CN107902822A - The recovery and treatment method of the high-salt wastewater of sodium chloride-containing and sodium sulphate - Google Patents
The recovery and treatment method of the high-salt wastewater of sodium chloride-containing and sodium sulphate Download PDFInfo
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- CN107902822A CN107902822A CN201710968292.1A CN201710968292A CN107902822A CN 107902822 A CN107902822 A CN 107902822A CN 201710968292 A CN201710968292 A CN 201710968292A CN 107902822 A CN107902822 A CN 107902822A
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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
- 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
- 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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- 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
- C02F1/043—Details
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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
- C02F1/048—Purification of waste water by evaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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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
- C02F1/72—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
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- 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 invention discloses sodium chloride-containing and the recovery and treatment method of the high-salt wastewater of sodium sulphate, belong to field of industrial waste water treatment, pass through nanofiltration membrane, through the filtered fluid of NF membrane sodium chloride is obtained through evaporative crystallization, the trapped fluid for not passing through NF membrane obtains sodium sulphate through evaporative crystallization, and a mother liquor return system is mixed with raw material continues cycling through utilization.The method of the present invention can carry out effective recycling to the sodium sulphate in high-salt wastewater and sodium chloride, not only achieve the purpose that to handle high-salt wastewater, met current Environmental Protection Situation needs, and turn waste into wealth, the recycling of salt is realized, improves the income of factory.
Description
The application is the 201510375661.7 entitled " chloride containing of Application No. submitted on June 30th, 2015
The divisional application of China's application of the recovery and treatment method of the high-salt wastewater of sodium and sodium sulphate ".
Technical field
The present invention relates to a kind of processing method of waste water, the high-salt wastewater of especially a kind of sodium chloride-containing and sodium sulphate returns
Receiving processing method.
Background technology
There is large amount of sewage discharge in coal chemical industry production process.These sewage also include a large amount of in addition to organic matter is included
Salt.Coal chemical industry sewage cuts down organic matter by biochemical treatment, solid matter is filtered out by filtration treatment, in remaining waste water
Sodium sulphate, vulcanized sodium and other micro salts are consisted predominantly of, normally referred to as high-salt wastewater.
On the treatment technology of high-salt wastewater, decades are had studied both at home and abroad, and the method for generally use is main at present
Including bioanalysis, SBR Process and evaporative desalination method etc..In numerous high-salt wastewater treatment technologies, evaporative desalination method has
Technology maturation, can handle the advantages that waste water scope is wide, processing speed is fast, energy saving, thus have larger development prospect at home.
Evaporative desalination method is to make the part water vapor in high-salt wastewater with the method for heating and remove, and is molten to improve the concentration of solution
Matter is separated out and created conditions.However, be all the mixed salt that includes a variety of salts at the same time using the solid that evaporative desalination method separates out, purity
It is low, it can not industrially reuse, usually mixed salt is directly discarded or gives dangerous waste processing mechanism with per ton 300~5000
The price of member carries out professional treatment, so not only increases environmental protection pressure, also considerably increases the cost for wastewater treatment of factory.
Industrially, sodium sulphate and both salt usage amounts of sodium chloride are very big, and a large amount of sodium sulphate in high-salt wastewater,
Sodium chloride is all discarded in vain, unfortunately.
The content of the invention
The technical problem to be solved in the invention is to provide a kind of recycling of the high-salt wastewater containing sodium chloride and sodium sulphate
Processing method, can carry out effective recycling to the sodium sulphate in high-salt wastewater and sodium chloride by this method, substantially reduce
Environmental protection pressure and cost for wastewater treatment.
In order to solve the above technical problems, the technical solution adopted in the present invention is：
The recovery and treatment method of the high-salt wastewater of sodium chloride-containing and sodium sulphate, the high-salt wastewater containing sodium chloride and sodium sulphate
By nanofiltration membrane, sodium chloride is obtained through evaporative crystallization through the filtered fluid of NF membrane, is not passed through through the trapped fluid of NF membrane
Evaporative crystallization obtains sodium sulphate, and a mother liquor return system is mixed with raw material continues cycling through utilization.
Technical solution of the present invention further improvement lies in that：Concretely comprise the following steps：
A, nanofiltration membrane
High-salt wastewater is pumped into the feeding liquid side of nano-filtration unit, high-salt wastewater is divided into through NF membrane through nanofiltration membrane
Filtered fluid and do not pass through NF membrane trapped fluid；
The filtered fluid enters step C processing into step B processing, the trapped fluid；
B, filtered fluid evaporative crystallization
Will filtered fluid be sent into crystallizing evaporator in be evaporated concentration output sodium chloride, be concentrated by evaporation temperature for 50 DEG C~
150℃；
C, trapped fluid evaporative crystallization
Trapped fluid feeding crystallizing evaporator is evaporated concentration, it is 50 DEG C~150 DEG C to be concentrated by evaporation temperature, when solution
After solid content reaches 2%~30%, stop evaporation；Separation of solid and liquid is carried out under the conditions of 50 DEG C~100 DEG C, obtains sodium sulfate crystal
With a mother liquor；
The sodium sulfate crystal directly produces, and a mother liquor sends progress step A circulations in high-salt wastewater back to again.
Technical solution of the present invention further improvement lies in that：The processing equipment includes passing through high-salt wastewater with high-salt wastewater
The intake pool of input channel connection, the intake pool and receives membrane module and be connected, and the filtrate outlet of membrane module received adds with being imitated by one
Hot cell A provides an effect separation chamber A connections of heat, an effect separation chamber A and the two effect crystallizers that heat is provided by two effect heating chamber As
A connections, two effect crystallizer A are connected with thickener, and thickener is connected with centrifuge A, and crystal passes through crystal efferent duct in centrifuge A
Road A is produced；Receive the trapped fluid outlet of membrane module be connected with providing an effect separation chamber B of heat by an effect heating chamber B, and one imitates and separates
Room B is connected with providing two effect crystallizer B of heat by two effect heating chamber B, and two effect crystallizer B are connected with centrifuge B, centrifuge B
Interior crystal is produced by crystal output channel B, and a mother liquor of centrifuge B is back in intake pool.
Technical solution of the present invention further improvement lies in that：Steam respectively enters an effect heating chamber by steam input pipe road
The shell side of the effect heating chambers of A and one B carries out heat exchange condensation, is discharged after the mixing of the two condensed water through condensate output transistor road；By an effect
The secondary vapour that the effects of separation chamber A and one separation chamber B is produced respectively enters two effect heating chamber As and the shell side of two effect heating chamber B is changed
Heat condensation, condensed water are kept in into condensate water pot；Two effect crystallizer A and the condensed device of secondary vapour that two effect crystallizer B are produced are cold
Enter condensate water pot after solidifying.
Technical solution of the present invention further improvement lies in that：The operating environment of nanofiltration membrane is in the step A：High salt
PH=5~10 of waste water, concentration about 1wt%, waste water temperature are 4 DEG C~45 DEG C, and operating pressure is 0.5~1.5MPa；
The membrane material of the membrane module of the nano-filtration unit is polyamide material, and membrane aperture is less than 2nm.
Technical solution of the present invention further improvement lies in that：High-salt wastewater, filtered fluid, once trapped fluid, mother are detected respectively
Organic matter in liquid, when the organic concentration in any liquid in high-salt wastewater, filtered fluid, trapped fluid, a mother liquor exceedes
During 1000mg/L, using the organic matter in the exceeded solution of activated carbon adsorption or by catalysis oxidation to the organic matter in exceeded solution
Handled, treat that organic concentration is down to 100~below 300mg/L and enters back into next processing step.
Technical solution of the present invention further improvement lies in that：The crystallizing evaporator includes evaporator and crystallizer；It is described
Evaporator is any one in natural-circulation evaporator, falling film evaporator, forced-circulation evaporator.
Technical solution of the present invention further improvement lies in that：The evaporator is single effect evaporator, multi-effect evaporator, MVR
Evaporator or TVR evaporators.
Technical solution of the present invention further improvement lies in that：Crystallizer be Oslo crystallizers, DTB crystallizers, DP crystallizers,
Any one in the mutation of Flash Type crystallizer or pattern above.
Technical solution of the present invention further improvement lies in that：The crystallizer is provided with eluriating the vertical crystallizer of leg.
By adopting the above-described technical solution, the technological progress that the present invention obtains is：
The present invention provides a kind of sodium chloride-containing and the recovery and treatment method of the high-salt wastewater of sodium sulphate, to coal chemical industry
Sodium chloride and sodium sulphate in high-salt wastewater have carried out effective recycling, process conditions simple and stable, easy to industrialization promotion.Pass through
The method of the present invention, the sodium chloride and sodium sulphate of the high-purity that can be recycled, meet the quality requirement of technical grade product, can be straight
Connect recovery or sold as byproduct, not only achieveed the purpose that to handle high-salt wastewater, met current Environmental Protection Situation
Need, and turn waste into wealth, realize the recycling of salt, improve the income of factory.
The method of the present invention is a kind of processing method of iterative cycles, and the mother liquor and water produced in processing procedure can return to
Into high-salt wastewater, circulation and stress is handled.In whole processing procedure, other no sewage discharges in addition to moisture evaporation, therefore ring
Packing pressure die-offs, and without being handled again to the payment of dangerous waste processing mechanism, greatly reduces cost for wastewater treatment.Recycling
Cheng Zhong, always has certain salt to be dissolved in mother liquor, can not separate out completely, circulation process method of the invention, can make molten
Do not separate out salt of the solution in mother liquor is constantly enriched with, finally separates out, it is achieved thereby that salt returns to greatest extent in high-salt wastewater
Receive.
The present invention be according to nanofiltration membrane property and sodium sulphate, sodium chloride dissolubility property and especially set, sodium chloride
Can be by NF membrane, the filtered fluid by NF membrane enters evaporative crystallization program, evaporates endpoint concentration by controlling, and ensures a large amount of
Sodium chloride crystallizes, and remaining water can directly discharge pollution-free.Contain sodium sulphate and a small amount of chlorine without the trapped fluid of NF membrane
Change sodium, dramatically increased when the solubility of sodium sulphate is below about 40 DEG C with the rise of temperature, and when more than this temperature with
The rise of temperature and reduce, though the solubility of sodium chloride increases and is increased slightly with temperature, be influenced by temperature less.Cause
This, when recycling sodium sulphate, using being first concentrated by evaporation high-salt wastewater and then separating out sodium sulfate crystal at relatively high temperatures, passes through
Control evaporation endpoint concentration, ensures that evaporation endpoint concentration falls and is separated out in the crystal region of sodium sulphate, without sodium chloride, so as to obtain height
The sodium sulphate of purity.A mother liquor after separating sodium sulfate returns to circular treatment in high-salt wastewater, by moving in circles, can make
Most sodium sulphate and sodium chloride are recycled in high-salt wastewater.
The present invention is directly separated sodium chloride and sodium sulphate using NF membrane, with using multiple evaporative crystallization and cooling in the past
Compared to easier, the purity for crystallizing two kinds of salt of gained is all improved the recovery method of crystallization.Pass through NF membrane point at the same time
The filtered fluid and trapped fluid opened can each crystallize out sodium chloride and sodium sulphate by evaporative crystallization at the same time, in step different from the past
First evaporative crystallization separates out a kind of salt, then the evaporative crystallization of surplus solution progress next step is gone to separate out another salt, this stringent
Sequencing cause inefficiency, whole process of the present invention saves the time of a quarter than existing recovery and treatment method,
Improve 25% efficiency.
Filtration treatment is carried out to high-salt wastewater using NF membrane in step A, the membrane material of the membrane module of nano-filtration unit is poly-
Acid amides material, membrane aperture is in below 2nm, feeding liquid side, high-salt wastewater pH5~10,4~45 DEG C of waste water temperature, operating pressure 0.5
~1.5MPa, it is ensured that in the range of NF membrane ability to bear, avoid the performance of infringement film, solute point can be more effectively carried out
Level.
Multi-effect evaporator is used in step B, it is no crystallization separate out when optional falling film evaporator, natural-circulation evaporator,
Any one in forced-circulation evaporator, preferably falling film evaporator.Falling film evaporator is with very high heat exchange area and well
Heat exchange property, and solution internal circulating load very little, are very suitable for the big flush distillation step of evaporation capacity, can effectively accelerate evaporation speed
Degree, reduces evaporation cost.
Multi-effect evaporator is used in step C, it is no crystallization separate out when optional falling film evaporator, natural-circulation evaporator,
Any one in forced-circulation evaporator, selects forced-circulation evaporator, forced-circulation evaporator is when there is crystallization to separate out
The evaporator that a kind of heat transfer coefficient is big, resistive connection scar ability is strong, circulation of the solution in equipment are relied primarily on produced by additionaling power
Forced flow, circulation rate is generally up to 1.5~5 meter per seconds；It is heated when circulating liquid flows through heating chamber, is then dividing
Part is evaporated when being reduced from pressure in room, i.e., by the boiling temperature under liquid cooling to corresponding pressure, due to circulating pump,
The operation of forced-circulation evaporator is substantially unrelated with temperature, and the recirculation rate of material can be adjusted accurately, evaporation rate setting
Within the specific limits；Feed liquid separates again into separator, with idetified separation effect integral device can be made to have larger separation bullet
Property；Evaporating the crystal separated out can be divided by adjusting circulation flow rate and being designed using special separator from loop slurry
Separate out and, be conducive to handle larger viscosity, easy fouling, the material easily crystallized or the higher solution of concentrating degree, thus it is very suitable
Use, sodium chloride crystal can be efficiently separated for evaporative crystallization steps.
Step B, the crystallizer that step C is used is selected from Oslo crystallizers, DTB crystallizers, DP crystallizers, Flash Type crystallizer
In any one, be preferably provided with eluriate leg vertical DTB crystallizers.DTB crystallizers are a kind of typical magma inner circulation types
Crystallizer, has good fluid dynamic effect；Pressure head in it needed for circulation is very low, and propeller or axial-flow pump are relatively low
Rotating speed under work, so as to greatly reduce impeller to secondary nucleation caused by the collision of crystal, and then ensure that crystallizer
The crystal of middle generation has larger granularity, and size distribution is good, inner wall seldom occurs and scabs phenomenon；DTB crystallizer operations week
Phase is long, energy consumption is low, reliable, failure is few.It can realize that continuous production operates equipped with the vertical DTB crystallizers for eluriating leg, it is real
Now the circulation and stress of high-salt wastewater is handled.Vertical elutriation leg can carry out counter flow washing when producing crystal with material liquid, ensure
It is minimum that the crystal of extraction contains impurity, to reach technical grade quality standard.
Brief description of the drawings
The step of Fig. 1 is processing method of the present invention and the schematic diagram of separation product；
Fig. 2 is the concrete technology flow process schematic diagram of embodiment 1；
Wherein, 1, water feeder, 2, membrane module, 3, one effect heating chamber A, 4, one effect separation chamber A, 5, two effect heating chamber As, 6, two
Imitate crystallizer A, 7, thickener, 8, centrifuge A, 9, mother liquor tank A, 10, one effect heating chamber B, 11, one effect separation chamber B, 12, two effects
Heating chamber B, 13, two effect crystallizer B, 14, centrifuge B, 15, mother liquor tank B, 16, steam input pipe road, 17, condensate output transistor
Road, 18, crystal output channel B, 19, high-salt wastewater input channel, 20, crystal output channel A, 21, condensate output transistor road,
22nd, outlet conduit, 23, water supply pipeline, 24, water return pipeline, 25, condenser, 26, condensate water pot.
Embodiment
The present invention is described in further details with reference to embodiment：
The recovery and treatment method of the high-salt wastewater of sodium chloride-containing and sodium sulphate, by nanofiltration membrane, through NF membrane
Mother liquid evaporation crystallizes to obtain sodium chloride, and the trapped fluid evaporative crystallization through NF membrane does not obtain sodium sulphate, and remaining mother liquor returns
The system of returning is mixed with raw material continues cycling through utilization；This recovery and treatment method concretely comprises the following steps：
A, nanofiltration membrane
High-salt wastewater is pumped into the feeding liquid side of nano-filtration unit, the operating condition of nano-filtration unit is：Feeding liquid side, wastewater pH
For 5~10,4~45 DEG C, 0.5~1.5MPa of operating pressure of waste water temperature, feeding liquid side 1~2m/s of crossflow velocity.Through NF membrane
High-salt wastewater is divided into through the filtered fluid of NF membrane and through the trapped fluid of NF membrane by filtering, and sodium chloride can pass through nanofiltration
Film, therefore sodium chloride is mainly contained in filtered fluid, sodium sulphate and a small amount of sodium chloride are mainly contained in trapped fluid.
Filtered fluid is sent into step B processing, trapped fluid is sent into step C processing；
B, filtered fluid evaporative crystallization
Filtered fluid feeding evaporative crystallization section is evaporated concentration, it is 50 DEG C~150 DEG C to be concentrated by evaporation temperature；With dampening
Constantly evaporating, the sodium chloride in filtered fluid gradually crystallizes precipitation, when solid-to-liquid ratio reaches 2%~30% in raffinate, sodium chloride
It is basic to separate out completely；Separation of solid and liquid is carried out at a temperature of 30 DEG C~50 DEG C, and solid is washed with clear water, obtains high-purity
Sodium chloride crystal and water.
Gained sodium chloride crystal directly produces, and after drying process, its purity reaches technical grade, can be re-used as industrial chlorine
Change sodium to sell using or directly as byproduct, water enters pond, reuse or outer row.
In this step, it is concentrated by evaporation preferably 50~100 DEG C of temperature；The remaining fluid solid content for evaporating terminal is preferably 15%
~25%.
C, trapped fluid evaporative crystallization
Trapped fluid feeding evaporative crystallization section is evaporated concentration, it is 50~150 DEG C to be concentrated by evaporation temperature；During this,
Moisture evaporation in trapped fluid so that the concentration of wherein salt gradually rises, until separating out, the crystal separated out at this time is ten water sulphur
Sour sodium；After the solid content in raffinate is up to 2%~30%, most of sodium sulphate in trapped fluid has all crystallized precipitation, chlorination
Sodium is remained in liquid phase.Separation of solid and liquid is carried out under the conditions of 50~100 DEG C, obtains the sodium sulfate crystal of high-purity and once female
Liquid；
The sodium sulfate crystal separated out in evaporation and crystal process is washed in a pan in the elutriation leg of crystallizer with high-salt wastewater first
Wash, then obtained solid is washed with clear water in separation of solid and liquid, finally obtain the sodium sulfate crystal of high-purity, directly adopt
Go out.For the sodium sulfate crystal of extraction after drying process, its purity reaches technical grade quality, can be re-used as the use of industrial sulphuric acid sodium
Or sold directly as byproduct.
Mother liquor of gained sends progress step A circulation and stress in high pressure waste water back to again.
In this step, it is concentrated by evaporation preferably 70~100 DEG C of temperature；The remaining fluid solid content for evaporating terminal is preferably 15%
~25%；Preferably 60~80 DEG C of separation of solid and liquid temperature.
Due to inevitably containing some organic matters in coal chemical industrial waste water, influenced whether if organic matter too high levels
The precipitation of salt.Therefore, need in the actual production process to organic in high-salt wastewater, filtered fluid, trapped fluid, a mother liquor
Thing content is monitored；When organic concentration is higher than 1000mg/L, activated carbon, activated coke need to be used to inhale organic matter
It is attached, or trim process is carried out to organic matter by catalysis oxidation, after organic concentration is down to 100~below 300mg/L, then
Be sent into next processing step, i.e., high-salt wastewater after treatment is returned in high-salt wastewater pond, filtered fluid after treatment into
Enter in step B, trapped fluid after treatment is entered step in C, and a mother liquor after treatment enters in high-salt wastewater.
Organic matter, which is handled, can not only ensure the purity and color and luster of salinity, but also can ensure the normal use of NF membrane, more
Avoid causing to influence evaporation process the elevation of boiling point is serious because organic matter is constantly accumulative.It is adsorbed with the activated carbon or activity of organic matter
Jiao can send to boiler and burn.Since the amount of filtered fluid, trapped fluid and a mother liquor is few, biochemical sewage process can also be directly returned
COD is reduced, avoids unnecessary lengthy and jumbled treatment process, unified detection process can be more effectively carried out to organic matter.
Example 1：
The technological process of the present embodiment is as shown in Fig. 2, using secondary two effect following current evaporation flows.
In the present embodiment, trapped fluid evaporative crystallization uses economic benefits and social benefits following current flow；1st effective evaporator uses falling film evaporator, bag
Include the effect heating chambers of an effect separation chamber B11 and one B10；2nd effect evaporator uses forced-circulation evaporation crystallizer, including two effect crystallizations
The effect heating chambers of device B13 and two B12.Filtered fluid evaporative crystallization section uses economic benefits and social benefits following current flow；1st effective evaporator uses falling film evaporation
Device, including an effect separation chamber A4 and an effect heating chamber A 3；2nd effect evaporator uses forced-circulation evaporation crystallizer, including two effect knots
The effect heating chamber As 5 of brilliant device A6 and two.
Flow direction of material：
A, nanofiltration membrane
High-salt wastewater from high-salt wastewater input channel 19 initially enters water feeder 1, then under the action of feeding pump
It is admitted to membrane module 2 and carries out nanofiltration membrane, the operating environment of nanofiltration membrane is：PH=5~10 of high-salt wastewater, concentration is about
1wt%, waste water temperature are 4~45 DEG C, and operating pressure is 0.5~1.5MPa.High-salt wastewater is divided into transmission through nanofiltration membrane
The filtered fluid (sodium chloride) of NF membrane and the trapped fluid (a small amount of sodium chloride and sodium sulphate mixture) for not passing through NF membrane, will filter
Liquid is sent into step B processing, and trapped fluid is sent into step C processing.
B, filtered fluid evaporative crystallization
Filtered fluid evaporative crystallization uses economic benefits and social benefits following current flow；1st effective evaporator uses falling film evaporator, including an effect separation
The effect heating chamber As 3 of room A4 and one, are concentrated by evaporation temperature and are set in 80 DEG C；2nd effect evaporator uses forced-circulation evaporation crystallizer, bag
The effect heating chamber As 5 of two effect crystallizer A6 and two are included, temperature is concentrated by evaporation and is set as 80 DEG C, treat that solid-to-liquid ratio reaches 20% in raffinate
When, through two effect discharging pumps are delivered to thickener 7, centrifuge A8 carries out concentrating and separating.Sodium chloride crystal and water are separated to obtain, NaCl is brilliant
Body, which directly produced through crystal output channel A20, can be used as finished product after washed drying process sells, and water is returned through outlet conduit 22
With or outer row.
C, trapped fluid evaporative crystallization
Trapped fluid evaporative crystallization uses economic benefits and social benefits following current flow；1st effective evaporator uses falling film evaporator, including an effect separation
The effect heating chamber B10 of room B11 and one, it is 80 DEG C to be concentrated by evaporation temperature；2nd effect evaporator uses forced-circulation evaporation crystallizer, including
Two effect crystallizer B13 and two effect heating chamber B12, it is 80 DEG C to be concentrated by evaporation temperature, when solid-to-liquid ratio reaches 20% in raffinate, warp
Two effect discharging pumps are delivered to centrifuge B14 and are separated.Sodium sulfate crystal and a mother liquor are separated to obtain, sodium sulfate crystal is through crystal
Output channel B18 is directly produced, be can be used as finished product sale after washed drying process, and a mother liquor returns to pool circulating profit
With.
Steam and condensation flow to：
The shell side that steam respectively enters an effect heating chamber A 3 and an effect heating chamber B10 by steam input pipe road 16 is changed
Heat condensation, is discharged after the mixing of the two condensed water through condensate output transistor road 17；By an effect separation chamber A4 and an effect separation chamber B11 productions
Raw secondary vapour respectively enters two effect heating chamber As 5 and the shell side of two effect heating chamber B12 carries out heat exchange condensation, and condensed water enters cold
Condensate tank 26 is temporary；The condensed device 25 of secondary vapour that two effect crystallizer A6 and two effect crystallizer B13 are produced enters condensation after condensing
Water pot 26.Condensed water in condensate water pot 26 is driven by condensate pump, is discharged by condensate output transistor road 21 again, into traveling one
Step recycling.The secondary vapour that two effect crystallizer A6 and two effect crystallizer B13 are produced is after the condensation of indirect condenser 25, fixed gas
Body is discharged into air by vacuum pumped.
Circulating water flow to：
Come self-circulating water water supply pipeline 23 recirculated water enter condenser 25 exchange heat after, directly through recirculated water water return pipeline 24
Discharge.
The present invention is directly separated sodium chloride and sodium sulphate using NF membrane, with using multiple evaporative crystallization and cooling in the past
The recovery method of crystallization is compared to easier, and the purity for crystallizing two kinds of salt of gained is all improved, the mass fraction of sodium chloride
Reach 95.9%, the mass fraction of sodium sulphate reaches 96.2%.At the same time can be same by the separated filtered fluid of NF membrane and trapped fluid
When sodium chloride and sodium sulphate each crystallized out by evaporative crystallization, first evaporative crystallization separates out a kind of salt in step different from the past,
The evaporative crystallization that next step is carried out to surplus solution again goes to separate out another salt, and this strict sequence causes efficiency low
Under, whole process of the present invention saves the time of a quarter than existing recovery and treatment method, improves 25% efficiency.
The sodium sulfate crystal and sodium chloride crystal that this technique is produced, after drying, carry out performance detection, testing result
1, table 2 is shown in Table respectively.
1 sodium sulphate properties of product of table detect
| Project | 1 sodium sulphate product of embodiment | Technical grade sulfuric acid sodium performance indicator |
| Sodium sulfate quality fraction | 96.2% | III class Grade A：95% |
2 sodium chloride properties of product of table detect
| Project | 1 sodium chloride product of embodiment | Industrial grade sodium chloride performance indicator |
| Sodium chloride mass fraction | 95.9% | Level-one solarization Nacl：94.5% |
By data above as can be seen that the sodium sulphate product obtained by the method for the present invention, sodium chloride product reach respectively
To technical grade sulfuric acid sodium, the performance requirement of industrial grade sodium chloride, can sell as technical grade product.
Claims (10)
1. the recovery and treatment method of the high-salt wastewater of sodium chloride-containing and sodium sulphate, it is characterised in that：Contain sodium chloride and sodium sulphate
High-salt wastewater by nanofiltration membrane, sodium chloride is obtained through evaporative crystallization through the filtered fluid of NF membrane, not through NF membrane
Trapped fluid obtain sodium sulphate through evaporative crystallization, a mother liquor return system is mixed with raw material continues cycling through utilization.
2. the recovery and treatment method of the high-salt wastewater of sodium chloride-containing according to claim 1 and sodium sulphate, it is characterised in that
Concretely comprise the following steps：
A, nanofiltration membrane
High-salt wastewater is pumped into the feeding liquid side of nano-filtration unit, high-salt wastewater is divided into the mistake through NF membrane through nanofiltration membrane
Filtrate and the trapped fluid for not passing through NF membrane；
The filtered fluid enters step C processing into step B processing, the trapped fluid；
B, filtered fluid evaporative crystallization
Filtered fluid is sent into crystallizing evaporator and is evaporated concentration output sodium chloride, it is 50 DEG C~150 DEG C to be concentrated by evaporation temperature；
C, trapped fluid evaporative crystallization
Trapped fluid feeding crystallizing evaporator is evaporated concentration, it is 50 DEG C~150 DEG C to be concentrated by evaporation temperature, when consolidating for solution contains
After amount reaches 2%~30%, stop evaporation；Separation of solid and liquid is carried out under the conditions of 50 DEG C~100 DEG C, obtains sodium sulfate crystal and once
Mother liquor；
The sodium sulfate crystal directly produces, and a mother liquor sends progress step A circulations in high-salt wastewater back to again.
3. the recovery and treatment method of the high-salt wastewater of a kind of sodium chloride-containing according to claim 1 and sodium sulphate, its feature
It is：The processing equipment includes the intake pool being connected with high-salt wastewater by high-salt wastewater input channel（1）, the intake pool
（1）With receiving membrane module（2）Connection, receives membrane module（2）Filtrate outlet with by one effect heating chamber A（3）One effect of heat is provided
Separation chamber A（4）Connection, an effect separation chamber A（4）With imitating heating chamber As by two（5）Two effect crystallizer A of heat are provided（6）Connection,
Two effect crystallizer A（6）With thickener（7）Connection, thickener（7）With centrifuge A（8）Connection, centrifuge A（8）Interior crystal passes through
Crystal output channel A（20）Extraction；Receive membrane module（2）Trapped fluid outlet with by an effect heating chamber B（10）The one of heat is provided
Imitate separation chamber B（11）Connection, an effect separation chamber B（11）With imitating heating chamber B by two（12）Two effect crystallizer B of heat are provided（13）
Connection, two effect crystallizer B（13）With centrifuge B（14）Connection, centrifuge B（14）Interior crystal passes through crystal output channel B（18）
Extraction, centrifuge B（14）A mother liquor be back to intake pool（1）In.
4. the recovery and treatment method of the high-salt wastewater of a kind of sodium chloride-containing according to claim 3 and sodium sulphate, its feature
It is：Steam passes through steam input pipe road（16）Respectively enter an effect heating chamber A（3）With an effect heating chamber B（10）Shell side into
Row heat exchange condensation, through condensate output transistor road after the mixing of the two condensed water（17）Discharge；By an effect separation chamber A（4）With an effect point
From room B（11）The secondary vapour produced respectively enters two effect heating chamber As（5）With two effect heating chamber B（12）Shell side exchange heat it is cold
Solidifying, condensed water enters condensate water pot（26）It is temporary；Two effect crystallizer A（6）With two effect crystallizer B（13）The secondary vapour produced is through cold
Condenser（25）Enter condensate water pot after condensation（26）.
5. the recovery and treatment method of the high-salt wastewater of sodium chloride-containing according to claim 2 and sodium sulphate, it is characterised in that：
The operating environment of nanofiltration membrane is in the step A：PH=5~10 of high-salt wastewater, concentration about 1wt%, waste water temperature are 4 DEG C
~45 DEG C, operating pressure is 0.5~1.5MPa；
The membrane material of the membrane module of the nano-filtration unit is polyamide material, and membrane aperture is less than 2nm.
6. the recovery and treatment method of the high-salt wastewater of sodium chloride-containing according to claim 2 and sodium sulphate, it is characterised in that：
The organic matter in high-salt wastewater, filtered fluid, trapped fluid, a mother liquor is detected respectively, as high-salt wastewater, filtered fluid, trapped fluid, one
When organic concentration in secondary mother liquor in any liquid is more than 1000mg/L, using organic in the exceeded solution of activated carbon adsorption
Thing is handled the organic matter in exceeded solution by catalysis oxidation, treats that organic concentration is down to 100~below 300mg/L
Enter back into next processing step.
7. the recovery and treatment method of the high-salt wastewater of sodium chloride-containing according to claim 2 and sodium sulphate, it is characterised in that：
The crystallizing evaporator includes evaporator and crystallizer；The evaporator is natural-circulation evaporator, falling film evaporator, pressure follow
Any one in ring evaporator.
8. the recovery and treatment method of the high-salt wastewater of sodium chloride-containing according to claim 7 and sodium sulphate, it is characterised in that：
The evaporator is single effect evaporator, multi-effect evaporator, MVR evaporators or TVR evaporators.
9. the recovery and treatment method of the high-salt wastewater of sodium chloride-containing according to claim 7 and sodium sulphate, it is characterised in that：
Crystallizer is any in the mutation of Oslo crystallizers, DTB crystallizers, DP crystallizers, Flash Type crystallizer or pattern above
It is a kind of.
10. the recovery and treatment method of the high-salt wastewater of sodium chloride-containing according to claim 9 and sodium sulphate, its feature exist
In：The crystallizer is provided with eluriating the vertical crystallizer of leg.
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