CN110342544A - A kind of the salt resource recovering system and method for organic wastewater with high concentration - Google Patents
A kind of the salt resource recovering system and method for organic wastewater with high concentration Download PDFInfo
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- CN110342544A CN110342544A CN201910069207.7A CN201910069207A CN110342544A CN 110342544 A CN110342544 A CN 110342544A CN 201910069207 A CN201910069207 A CN 201910069207A CN 110342544 A CN110342544 A CN 110342544A
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- 150000003839 salts Chemical class 0.000 title claims abstract description 82
- 239000002351 wastewater Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 31
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 168
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 168
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 104
- 239000011780 sodium chloride Substances 0.000 claims abstract description 83
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000002425 crystallisation Methods 0.000 claims abstract description 64
- 230000008025 crystallization Effects 0.000 claims abstract description 64
- 238000001704 evaporation Methods 0.000 claims abstract description 61
- 230000008020 evaporation Effects 0.000 claims abstract description 60
- 230000008014 freezing Effects 0.000 claims abstract description 56
- 238000007710 freezing Methods 0.000 claims abstract description 56
- PALNZFJYSCMLBK-UHFFFAOYSA-K magnesium;potassium;trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-].[Cl-].[K+] PALNZFJYSCMLBK-UHFFFAOYSA-K 0.000 claims abstract description 26
- 238000004064 recycling Methods 0.000 claims abstract description 18
- 238000013468 resource allocation Methods 0.000 claims abstract description 5
- 239000012452 mother liquor Substances 0.000 claims description 55
- 239000013078 crystal Substances 0.000 claims description 29
- 239000007832 Na2SO4 Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 24
- 239000012528 membrane Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 5
- 239000002910 solid waste Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 claims 1
- 238000003672 processing method Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002817 coal dust Substances 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- HHXYJYBYNZMZKX-UHFFFAOYSA-N 3,4:15,16-diepoxy-7-oxo-13(16),14-clerodadien-20,12-olide-(3alpha,4alpha)-form Natural products C12CCC3C4(C)CCCC(C)(C)C4CCC3(C)C1(C)CCC1C2(C)CCC1C(=C)C HHXYJYBYNZMZKX-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 210000000038 chest Anatomy 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The invention discloses the salt resource recovering system and method for a kind of organic wastewater with high concentration, processing system includes former pond, organic film upgrading unit, is concentrated by evaporation unit, sodium chloride evaporator, mixed salt evaporator and carnallite crystallizer；Recycling salt resource allocation method includes the concentration of step (1) film；Step (2) sodium sulphate evaporative crystallization；Step (3) freezing and crystallizing；Step (4) sodium chloride evaporative crystallization；Step (5) carnallite evaporative crystallization.The utility model has the advantages that processing system structure of the invention is simple, Yi Shixian；Processing method of the invention is simple, and processing cost is low, while treatment effeciency is higher；And present system is stable, is influenced by variation water quality smaller, can fully ensure that out salt quality and salt resource rate；Realize the resource utilization of organic wastewater with high concentration.
Description
Technical field:
The invention patent belongs to industry environmental protection field, and in particular to a kind of salt resource recovering system of organic wastewater with high concentration and
Method.
Background technique:
As the industrial water consumptions such as pharmacy, chemical industry, pesticide, dyestuff and discharge amount increasingly increase, high concentrated organic wastewater band
The problem of environmental pollution come is also increasingly severe.Organic cod is even as high as tens of thousands of or even tens generally in 2000mg/L or more
Ten thousand mg/L, while coloration is high, has peculiar smell, causes adverse effect to ambient enviroment.
Common organic wastewater with high concentration processing method includes materilization freatment method, biological method and catalysis oxidation etc..
Physical chemistry method is mainly using photochemistry Coagulation Method, oxidation-absorption method, incineration method as representative: photochemistry Coagulation Method is to pass through ultraviolet light
Irradiation generates free radicals and initiated polymerization, so that waste water small molecular organic matter is converted into macromolecular suspended matter, then coagulation
Precipitating removal；Oxidation-absorption method is mainly to carry out preliminary coagulation, adsorption treatment with coal dust after high-concentration waste water dilutes, and is then used
Fenton reagent catalysis oxidation and acid cohesion, then with coal dust coagulation, adsorb；Incineration method is suitable for processing high concentration organic waste
Water, pretreated waste water is pressurized, filters, send after metering to chimney arch, sprays into furnace by pressure-air atomization special nozzle
Evaporation burning in thorax.Biological method can be divided into aerobic method and anaerobic process two major classes；Aerobe method is generally used for handling low dense
Spend organic wastewater；Anaerobic process is using facultative anaerobic bacteria and obligate anaerobe come degradation of organic substances, and the organic matter of macromolecular is first
It is hydrolyzed into low molecular compound, is then converted to CH4And CO2Deng.Catalytic oxidation treatment method is deposited in efficient surface catalyst
Under the conditions, chlorine dioxide oxidation of high density organic wastewater at normal temperatures and pressures is utilized；During degrading COD, interrupt
Double bond chromophore in organic molecule, such as azo group, nitro, vulcanization carbonyl, carbon imino group, achieve the purpose that thoroughly to decolourize,
BOD is effectively improved simultaneously5/ COD value.
The salt recovery method as resource of common organic wastewater with high concentration is mainly recycled by evaporative crystallization technique, but is used
Above-mentioned recycling salt resource mode has the following problems: 1, using evaporation pond natural evaporation moisture, but evaporation effect is unsatisfactory,
But also will cause the waste of water resource, and cannot recycle to the salinity in waste water, the waste of resource is caused, is reduced
The economic benefit of enterprise；2, the inferior quality for the crystal salt produced is extremely difficult to production standard, and after processing useless
Water still has partial organic substances, is unsatisfactory for waste water recycling standard, can not directly recycle.
Summary of the invention:
The first purpose of this invention is to provide that a kind of structure is simple, and the salt resource of the organic wastewater with high concentration of Yi Shixian is returned
Receipts system.
Second object of the present invention is to provide a kind of process simple, and treatment effeciency is high, and has fully ensured that
The recycling salt resource allocation method of the organic wastewater with high concentration of salt quality and salt resource rate.
On the one hand technical solution of the present invention discloses a kind of salt resource recovering system of organic wastewater with high concentration comprising former
Pond, is concentrated by evaporation unit, sodium chloride evaporator, mixed salt evaporator and carnallite crystallizer at organic film upgrading unit；The raw water
The water outlet in pond is connected to the water inlet of the core type filter of the organic film upgrading unit by intake pump；The organic film is dense
The production water out of the membrane module of contracting unit is connected to the water inlet of the evaporation former pond for being concentrated by evaporation unit, and the evaporation is dense
The liquid outlet of the sodium sulphate evaporator of contracting unit is connected to the inlet of the sodium chloride evaporator, the sodium chloride evaporator
Liquid outlet is connected to the inlet of the mixed salt evaporator, the discharge port of the mixed salt evaporator and the feed inlet of the former pond
Connection；The liquid outlet of the mixed salt evaporator is connected to the inlet of the carnallite crystallizer.
It further, further include freezing and crystallizing tank；The liquid outlet of the sodium sulphate evaporator and the freezing and crystallizing tank
Inlet connection, the discharge port of the freezing and crystallizing tank is connected to the feed inlet of the sodium sulphate evaporator, and the freezing is tied
The liquid outlet of brilliant tank is connected to the inlet of the sodium chloride evaporator.
Further, the organic film upgrading unit includes the core type filter, the membrane module and high-pressure pump；It is described
The liquid outlet of core type filter is connected to the inlet of the membrane module by the high-pressure pump.
Further, the concentrated water outlet of the membrane module is connected to biochemical treatment system.
Further, the evaporation and concentration unit includes the evaporation former pond, bag filter, heat exchanger, the sulphur
Sour sodium evaporator and recycling can；The liquid outlet of the evaporation former pond and the inlet of the bag filter are connected by water-delivery pump
It is logical；The liquid outlet of the bag filter is connected to the cold medium entrance of the heat exchanger；The cold medium of the heat exchanger exports
It is connected to the inlet of the sodium sulphate evaporator；The gas outlet of the sodium sulphate evaporator and the thermal medium of the heat exchanger enter
Mouth connection；The thermal medium outlet of the heat exchanger is connected to the recycling can.
Further, the sodium sulphate evaporator is multi-effect evaporator or MVR evaporator.
Another aspect of the present invention also discloses a kind of recycling salt resource allocation method of organic wastewater with high concentration comprising following
Step: step (1) film concentration；Step (2) sodium sulphate evaporative crystallization；Step (3) freezing and crystallizing；Step (4) sodium chloride evaporation knot
It is brilliant；Step (5) carnallite evaporative crystallization.
Step (1) film concentration: TDS >=60000mg/L, mass ratio c (Na2SO4): c (NaCl) >=0.67, COD >=
The high concentrated organic wastewater of 30000mg/L, pH=5-8 pass through organic film concentration, obtain concentration and produce water and concentration concentrated water, dense
The removal rate of COD is 40% in contracting production, and the macromolecular hardly degraded organic substance in organic wastewater with high concentration is retained by organic film, is enriched with
Into concentration concentrated water, concentration concentrated water, which is sent in biochemical treatment system, to be further processed.
Step (2) sodium sulphate evaporative crystallization: producing water after filtering for concentration obtained in the concentration of the step (1) film,
It is evaporated crystallization at 80-100 DEG C and obtains sodium sulfate crystal and sodium sulphate evaporation mother liquor, total silicon in evaporation mother liquor≤
5000ppm, sodium nitrate≤18wppm, COD≤15000ppm, sodium chloride≤260000ppm；According to NaCl and Na2SO4In water
The difference of solubility under different temperatures, control sodium sulphate evaporator is in high temperature section, due to c (Na2SO4): c (NaCl) >=
0.67, at this time as evaporation carries out, Na2SO4It is precipitated, obtains Na2SO4Crystal salt.
Step (3) freezing and crystallizing: by the evaporation mother liquor cooling of sodium sulphate obtained in the step (2) sodium sulphate evaporative crystallization
To -5-0 DEG C, freezing and crystallizing obtains sal glauberi and freezing and crystallizing mother liquor, total silicon≤5000ppm, nitre in freezing and crystallizing mother liquor
Sour sodium≤18wppm, COD≤15000ppm, sodium sulphate≤46000ppm；In step (2) sodium sulphate evaporative crystallization later period, c
(Na2SO4): c (NaCl) is gradually reduced, and NaCl is also gradually precipitated, and is reduced sodium sulphate at this time and is evaporated mother liquor temperature, sodium sulphate is molten
Xie Du declines with temperature and sharply declines, thus sal glauberi is precipitated in supersaturation, can be evaporated and be tied with return step (2) sodium sulphate
Continue to crystallize in crystalline substance.
Step (4) sodium chloride evaporative crystallization: freezing and crystallizing mother liquor obtained in the step (3) freezing and crystallizing is warming up to
80-100 DEG C is evaporated crystallization, obtains sodium chloride crystal and sodium chloride evaporation mother liquor；It is cold after step (3) freezing and crystallizing
Freeze in crystalline mother solution based on sodium chloride, is largely precipitated after heating as evaporation carries out sodium chloride, obtains sodium chloride crystal salt.
Step (5) carnallite evaporative crystallization: sodium chloride obtained in the step (4) sodium chloride evaporative crystallization is evaporated into mother liquor
Continue to evaporate under conditions of temperature is 80-100 DEG C, obtains mixed salt crystal and mixed salt mother liquor, mixed salt crystal is delivered back into original
It is continued in water；The mixed salt mother liquor continues evaporative crystallization, obtains solid waste carnallite.
Further, in step (1) the film concentration, the organic wastewater with high concentration is under the conditions of 15 DEG C -25 DEG C, 1-3MPa
Carry out film concentration.
Further, the vapor after step (2) the sodium sulphate evaporative crystallization evaporation is in the concentration of the step (1) film
After obtained concentration produces water preheating, forms condensed water and be recovered.
Advantages of the present invention: 1, processing system structure of the invention is simple, Yi Shixian；2, processing method of the invention letter
Single, processing cost is low, while treatment effeciency is higher；And present system is stable, influenced by variation water quality it is smaller, can
Fully ensure that out salt quality and salt resource rate, that is, the sodium chloride recycled has reached GB/T 5462-2015 " Nacl " standard
The middle dry salt secondary standard of highly industry salt industrial, sodium sulphate have reached in GB/T 6009-2014 " industrial anhydrous sodium sulfate " standard
II class salt qualified product standard；By organic film upgrading unit, evaporation and process for freezing and crystallizing Combined Treatment, highly concentrated organic waste is realized
The resource utilization of water reduces carnallite amount.
Detailed description of the invention:
Fig. 1 is the overall structure diagram of the embodiment of the present invention.
Former pond 1, organic film upgrading unit 2, core type filter 2.1, membrane module 2.2, high-pressure pump 2.3 are concentrated by evaporation single
Member 3 evaporates former pond 3.1, bag filter 3.2, heat exchanger 3.3, sodium sulphate evaporator 3.4, recycling can 3.5, water-delivery pump
3.6, sodium chloride evaporator 4, mixed salt evaporator 5, carnallite crystallizer 6, freezing and crystallizing tank 7, intake pump 8, biochemical treatment system 9.
Specific embodiment:
Below in conjunction with attached drawing, by embodiment, the present invention is described in further detail.
Embodiment 1: as shown in Figure 1, a kind of salt resource recovering system of organic wastewater with high concentration comprising former pond 1, organic
Film upgrading unit 2 is concentrated by evaporation unit 3, sodium chloride evaporator 4, mixed salt evaporator 5, carnallite crystallizer 6 and freezing and crystallizing tank 7；
Organic film upgrading unit 2 includes core type filter 2.1, membrane module 2.2 and high-pressure pump 2.3；The water outlet and core type mistake of former pond 1
The water inlet of filter 2.1 is connected to by intake pump 8；The liquid outlet of core type filter 2.1 and the inlet of membrane module 2.2 pass through height
Press pump 2.3 is connected to；The concentrated water outlet of membrane module 2.2 is connected to biochemical treatment system 9；Being concentrated by evaporation unit 3 includes evaporation raw water
Pond 3.1, bag filter 3.2, heat exchanger 3.3, sodium sulphate evaporator 3.4 and recycling can 3.5；The production water out of membrane module 2.2
It is connected to the water inlet of evaporation former pond 3.1, the inlet for evaporating the liquid outlet and bag filter 3.2 of former pond 3.1 passes through
Water-delivery pump 3.6 is connected to；The liquid outlet of bag filter 3.2 is connected to the cold medium entrance of heat exchanger 3.3；Heat exchanger 3.3 it is cold
Media outlet is connected to the inlet of sodium sulphate evaporator 3.4；The gas outlet of sodium sulphate evaporator 3.4 and the heat of heat exchanger 3.3
Medium inlet connection；The thermal medium outlet of heat exchanger 3.3 is connected to recycling can 3.5, and steam is cooled into after condensed water and is returned
It receives, can reuse；Sodium sulphate evaporator 3.4 is multi-effect evaporator；The liquid outlet and freezing and crystallizing of sodium sulphate evaporator 3.4
The inlet of tank 7 is connected to, and the discharge port of freezing and crystallizing tank 7 is connected to the feed inlet of sodium sulphate evaporator 3.4, freezing and crystallizing tank 7
Liquid outlet be connected to the inlet of sodium chloride evaporator 4, the feed liquor of the liquid outlet of sodium chloride evaporator 4 and mixed salt evaporator 5
Mouth connection, the discharge port of mixed salt evaporator 5 are connected to the feed inlet of former pond 1；The liquid outlet and carnallite of mixed salt evaporator 5 crystallize
The inlet of device 6 is connected to；Processing system structure of the invention is simple, Yi Shixian.
Embodiment 2: the method for 1 system of embodiment recycling salt resource is utilized comprising following steps: the concentration of step (1) film；
Step (2) sodium sulphate evaporative crystallization；Step (3) freezing and crystallizing；Step (4) sodium chloride evaporative crystallization；Step (5) carnallite evaporation knot
It is brilliant.
Step (1) film concentration: TDS=60000mg/L, mass ratio c (Na2SO4): c (NaCl)=1, COD=30000mg/
The high concentrated organic wastewater of L, pH=8 pass through organic film concentration, and organic wastewater with high concentration is had under the conditions of 1MPa at 15 DEG C
Machine film concentration；It obtains concentration and produces water and concentration concentrated water, the removal rate that concentration produces COD in water is 40%, organic wastewater with high concentration
In macromolecular hardly degraded organic substance retained by organic film, be enriched to concentration concentrated water in, concentration concentrated water be sent to biochemical treatment system
It is further processed in system 9.
Step (2) sodium sulphate evaporative crystallization: producing water after filtering for concentration obtained in the concentration of the step (1) film,
It is evaporated crystallization at 80 DEG C and obtains sodium sulfate crystal and sodium sulphate evaporation mother liquor, evaporates total silicon≤5000ppm, the nitre in mother liquor
Sour sodium≤18wppm, COD≤15000ppm, sodium chloride≤260000ppm；According to NaCl and Na2SO4In water under different temperatures
Solubility difference, control sodium sulphate evaporator 3.4 be in high temperature section, due to c (Na2SO4): c (NaCl) >=0.67, this
When with evaporation carry out, Na2SO4It is precipitated, obtains Na2SO4Crystal salt；Vapor after evaporation is in the concentration of the step (1) film
After obtained concentration produces water preheating, forms condensed water and be recovered.
Step (3) freezing and crystallizing: by the evaporation mother liquor cooling of sodium sulphate obtained in the step (2) sodium sulphate evaporative crystallization
To -5 DEG C, freezing and crystallizing obtains sal glauberi and freezing and crystallizing mother liquor, total silicon≤5000ppm, nitric acid in freezing and crystallizing mother liquor
Sodium≤18wppm, COD≤15000ppm, sodium sulphate≤46000ppm；In step (2) sodium sulphate evaporative crystallization later period, c
(Na2SO4): c (NaCl) is gradually reduced, and NaCl is also gradually precipitated, and is reduced sodium sulphate at this time and is evaporated mother liquor temperature, sodium sulphate is molten
Xie Du declines with temperature and sharply declines, thus sal glauberi is precipitated in supersaturation, can be evaporated and be tied with return step (2) sodium sulphate
Continue to crystallize in crystalline substance.
Step (4) sodium chloride evaporative crystallization: freezing and crystallizing mother liquor obtained in the step (3) freezing and crystallizing is warming up to
80 DEG C are evaporated crystallization, obtain sodium chloride crystal and sodium chloride evaporation mother liquor；After step (3) freezing and crystallizing, freezing knot
In brilliant mother liquor based on sodium chloride, largely it is precipitated after heating as evaporation carries out sodium chloride, obtains sodium chloride crystal salt.
Step (5) carnallite evaporative crystallization: sodium chloride obtained in the step (4) sodium chloride evaporative crystallization is evaporated into mother liquor
Continue to evaporate under conditions of temperature is 80 DEG C, obtains mixed salt crystal and mixed salt mother liquor, mixed salt crystal is delivered back into raw water
It continues with；The mixed salt mother liquor continues evaporative crystallization, obtains solid waste carnallite.
Embodiment 3: the method for 1 system of embodiment recycling salt resource is utilized comprising following steps: the concentration of step (1) film；
Step (2) sodium sulphate evaporative crystallization；Step (3) freezing and crystallizing；Step (4) sodium chloride evaporative crystallization；Step (5) carnallite evaporation knot
It is brilliant.
Step (1) film concentration: TDS=65000mg/L, mass ratio c (Na2SO4): c (NaCl)=1.5, COD=
The high concentrated organic wastewater of 35000mg/L, pH=6.7 pass through organic film concentration, and organic wastewater with high concentration is at 20 DEG C, 2MPa item
Organic film concentration is carried out under part；It obtains concentration and produces water and concentration concentrated water, the removal rate that concentration produces COD in water is 40%, high
Macromolecular hardly degraded organic substance in dense organic wastewater is retained by organic film, is enriched in concentration concentrated water, and concentration concentrated water is sent to
It is further processed in biochemical treatment system 9.
Step (2) sodium sulphate evaporative crystallization: producing water after filtering for concentration obtained in the concentration of the step (1) film,
It is evaporated crystallization at 90 DEG C and obtains sodium sulfate crystal and sodium sulphate evaporation mother liquor, evaporates total silicon≤5000ppm, the nitre in mother liquor
Sour sodium≤18wppm, COD≤15000ppm, sodium chloride≤260000ppm；According to NaCl and Na2SO4In water under different temperatures
Solubility difference, control sodium sulphate evaporator 3.4 be in high temperature section, due to c (Na2SO4): c (NaCl) >=0.6, at this time
As evaporation carries out, Na2SO4It is precipitated, obtains Na2SO4Crystal salt；Vapor after evaporation is in the concentration of the step (1) film
After the concentration arrived produces water preheating, forms condensed water and be recovered.
Step (3) freezing and crystallizing: by the evaporation mother liquor cooling of sodium sulphate obtained in the step (2) sodium sulphate evaporative crystallization
To -2.5 DEG C, freezing and crystallizing obtains sal glauberi and freezing and crystallizing mother liquor, total silicon≤5000ppm, nitre in freezing and crystallizing mother liquor
Sour sodium≤18wppm, COD≤15000ppm, sodium sulphate≤46000ppm；In step (2) sodium sulphate evaporative crystallization later period, c
(Na2SO4): c (NaCl) is gradually reduced, and NaCl is also gradually precipitated, and is reduced sodium sulphate at this time and is evaporated mother liquor temperature, sodium sulphate is molten
Xie Du declines with temperature and sharply declines, thus sal glauberi is precipitated in supersaturation, can be evaporated and be tied with return step (2) sodium sulphate
Continue to crystallize in crystalline substance.
Step (4) sodium chloride evaporative crystallization: freezing and crystallizing mother liquor obtained in the step (3) freezing and crystallizing is warming up to
90 DEG C are evaporated crystallization, obtain sodium chloride crystal and sodium chloride evaporation mother liquor；After step (3) freezing and crystallizing, freezing knot
In brilliant mother liquor based on sodium chloride, largely it is precipitated after heating as evaporation carries out sodium chloride, obtains sodium chloride crystal salt.
Step (5) carnallite evaporative crystallization: sodium chloride obtained in the step (4) sodium chloride evaporative crystallization is evaporated into mother liquor
Continue to evaporate under the conditions of at a temperature of 90 °C, obtain mixed salt crystal and mixed salt mother liquor, mixed salt crystal is delivered back into raw water
It continues with；The mixed salt mother liquor continues evaporative crystallization, obtains solid waste carnallite.
Embodiment 4: the method for 1 system of embodiment recycling salt resource is utilized comprising following steps: the concentration of step (1) film；
Step (2) sodium sulphate evaporative crystallization；Step (3) freezing and crystallizing；Step (4) sodium chloride evaporative crystallization；Step (5) carnallite evaporation knot
It is brilliant.
Step (1) film concentration: TDS=70000mg/L, mass ratio c (Na2SO4): c (NaCl)=2, COD=40000mg/
The high concentrated organic wastewater of L, pH=7 pass through organic film concentration, and organic wastewater with high concentration is had under the conditions of 3MPa at 25 DEG C
Machine film concentration；It obtains concentration and produces water and concentration concentrated water, the removal rate that concentration produces COD in water is 40%, organic wastewater with high concentration
In macromolecular hardly degraded organic substance retained by organic film, be enriched to concentration concentrated water in, concentration concentrated water be sent to biochemical treatment system
It is further processed in system 9.
Step (2) sodium sulphate evaporative crystallization: producing water after filtering for concentration obtained in the concentration of the step (1) film,
Be evaporated at 100 DEG C crystallization obtain sodium sulfate crystal and sodium sulphate evaporation mother liquor, evaporate mother liquor in total silicon≤5000ppm,
Sodium nitrate≤18wppm, COD≤15000ppm, sodium chloride≤260000ppm；According to NaCl and Na2SO4Different temperatures in water
Under solubility difference, control sodium sulphate evaporator 3.4 be in high temperature section, due to c (Na2SO4): c (NaCl) >=0.6, this
When with evaporation carry out, Na2SO4It is precipitated, obtains Na2SO4Crystal salt；Vapor after evaporation is in the concentration of the step (1) film
After obtained concentration produces water preheating, forms condensed water and be recovered.
Step (3) freezing and crystallizing: by the evaporation mother liquor cooling of sodium sulphate obtained in the step (2) sodium sulphate evaporative crystallization
To 0 DEG C, freezing and crystallizing obtains sal glauberi and freezing and crystallizing mother liquor, total silicon≤5000ppm, sodium nitrate in freezing and crystallizing mother liquor
≤ 18wppm, COD≤15000ppm, sodium sulphate≤46000ppm；In step (2) sodium sulphate evaporative crystallization later period, c (Na2SO4):
C (NaCl) is gradually reduced, and NaCl is also gradually precipitated, and is reduced sodium sulphate at this time and is evaporated mother liquor temperature, sodium sulphate solubility is with temperature
Degree declines and sharply declines, thus sal glauberi is precipitated in supersaturation, can be to continue in return step (2) sodium sulphate evaporative crystallization
Crystallization.
Step (4) sodium chloride evaporative crystallization: freezing and crystallizing mother liquor obtained in the step (3) freezing and crystallizing is warming up to
100 DEG C are evaporated crystallization, obtain sodium chloride crystal and sodium chloride evaporation mother liquor；After step (3) freezing and crystallizing, freezing knot
In brilliant mother liquor based on sodium chloride, largely it is precipitated after heating as evaporation carries out sodium chloride, obtains sodium chloride crystal salt.
Step (5) carnallite evaporative crystallization: sodium chloride obtained in the step (4) sodium chloride evaporative crystallization is evaporated into mother liquor
Continue to evaporate under conditions of temperature is 100 DEG C, obtains mixed salt crystal and mixed salt mother liquor, mixed salt crystal is delivered back into raw water
It continues with；The mixed salt mother liquor continues evaporative crystallization, obtains solid waste carnallite.
Processing method of the invention is simple, and processing cost is low, while treatment effeciency is higher；And present system operation is steady
It is fixed, it is influenced by variation water quality smaller, can fully ensure that out that salt quality and salt resource rate, that is, the sodium chloride recycled reach
The dry salt secondary standard of highly industry salt industrial in GB/T 5462-2015 " Nacl " standard, sodium sulphate reaches GB/ in sodium sulphate
II class salt qualified product standard in T6009-2014 " industrial anhydrous sodium sulfate " standard；By organic film upgrading unit 2, evaporation and it is cold
Freeze brilliant process integration processing, realizes the resource utilization of organic wastewater with high concentration, reduce carnallite amount.
It is the preferred embodiment of the present invention above, for those skilled in the art, is not departing from
Under the premise of the principle of the invention, several improvements and modifications can also be made, these improvements and modifications also should be regarded as guarantor of the invention
Protect range.
Claims (9)
1. a kind of salt resource recovering system of organic wastewater with high concentration, which is characterized in that it includes former pond, organic film concentration list
Member is concentrated by evaporation unit, sodium chloride evaporator, mixed salt evaporator and carnallite crystallizer；The water outlet of the former pond with it is described
The water inlet of the core type filter of organic film upgrading unit is connected to by intake pump；The membrane module of the organic film upgrading unit
It produces water out to be connected to the water inlet of the evaporation former pond for being concentrated by evaporation unit, the sodium sulphate for being concentrated by evaporation unit steams
The liquid outlet of hair device is connected to the inlet of the sodium chloride evaporator, the liquid outlet and the mixed salt of the sodium chloride evaporator
The inlet of evaporator is connected to, and the discharge port of the mixed salt evaporator is connected to the feed inlet of the former pond；The mixed salt steams
The liquid outlet of hair device is connected to the inlet of the carnallite crystallizer.
2. a kind of salt resource recovering system of organic wastewater with high concentration according to claim 1, which is characterized in that it further includes
Freezing and crystallizing tank；The liquid outlet of the sodium sulphate evaporator is connected to the inlet of the freezing and crystallizing tank, the freezing and crystallizing
The discharge port of tank is connected to the feed inlet of the sodium sulphate evaporator, and the liquid outlet and the sodium chloride of the freezing and crystallizing tank steam
Send out the inlet connection of device.
3. a kind of salt resource recovering system of organic wastewater with high concentration according to claim 1, which is characterized in that described organic
Film upgrading unit includes the core type filter, the membrane module and high-pressure pump；The liquid outlet of the core type filter with it is described
The inlet of membrane module is connected to by the high-pressure pump.
4. a kind of salt resource recovering system of organic wastewater with high concentration according to claim 3, which is characterized in that the film group
The concentrated water outlet of part is connected to biochemical treatment system.
5. a kind of salt resource recovering system of organic wastewater with high concentration according to claim 1 or 2, which is characterized in that described
Being concentrated by evaporation unit includes the evaporation former pond, bag filter, heat exchanger, the sodium sulphate evaporator and recycling can；Institute
The liquid outlet for stating evaporation former pond is connected to the inlet of the bag filter by water-delivery pump；The bag filter goes out
Liquid mouth is connected to the cold medium entrance of the heat exchanger；The cold medium outlet of the heat exchanger and the sodium sulphate evaporator into
The connection of liquid mouth；The gas outlet of the sodium sulphate evaporator is connected to the thermal medium entrance of the heat exchanger；The heat of the heat exchanger
Media outlet is connected to the recycling can.
6. a kind of salt resource recovering system of organic wastewater with high concentration according to claim 5, which is characterized in that the sulfuric acid
Sodium evaporator is multi-effect evaporator or MVR evaporator.
7. the recycling salt resource side of the salt resource recovering system using a kind of any organic wastewater with high concentration of claim 1-6
Method, which is characterized in that it is the following steps are included: step (1) film is concentrated；Step (2) sodium sulphate evaporative crystallization；Step (3) freezing
Crystallization；Step (4) sodium chloride evaporative crystallization；Step (5) carnallite evaporative crystallization；
Step (1) film concentration: TDS >=60000mg/L, c (Na2SO4): c (NaCl) >=0.67, COD >=30000mg/L, pH=5-
8 high concentrated organic wastewater passes through organic film concentration, obtains concentration and produces water and concentration concentrated water；
Step (2) sodium sulphate evaporative crystallization: concentration obtained in the concentration of the step (1) film is produced into water after filtering, in 80-
100 DEG C are evaporated crystallization and obtain sodium sulfate crystal and sodium sulphate evaporation mother liquor；
Step (3) freezing and crystallizing: by sodium sulphate obtained in the step (2) sodium sulphate evaporative crystallization evaporation mother liquor cool to-
5-0 DEG C, freezing and crystallizing obtains sal glauberi and freezing and crystallizing mother liquor；
Step (4) sodium chloride evaporative crystallization: freezing and crystallizing mother liquor obtained in the step (3) freezing and crystallizing is warming up to 80-
100 DEG C are evaporated crystallization, obtain sodium chloride crystal and sodium chloride evaporation mother liquor；
Step (5) carnallite evaporative crystallization: by the evaporation mother liquor of sodium chloride obtained in the step (4) sodium chloride evaporative crystallization in temperature
Degree continues to evaporate under conditions of being 80-100 DEG C, obtains mixed salt crystal and mixed salt mother liquor, mixed salt crystal is delivered back into raw water
It continues with；The mixed salt mother liquor continues evaporative crystallization, obtains solid waste carnallite.
8. a kind of recycling salt resource allocation method of organic wastewater with high concentration according to claim 7, which is characterized in that the step
(1) in film concentration, the organic wastewater with high concentration carries out film concentration under the conditions of 15 DEG C -25 DEG C, 1-3MPa.
9. a kind of recycling salt resource allocation method of organic wastewater with high concentration according to claim 7, which is characterized in that the step
(2) it after the vapor after the evaporation of sodium sulphate evaporative crystallization produces water preheating to concentration obtained in the concentration of the step (1) film, is formed
Condensed water is simultaneously recovered.
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