production water that hair generates is sent to reclaiming system；
(6) the concentration waste water after step (5) concentration enters cooling down system, will concentration waste water temperature be reduced to 40~
50℃；
(7) the concentration waste water after step (6) cooling enters purification process system, to remove the COD in concentration waste waterCr、
Silicon and suspended matter；
(8) the concentration waste water after step (7) purification process carries out heat exchange cooling before entering freezing and crystallizing again；Heat exchange
Device cold side medium is the mother liquor of freezing and crystallizing；
(9) the concentration waste water after step (8) heat exchange enters freezing and crystallizing system；The mother liquor point of freezing and crystallizing system discharge
For two parts: a part of (mother liquor 1) send to step (13) and handles, and another part is reprocessed after sending to step (8) heat exchange；
(10) saltcake of step (9) freezing and crystallizing institute output is sent into fusion-crystallization system, wherein the production water of fusion-crystallization is sent
To reclaiming system；
(11) mother liquor of freezing and crystallizing, in addition to arranging a part of (mother liquor 1) to carnallite crystal system, remaining is changed through heat exchanger
Two-stage nanofiltration system is sent into after heat heating；The production water of two-stage nanofiltration send to step (12) and is concentrated and is crystallized；Two-stage nanofiltration
Concentrated water then returns to step (9) and carries out freezing and crystallizing, to recycle sodium sulphate；
(12) the production water of step (11) is sent into sodium chloride crystal system, and the production water of sodium chloride crystal system is sent to reuse system
System is discharged a certain amount of mother liquor (mother liquor 2) to step (13) and handles to guarantee to crystallize purity salt；
(13) partial mother liquid that step (9) and step (12) are discharged enters carnallite crystal system；The production water of carnallite crystallization
It send to reclaiming system, the carnallite of output is separately disposed.
In the present invention, before step (1) enters efficiently softening clarification unit, the brine waste of plant area initially enters waste water
Conditioning tank realizes runoff investigation and water quality homogeneous.
In the present invention, be guarantee product salt quality, brine waste need by efficiently softening clarification, filter,
The pretreatment process such as resin softening, decarburization, to remove most of hardness, basicity, heavy metal, suspended matter and the part in waste water
Silicon and organic matter.Preferably, after above-mentioned pretreatment process, it is discharged each pollutant catabolic gene are as follows: CODCrRemoval rate be 10%~
20%, total hardness is (with CaCO3Meter) it is 1~3mmol/l, total alkalinity is (with CaCO3Meter) it is 100~200mg/l.
In aforementioned present invention step (5), it is preferred to use it is 22% or more that MVR vapo(u)rization system, which is concentrated into TDS,.
In aforementioned present invention step (6), the form that shwoot cooling+recirculated cooling water cools is can be used in cooling down,
Concentration waste water temperature is reduced to 40~50 DEG C.
In aforementioned present invention step (7), purification process system may include except CODCrDevice removes silicon device and filter, with
Remove the COD in concentrated waterCr, silicon, suspended matter；Preferably, each pollutant concentration of water outlet of purification process system is controlled are as follows: CODCr
For 100~250mg/l, total silicon is 20~40mg/l.
In aforementioned present invention step (8), plate and frame or shell-and-tube is can be used in heat exchanger, and heat exchanger cold side medium is freezing knot
Brilliant mother liquor.There are two effects for heat exchanger: 1) further concentrated water cooling down, to reduce the thermic load of freezing and crystallizing as far as possible；2) it mentions
The temperature of freezing and crystallizing mother liquor is risen, to guarantee the efficient operation of subsequent membranous system (step (11)).
In aforementioned present invention step (9), the freezing and crystallizing temperature of preferably control freezing and crystallizing system is 0~-5 DEG C, refrigerant
Using calcium chloride solution.
In aforementioned present invention step (10), melting evaporation is can be used in fusion-crystallization system, and saltcake melting temperature is controllable
At 70~80 DEG C, and MVR forced circulation crystallization processes can be used, to realize the crystallization precipitation and purity of sodium sulphate.With complete molten steaming
Hair evaporation is compared, and energy consumption about 30%~40% can be saved.
Further, in aforementioned present invention step (10), to guarantee sulfate crystal purity salt, fusion-crystallization system at regular intervals
A certain amount of mother liquor is discharged to step (6), merges with the MVR concentrated water being concentrated by evaporation, again processing recycling salinity.
In the present invention, due to using freezing and crystallizing+fusion-crystallization system, thus crystallization rate is slow, crystalline particle partial size
Greatly, sodium sulphate purity is high, the standard that can reach I class Grade A in " GB/T6009-2014 industrial anhydrous sodium sulfate " standard are wanted
It asks.
In aforementioned present invention step (11), the pre-heat treatment is can be used in the water inlet of two-stage nanofiltration system, and inflow temperature is can be controlled in
15~20 DEG C.
Further, in aforementioned present invention step (11), which can be used the technique separation for having point salt action
Nanofiltration membrane component, and one bivalent ions point is improved using the form of two-stage nanofiltration to strengthen the transmitance of membranous system sodium chloride
From effect.For two-stage nanofiltration system to rejection >=99% of sodium sulphate, the rejection to sodium chloride is -20%~5%.
In aforementioned present invention step (12), there are three types of modes for usual sodium chloride crystal system: first is that multiple-effect evaporation crystallizes, two
It is MVR evaporative crystallization, third is that TVR evaporative crystallization.Preferably, according to inlet amount, feed component and concentration and Multi-Component Phase Diagram
Balance, by control evaporation capacity, residence time and outlet mother liquor amount, to realize the maximum crystallization amount of precipitation and purity of sodium chloride,
Sodium chloride crystal salt can reach the requirement of the refining industrial salt primary standard in " GB/T5462-2015 Nacl " standard.
Further, in aforementioned present invention step (12), to guarantee to crystallize purity salt, a certain amount of mother liquor (mother liquor 2) is discharged
It is handled to step (13).
In aforementioned present invention step (13), TVR crystal form is can be used in carnallite crystal system.
On the other hand, foregoing invention purpose to realize the present invention, the present invention also provides one kind to be used for above-mentioned technique side
The sub-prime crystal system of method, the system include:
Efficiently softening clarification unit, for remove most of hardness in the brine waste after homogeneous, basicity, heavy metal with
And part silicon and organic matter；
Filter unit, for removing the suspended matter efficiently softened after clarification unit softens in waste water；
Resin pliable cell, for further removing the total hardness after filter unit filters in waste water；
Decarburization unit, for further removing the total alkalinity in resin pliable cell processed waste water；
MVR vapo(u)rization system, for the waste water TDS after decarburization cell processing to be concentrated into 20%~23%；
Cooling down system, for reducing the temperature of the concentration waste water after the concentration of MVR vapo(u)rization system；
Purification process system, for removing the COD in the concentration waste water after the cooling of cooling down systemCr, silicon and suspension
Object；
Heat exchanger, for carrying out the concentration waste water after purification process system purification process again before entering freezing and crystallizing
Heat exchange cooling；
Freezing and crystallizing system, for the concentration waste water after heat exchanger exchanges heat to be carried out freezing and crystallizing；
Fusion-crystallization system, for the saltcake of freezing and crystallizing system institute output to be carried out fusion-crystallization；
Two-stage nanofiltration system, for handling the mother liquor of the freezing and crystallizing system after heat exchanger heat exchange heating；
Sodium chloride crystal system, for the production water of two-stage nanofiltration system to be carried out sodium chloride crystallization；
Carnallite crystal system, the partial mother liquid for handling freezing and crystallizing system and sodium chloride crystal system is discharged.
Compared with prior art, in sub-prime crystallization technique of the invention, since freezing mother liquor is carried out using two-stage nanofiltration
The separation of sodium chloride and sodium sulphate greatly reduces the discharge amount of freezing and crystallizing mother liquor and sodium chloride crystalline mother solution, and sufficiently returns
Sodium chloride and sodium sulphate salinity are received, the total salt rate of recovery of system is improved.The total salt rate of recovery of system can reach 85%~90%, be
Carnallite rate of uniting is only 10%~15%.
Further, compared with prior art, in the sub-prime crystallization technique of brine waste of the invention, freezing mother liquor into
It is handled before entering sodium chloride crystallization using two-stage nanofiltration, not only increases sal prunella ratio, substantially increase the crystallization amount of precipitation of sodium chloride,
It is also greatly reduced the impurity concentration (COD of sodium chloride crystallization water inletCr, silicon etc.), thus promoted sodium chloride crystal salt purity and
Quality.
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 that sub-prime crystallization is carried out to brine waste.
Specific embodiment
It elaborates below in conjunction with drawings and examples to a specific embodiment of the invention:
(1) certain brine waste is plant area's coal chemical industrial waste water through front process treated reverse osmosis membrane dope, each main dirt
Contaminate object mean concentration are as follows: CODCrFor 205mg/l, Ca2+For 120mg/l, Mg2+For 40mg/l, total alkalinity is (with CaCO3Meter) be
500mg/l, total silicon 75mg/l, TDS 55730mg/l, Cl?For 12470mg/l, SO4 2-For 20758mg/l, Na+For
18010mg/l.Design inflow is 50t/h.
(2) efficiently soften each total quantity control on emission of clarification and effluent are as follows: CODCrFor 156.8mg/l, Ca2+For 22.5mg/l,
Mg2+For 10.8mg/l, total alkalinity is (with CaCO3Meter) it is 73mg/l, total silicon 15.6mg/l, TDS 54369.9mg/l, Cl?For
12467.8mg/l SO4 2-For 21595.1mg/l, Na+For 18530.3mg/l, SS 10mg/l.
(3) filter is discharged each total quantity control on emission are as follows: CODCrFor 156.8mg/l, Ca2+For 22.5mg/l, Mg2+
For 10.8mg/l, total alkalinity is (with CaCO3Meter) it is 73mg/l, total silicon 15.6mg/l, TDS 54369.9mg/l, Cl?For
12467.8mg/l SO4 2-For 21595.1mg/l, Na+For 18530.3mg/l, SS 2mg/l.
(4) resin softening is discharged each total quantity control on emission are as follows: CODCrFor 156.8mg/l, Ca2+For 0.3mg/l, Mg2+For
0.2mg/l, total alkalinity is (with CaCO3Meter) it is 73mg/l, total silicon 15.6mg/l, TDS 54382.7mg/l, Cl?For
12467.8mg/l SO4 2-For 21595.1mg/l, Na+For 18575.9mg/l.
(5) decarburization is discharged each total quantity control on emission are as follows: CODCrFor 156.8mg/l, Ca2+For 0.3mg/l, Mg2+For
0.2mg/l, total alkalinity is (with CaCO3Meter) it is 13.1mg/l, total silicon 15.6mg/l, TDS 54368.5mg/l, Cl?For
12467.8mg/l SO4 2-For 21652.7mg/l, Na+For 18575.9mg/l.
By pretreated brine waste, some variations of salt content remove most hardness basicity, while reduction has
The impurity compositions such as machine pollutant, silicon, heavy metal greatly improve the operation stability of subsequent technique.
(6) vertical falling film evaporator+MVR vapour compression machine+forced-circulation evaporation form is used, after MVR evaporates
Each total quantity control on emission of concentrated water are as follows: CODCrFor 617.3mg/l, total silicon 68.6mg/l, TDS 238929.3mg/l, Cl?For
54765.7mg/l SO4 2-For 95225.6mg/l, Na+For 81651.6mg/l.Concentrated water water after MVR evaporates is 10t/h,
The treatment scale of subsequent technique is greatly reduced, to substantially reduce operating cost.
(7) purification process efficiently removes silicon+multi-medium filtering technique using ozone catalytic advanced oxidation+magnesia mixture/aluminium agent, through pure
Each total quantity control on emission after change processing are as follows: CODCrFor 197.5mg/l, total silicon 20.6mg/l.It is removed according to Water-quality control ozone &
Silicon medicament adds proportion and reaction time, to control the performance of purification process, guarantees the influent quality requirement of freezing and crystallizing.
(8) for freezing and crystallizing controlled at 0 DEG C, refrigerant uses calcium chloride solution.According to charging water quality characteristics, can will freeze
Water inlet approximation regards " NaCl-Na as2SO4- H2O system ".According to Phase Diagram for Aqueous Salt Solutions data, influent quality, two-stage nanofiltration concentrated water
Water quality etc. does not transfinite by adjusting outlet mother liquor amount to control the impurity concentration of freezing and crystallizing circulation feed liquid, to ensure that saltcake is analysed
Output and purity.Final discharge mother liquor amount (mother liquor 1) is 0.5t/h, and the saltcake amount that COMPREHENSIVE CALCULATING obtains freezing and crystallizing output is
3.04t/h (based on solid content 95% after dehydration).At this point, the major impurity index of freezing and crystallizing circulation feed liquid are as follows: CODCrFor
1276.6mg/l Ca2+For 25.4mg/l, Mg2+For 16.9mg/l, total silicon 55.7mg/l.
(9) saltcake of freezing and crystallizing output uses MVR fusion-crystallization, female by control evaporation capacity, residence time and outlet
Liquid measure (discontinuous, a small amount of) guarantees the amount of precipitation and purity of sodium sulphate.Final sodium sulphate finished product salt amount is 1.29t/h.
(10) sulfate crystal salt can reach " GB/T6009-2014 industry anhydrous slufuric acid by dehydration, dry and packaging
The standard requirements of I class Grade A in sodium " standard.The safeguard measure of sulfate crystal purity salt mainly has:
● process route mature and reliable: freezing and crystallizing+fusion-crystallization；
● technology controlling and process: control freezing and crystallizing temperature, control freezing and crystallizing circulation feed liquid impurity concentration, control mother liquor outlet
It measures, according to water quality survey evaporation capacity；
● lectotype selection: salt leg structure of the crystallizer with functions such as collection salt, classification, elutriation, back dissolving, coolings mentions significantly
Quality with high salt；Dewaterer with washing function is selected, crystal salt is further washed and purified using distilled water.
(11) according to the cycle calculations of freezing and crystallizing and two-stage nanofiltration, determine that the amount of inlet water of two-stage nanofiltration is 20t/h.Control
Fine frozen crystallization discharge mother liquor into temperature before two-stage nanofiltration be 15 DEG C, with this determine heat exchanger area and freezing and crystallizing into
Coolant-temperature gage.The two-stage nanofiltration rate of recovery about 32.3%, i.e. the production water of two-stage nanofiltration are 6.46t/h.Two-stage nanofiltration produces each pollutant of water
Mean concentration are as follows: CODCrFor 204.3mg/l, total silicon 27.3mg/l, TDS 139120mg/l, Cl?For 77983.8mg/l,
SO4 2-For 67.7mg/l, Na+For 51345.9mg/l, NO3 ?For 6472mg/l.Two-stage nanofiltration concentrated water is back to freezing and crystallizing system
Sodium sulphate is recycled, the impurity such as organic matter, silicon, the chloride of accumulation pass through freezing and crystallizing outlet mother liquor discharge system.
(12) the production water of two-stage nanofiltration uses MVR crystallization mode, passes through control evaporation capacity, residence time and outlet mother liquor amount
To guarantee the amount of precipitation and purity of sodium chloride.Final sodium chloride finished product salt amount is 0.60t/h.Mother liquor amount (mother liquor 2), which is discharged, is
When 0.5t/h, the major impurity index of sodium chloride crystallisation cycle feed liquid are as follows: CODCrFor 2786.6mg/l, Ca2+For 0.96mg/l,
Mg2+For 0.64mg/l, NO3 ?For 97635.9mg/l, total silicon 412.8mg/l.
(13) sodium chloride crystal salt can reach " GB/T5462-2015 Nacl " standard by dehydration, dry and packaging
In refining industrial salt primary standard requirement.The safeguard measure of sodium chloride crystallization purity salt mainly has:
● two-stage nanofiltration is to SO4 2-Rejection >=99%, substantially increase sal prunella ratio, and nitrate because of solubility height not
Can be precipitated, thus two-stage nanofiltration admirably ensure that sodium chloride be precipitated while sodium sulphate and sodium nitrate will not be precipitated；In addition, two
Retention of the grade nanofiltration to impurity such as organic pollutant, silicon, also greatly improves the quality of sodium chloride crystallization water inlet, to mention significantly
The quality of high sodium chloride crystal salt, can also reduce the discharge amount of mother liquor.
● technology controlling and process: control crystallisation cycle feed liquid impurity concentration, the outer discharge capacity of control mother liquor are evaporated according to water quality survey
Amount；
● lectotype selection: salt leg structure of the crystallizer with functions such as collection salt, classification, elutriation, back dissolving, coolings mentions significantly
Quality with high salt；Dewaterer with washing function is selected, crystal salt is further washed and purified using distilled water.
(14) to sum up, output sodium chloride crystal salt finished product is 0.60t/h, and output sulfate crystal salt finished product is 1.29t/h,
Output carnallite amount is 0.29t/h, and the system salt rate of recovery is 86.70%, and system carnallite rate is 13.30%.
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 sub-prime crystallization processes method of brine waste, which includes following processing step:
(1) brine waste after homogeneous enters efficiently softening and clarifies unit, to remove most of hardness in waste water, basicity, again
Metal and part silicon and organic matter；
(2) waste water after step (1) softening, into filter unit, to remove the suspended matter in waste water；
(3) through step (2) filtered waste water, into resin pliable cell, further to remove the total hardness in waste water；
(4) through step (3) treated waste water, into decarburization unit, further to remove the total alkalinity in waste water；
(5) waste water TDS is concentrated into 20%~23% into MVR vapo(u)rization system through step (4) treated waste water；Evaporation produces
Raw production water is sent to reclaiming system；
(6) the concentration waste water after step (5) concentration enters cooling down system, and concentration waste water temperature is reduced to 40 ~ 50
℃；
(7) the concentration waste water after step (6) cooling enters purification process system, to remove the COD in concentration waste waterCr, silicon and
Suspended matter；
(8) the concentration waste water after step (7) purification process carries out heat exchange cooling before entering freezing and crystallizing again；Heat exchanger is cold
Side medium is the mother liquor of freezing and crystallizing；
(9) the concentration waste water after step (8) heat exchange enters freezing and crystallizing system；The mother liquor of freezing and crystallizing system discharge is divided into two
Part: a part of (mother liquor 1) send to step (13) and handles, and another part is reprocessed after sending to step (8) heat exchange；
(10) step (9) freezing and crystallizing institute output saltcake be sent into fusion-crystallization system, wherein the production water of fusion-crystallization send to return
Use system；
(11) mother liquor of freezing and crystallizing, in addition to arranging a part of (mother liquor 1) to carnallite crystal system, remaining exchanges heat through heat exchanger and rises
Two-stage nanofiltration system is sent into after temperature；The production water of two-stage nanofiltration send to step (12) and is concentrated and is crystallized；The concentrated water of two-stage nanofiltration
It then returns to step (9) and carries out freezing and crystallizing, to recycle sodium sulphate；
(12) the production water of step (11) is sent into sodium chloride crystal system, and the production water of sodium chloride crystal system is sent to reclaiming system；
(13) partial mother liquid that step (9) and step (12) are discharged enters carnallite crystal system；Carnallite crystallization production water send to
The carnallite of reclaiming system, output is separately disposed.
2. sub-prime crystallization processes method as described in claim 1, wherein TDS after using MVR vapo(u)rization system to be concentrated for
22% or more.
3. sub-prime crystallization processes method as described in claim 1, wherein each pollutant control of control purification process system water outlet
Concentration processed are as follows: CODCrFor 100~250mg/l, total silicon is 20~40mg/l.
4. sub-prime crystallization processes method as described in claim 1, wherein control freezing and crystallizing system freezing and crystallizing temperature be
0~-5 DEG C, refrigerant uses calcium chloride solution.
5. sub-prime crystallization processes method as described in claim 1, wherein the fusion-crystallization system is using melting evaporation
Method, saltcake melting temperature are controlled at 70~80 DEG C, and use MVR forced circulation crystallization processes, to realize the crystallization analysis of sodium sulphate
Out and purity.
6. sub-prime crystallization processes method as described in claim 1, wherein the fusion-crystallization system at regular intervals discharge unit denominator
Liquid is to step (6), and simultaneously, processing recycling salinity, pure to improve sulfate crystal salt again for the thickened waste hydration with MVR vapo(u)rization system
Degree.
7. sub-prime crystallization processes method as described in claim 1, wherein the two-stage nanofiltration system water inlet is using at preheating
Reason, inflow temperature are controlled at 15~20 DEG C.
8. sub-prime crystallization processes method as claimed in claim 7, wherein the nanofiltration system, which uses, has point salt action
Technique separates nanofiltration membrane component, and using the form of two-stage nanofiltration, to strengthen the transmitance of membranous system sodium chloride.
9. sub-prime crystallization processes method as described in claim 1, wherein in step (12), to guarantee to crystallize purity salt, row
A certain amount of mother liquor (mother liquor 2) to step (13) are handled out.
10. a kind of sub-prime crystal system for the process as described in one of claim 1-9, the system include:
Efficiently softening clarification unit, for removing most of hardness, basicity, heavy metal and portion in the brine waste after homogeneous
Divide silicon and organic matter；
Filter unit, for removing the suspended matter efficiently softened after clarification unit softens in waste water；
Resin pliable cell, for further removing the total hardness after filter unit filters in waste water；
Decarburization unit, for further removing the total alkalinity in resin pliable cell processed waste water；
MVR vapo(u)rization system, for the waste water TDS after decarburization cell processing to be concentrated into 20%~23%；
Cooling down system, for reducing the temperature of the concentration waste water after the concentration of MVR vapo(u)rization system；
Purification process system, for removing the COD in the concentration waste water after the cooling of cooling down systemCr, silicon and suspended matter；
Heat exchanger, for the concentration waste water after purification process system purification process to exchange heat again before entering freezing and crystallizing
Cooling；
Freezing and crystallizing system, for the concentration waste water after heat exchanger exchanges heat to be carried out freezing and crystallizing；
Fusion-crystallization system, for the saltcake of freezing and crystallizing system institute output to be carried out fusion-crystallization；
Two-stage nanofiltration system, for handling the mother liquor of the freezing and crystallizing system after heat exchanger heat exchange heating；
Sodium chloride crystal system, for the production water of two-stage nanofiltration system to be carried out sodium chloride crystallization；
Carnallite crystal system, the partial mother liquid for handling freezing and crystallizing system and sodium chloride crystal system is discharged.
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