CN107867707B - The sub-prime method for crystallising of sodium sulfate in high purity and sodium chloride that resourcebility utilizes is extracted from high-salt wastewater - Google Patents

The sub-prime method for crystallising of sodium sulfate in high purity and sodium chloride that resourcebility utilizes is extracted from high-salt wastewater Download PDF

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CN107867707B
CN107867707B CN201710994394.0A CN201710994394A CN107867707B CN 107867707 B CN107867707 B CN 107867707B CN 201710994394 A CN201710994394 A CN 201710994394A CN 107867707 B CN107867707 B CN 107867707B
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sodium chloride
sodium
quality
salt
product
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CN107867707A (en
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郝红勋
卢海娇
苏楠楠
尹秋响
谢闯
王召
侯宝红
黄欣
王永莉
鲍颖
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Tianjin University
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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
    • 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
    • C01D5/18—Dehydration
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
    • 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
    • C02F2101/101—Sulfur compounds
    • 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
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds
    • 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
    • C02F2101/16—Nitrogen compounds, e.g. ammonia

Abstract

The present invention relates to a kind of from high-salt wastewater extracts the sub-prime method for crystallising of sodium sulfate in high purity and sodium chloride that resourcebility utilizes.Decoloration pretreatment is carried out using active carbon, COD can be significantly reduced, while can remove insoluble impurities, Ca2+、Mg2+, the solable matters such as silicate；It after pretreatment, is successively sent into electrodialysis and mechanical steam recompression device is concentrated, according to the initial composition of waste water sodium sulphate and sodium chloride, reach sodium sulphate and sodium chloride content close to saturation by concentration；Waste water is concentrated and is sent into crystallizer, crystallisation by cooling obtains saltcake, and saltcake directly produces, and washs, and it is dry, obtain anhydrous sodium sulfate product；The concentrate of denitration mother liquor carries out double flash evaporation crystallization, and sodium chloride product directly produces, and washs, dry；Partial mother liquid return system and charging waste water mixing circulation after dual evaporation salt extraction utilize, remaining mother liquor goes to carnallite crystallizing evaporator.The sodium sulphate and sodium chloride product being up to state standards.

Description

The sodium sulfate in high purity that utilizes of resourcebility and sodium chloride are extracted from high-salt wastewater Sub-prime method for crystallising
Technical field
The present invention relates to a kind of sub-prime method for crystallising of high-salt wastewater, are the high-salt wastewaters of a kind of sulfur acid sodium and sodium chloride Sub-prime method for crystallising, in particular to point of the sodium sulfate in high purity that utilizes of resourcebility and sodium chloride is extracted from high-salt wastewater Matter method for crystallising；Belong to environmental protection and chemical field.
Background technique
High-salt wastewater is from a wealth of sources, is concentrated mainly on the industries such as coal, electric power, oil refining, chemical industry, metallurgy, papermaking, pesticide. With the development of modern industrial technology, high-salt wastewater amount is increased rapidly, is brought to current wastewater treatment with recovery and utilization technology Huge challenge.High-salt wastewater contains many kinds of substance, including organic matter, inorganic salts, oil, organic heavy metal and radioactive substance Deng therefore, it is difficult to be handled with biochemical method, therefore being internationally recognized difficulty since salt content height causes strain to be difficult to survive One of waste water of reason has bigger pollution compared with Normal wastewater to environment.
According to production process difference, substance classes and chemical property differ greatly organic matter in high-salt wastewater, but contained Inorganic salts substance is mostly Cl‐、SO4 2‐、Na+、Ca2+Deng.Currently, evaporative desalination method is to handle the most commonly used side of high-salt wastewater Method, basic procedure are that high-salt wastewater is sent into evaporation pond evaporation after being concentrated by evaporation or crystallizing evaporator evaporation, generation are consolidated Body is filled.The law technology is mature, can handle that waste water range is wide, processing speed is fast.But the method is not to sodium sulphate and chlorine Change sodium and carry out classification processing, what is obtained is mixed salt, and organic matter and content of beary metal are exceeded in mixed salt, can not be downstream chlor-alkali etc. Industry is received.Therefore, it can only generally be handled by hazardous waste, processing cost is quite high, brings to enterprises such as coal chemical industries Heavy environmental protection pressure, largely constrains the development of the industries such as coal chemical industry.
In recent years, in order to make full use of the available resources in high-salt wastewater, sodium sulfate in high purity and sodium chloride is extracted, is ground Study carefully personnel and carried out extensive work, the patent literature report delivered at present include CN201510054597.2, CN201510372851.3、CN201510375661.7、CN201510510673.6、CN201510511463.9、 CN201510511464.3, CN201510581032.X etc..Publication number CN201510054597.2 is crystallized by flush distillation, is cold But crystallization, double evaporation-cooling crystallization recycling sodium sulphate and sodium chloride.But this method needs first evaporative crystallization to extract sodium sulphate, so Crystallisation by cooling mentions saltcake again afterwards, and sodium chloride is extracted in last re-evaporation crystallization.Meanwhile in this method, the saltcake of crystallisation by cooling extraction Need to re-dissolve into flush distillation crystal system to keep system in sulfate crystal area.Therefore, process flow is complicated, steady Qualitative difference, and since overall process takes thermal concentration, energy consumption is high.Publication number CN201510372851.3 by flush distillation crystallize, Material is added and generates precipitating removal sulfate ion, double evaporation-cooling crystallization recycling sodium sulphate and sodium chloride, precipitation method removal is remaining Sodium sulphate is more thorough, and sodium chloride obtained by next stage evaporative crystallization is purer, and easy to operate, energy consumption is lower, and the production cycle is shorter. But precipitating reagent (such as calcium chloride, barium chloride), which is added, can introduce new impurity, cause the reduction of sodium chloride product purity.Publication number High-salt wastewater is carried out nanofiltration membrane by CN201510375661.7, obtains chlorination through evaporative crystallization through the trapped fluid of nanofiltration membrane Sodium does not obtain sodium sulphate through evaporative crystallization through the trapped fluid of nanofiltration membrane.The method is easy to operate, product purity is relatively high.But This method needs to carry out a point salt using sodium filter membrane first, increases the cost in membrane material use；Nanofiltration membrane operating pressure simultaneously Greatly, very high to the requirements such as the ability to bear of film and the stifled performance of anti-pollution, film service life is short, and operation expense is high.
The present invention is using electrodialysis concentration, MVR evaporation and concentration, the integrated processing skill of crystallisation by cooling and double flash evaporation crystallization Art recycles sodium sulphate and sodium chloride product from high-salt wastewater efficiently at low cost.With the method phase mentioned in other patents Than the method is successively concentrated using electrodialysis and mechanical steam recompression device, and therefore, process total energy consumption is lower；The method Without using precipitating reagent, new impurity will not be introduced；Meanwhile the method extracts sodium sulphate, salt in anti-upland water first with crystallisation by cooling The ability for dividing content to fluctuate is strong, process stability is higher, and obtained anhydrous sodium sulfate product purity is not less than 98.5%, granularity More evenly, product quality is up to state standards level as defined in (GB/T6009-2014)；In addition, utilizing double flash evaporation crystallization Method extracts sodium chloride, it is ensured that the suspension density of particle is in proper level in crystallizer, to effectively control crystal Secondary nucleation, ensure that the granularity and purity of sodium chloride product, while improve the steady of crystallizing evaporator long period continuous operation Qualitative and reliability, obtained sodium chloride product quality can achieve level as defined in national standard (GB/T5462-2015) and The size distribution of crystal product is more evenly；Finally, this method takes the method for mother liquor fraction reflux to guarantee sodium chloride and sulfuric acid The rate of recovery of sodium product, therefore, the rate of recovery of salt are high, can achieve 90% or more, and partial reflux can be in guarantee system The impurity such as heavy metal and organic matter have reasonable outlet, it is ensured that the stable operation of entire sub-prime crystal system.Therefore, this method The sodium sulphate of high-purity and sodium chloride product in high-salt wastewater can sufficiently be recycled, realize product salt resource utilization and water zero Discharge, with good economic efficiency and social benefit.
Summary of the invention
The technical problem to be solved by the invention is to provide at the recycling of a kind of sulfur acid sodium and the high-salt wastewater of sodium chloride Reason method can inexpensive, expeditiously be realized the recycling of sodium sulphate and sodium chloride in high-salt wastewater by this method, be subtracted The environmental protection pressure of the enterprises such as light coal chemical industry reduces high-salt wastewater processing cost, realizes waste water resource comprehensive utilization.
In order to solve the above technical problems, the technical scheme adopted by the invention is that:
A kind of recovery and treatment method of the high-salt wastewater of sulfur acid sodium and sodium chloride: high-salt wastewater is carried out using active carbon Decoloration pretreatment, is successively sent into electrodialysis and mechanical steam recompression (MVR) device is concentrated, using the side of crystallisation by cooling Method recycles the sodium sulphate in concentrate, and denitration mother liquor is sent into crystallizing evaporator, recycles denitration using the method for double flash evaporation crystallization Sodium chloride in mother liquor concentrations liquid, partial mother liquid return system and charging waste water mixing circulation after dual evaporation salt extraction utilize, Remaining mother liquor goes to carnallite crystallizing evaporator.
As shown in Figure 1, this method includes the following steps:
(1) decoloration pretreatment is carried out using active carbon, removes insoluble impurities, Ca2+、Mg2+, silicate soluble object Matter；
(2) it after pre-processing, is successively sent into electrodialysis and mechanical steam recompression device is concentrated, according to waste water sulfuric acid The initial composition of sodium and sodium chloride reaches sodium sulphate and sodium chloride content close to saturation by concentration；
(3) concentration waste water is sent into crystallizer, and crystallisation by cooling obtains saltcake, and saltcake directly produces, and washs, dry, obtains nothing Aqueous sodium persulfate product；As shown in Figure 2；
(4) concentrate of denitration mother liquor carries out double flash evaporation crystallization, and sodium chloride product directly produces, and washs, dry；
(5) the partial mother liquid return system after dual evaporation salt extraction and charging waste water mixing circulation utilize, remaining mother liquor is gone Toward carnallite crystallizing evaporator.
Activated carbon dosage is 7-9g/L waste water in active carbon decoloring pretreatment in the method step (1)；
COD removal rate is about 75-85% in active carbon decoloring pretreatment in the method step (1)；
The sodium chloride of charging waste water and the total salt amount of sodium sulphate are within the scope of 3-10% in the method step (1), sodium chloride With the ratio between sodium sulfate quality score within the scope of 1-3.2；
Charging waste water is successively concentrated into total salinity about 18-20% with electrodialysis in the method step (2), then with mechanical The concentration of formula vapor recompression (MVR) device, it is 6.5-20.58%, sodium sulphate matter that afterchlorinate sodium mass fraction range is concentrated twice Measuring fraction range is 6.0-9.0%；
The temperature that crystallisation by cooling extracts saltcake in the method step (3) controls within the scope of -5-0 DEG C, and -5 DEG C best；
Sodium sulfate quality score is 0.8- in denitration mother liquor after crystallisation by cooling extraction saltcake in the method step (3) 1.0%；
The condition that I and II evaporative crystallization extracts sodium chloride in step (4) in the method is 65-70 DEG C of heating temperature, Absolute pressure 0.05-0.06MPa；
Sodium chloride product quality flow and crystallizer feeding liquid quality stream in the method step (4) in two-stage crystallizer The ratio between amount range is 0.9-1.1；
Evaporated water accounts for crystallizer inlet amount when level-one evaporative crystallization extracts sodium chloride in the method step (4) 37%-83%, preferably 37.8%-82.3% (are determined) according to high-salt wastewater feed composition；
Evaporated water accounts for crystallizer inlet amount when sodium chloride is extracted in dual evaporation crystallization in the method step (4) 4.0%-48%, preferably 4.0%-47.7% (are determined) according to high-salt wastewater feed composition；
Desalting mother liquor reclamation rate range in the method step (5) after dual evaporation crystallization is 38-42%.
The method, which has the advantages that, provides a kind of efficient high-salt wastewater, low cost, the sub-prime of high stability Method for crystallising, can effectively in the industries high-salt wastewater such as coal chemical industry sodium sulphate and sodium chloride be separately recovered, obtain Sodium sulfate quality be up to state standards two class Grade A standard as defined in (GB/T6009-2014), the purity of sodium sulphate >= 98.5%, sodium chloride product reaches refining industrial salt primes standard as defined in Nacl national standard (GB/T5462-2015), The rate of recovery of sodium chloride purity >=98.5%, sodium chloride and sodium sulphate reaches 90% or more, realizes the comprehensive benefit of waste water resource With.This method process conditions are simple, and process stability is high, and moisture removal evaporation is outer in entire treatment process, arrange without any waste water Out, the zero discharge treatment for realizing high-salt wastewater, reduces cost for wastewater treatment, alleviates enterprise's pressure, and meeting environmental protection needs It wants, with good economic efficiency and social benefit.
Detailed description of the invention
Fig. 1 is the operating procedure and product seperated schematic diagram of the method for the present invention.
Fig. 2 is the anhydrous sodium sulfate product after the saltcake drying that the method for the present invention obtains.
Specific embodiment
Embodiment 1:
The charging high-salt wastewater mass flow of certain coal chemical industry enterprises is 1000kg/h, and through analyzing, wherein sodium chloride quality is divided Number is 2.28%, and sodium sulfate quality score is 0.72%, COD value 500mg/L.
1. a pair high-salt wastewater pre-processes, decoloration pretreatment is carried out using active carbon, active carbon additional amount is useless for 7g/L Water, COD removal rate is 75%, while can remove insoluble impurities, Ca2+、Mg2+, the solable matters such as silicate；
2. pretreated high-salt wastewater charging waste water is first concentrated with electrodialysis, the water quality flow isolated is 833.33kg/h, then with mechanical steam recompression (MVR) device be concentrated, the water quality flow isolated be 55.90kg/h, two Secondary concentration afterchlorinate sodium mass fraction is 20.58%, and sodium sulfate quality score is 6.5%；
3. concentrate is sent into crystallizer, -5 DEG C are cooled to, the saltcake that 13.60kg/h is isolated in centrifugal filtration after constant temperature 3h produces Product, sodium chloride mass fraction 23.46% in denitration mother liquor, sodium sulfate quality score 0.8%；
4. a pair saltcake product washs, dry, anhydrous sodium sulfate product 6.42kg/h is obtained；
5. 97.17kg/h denitration mother liquor is sent into level-one crystallizing evaporator, 70 DEG C of heat source heating temperature, absolute pressure Under the conditions of 0.05MPa, level-one evaporates the vapor of 36.72kg/h, and centrifugal filtration separates the sodium chloride of 13.4kg/h；
6. sending the mother liquor 47.05kg/h after level-one evaporative crystallization into dual evaporation crystallizer, dual evaporation goes out The sodium chloride of 4.95kg/h is isolated in the vapor of 22.41kg/h, centrifugal filtration；
7. a pair sodium chloride product washs, dry；
8. dual evaporation salt extraction post mother liquor mass flow is that 19.69kg/h, wherein 7.88kg/h return system and charging are useless Water mixing circulation utilizes, remaining mother liquor goes to carnallite crystallizing evaporator.
The anhydrous sodium sulfate and sodium chloride product that this technique obtains carry out purity detecting, and testing result is shown in Table 1, table 2 respectively, Contents of heavy metal elements testing result is shown in Table 3 in two product leachates.
1. embodiment of table, 1 anhydrous sodium sulfate product purity detection
2. sodium chloride product purity detection of table
Constituent concentration limit value is endangered in 3. product leachate of table and product leachate endangers constituent concentration
Anhydrous sodium sulfate and sodium chloride product that this technique obtains carry out purity detecting, and (purity is anhydrous sodium sulfate 99.0%) up to the requirement of industrial anhydrous sodium sulfate national standard II class Grade A, sodium chloride (purity 99.0%) is up to work The rate of recovery of the requirement of industry salt national standard refining industrial salt first class product, sodium chloride and sodium sulphate reaches 90% or more, and a huge sum of money Belong to content and is lower than National Hazard waste judging standard.Two kinds of product purity height of sodium chloride and sodium sulphate, all can serve as Nacl It uses, realizes utilization of wastewater resource.
Embodiment 2:
The charging high-salt wastewater mass flow of certain coal chemical industry enterprises is 1000kg/h, and through analyzing, wherein sodium chloride quality is divided Number is 7.61%, and sodium sulfate quality score is 2.38%, COD value 580mg/L.
1. a pair high-salt wastewater pre-processes, decoloration pretreatment is carried out using active carbon, active carbon additional amount is useless for 8g/L Water, COD removal rate is 80%, while can remove insoluble impurities, Ca2+、Mg2+, the solable matters such as silicate；
2. pretreated high-salt wastewater charging waste water is first concentrated with electrodialysis, the water quality flow isolated is 444.44kg/h, then be concentrated with mechanical steam recompression (MVR) device, the water quality flow isolated is 185.78kg/h, Concentration afterchlorinate sodium mass fraction is 20.1% twice, and sodium sulfate quality score is 6.33%；
3. concentrate is sent into crystallizer, -3 DEG C are cooled to, centrifugal filtration after constant temperature 3h, the saltcake product of 48.24kg/h takes off Sodium chloride mass fraction 23.46% in nitre mother liquor, sodium sulfate quality score 0.83%；
4. a pair saltcake product washs, dry, anhydrous sodium sulfate product 21.23kg/h is obtained；
5. 321.54kg/h denitration mother liquor is sent into level-one crystallizing evaporator, 68 DEG C of heat source heating temperature, absolute pressure Under the conditions of 0.055MPa, level-one evaporates the vapor of 121.51kg/h, and centrifugal filtration separates the sodium chloride of 44.34kg/h；
6. sending the mother liquor 155.69kg/h after level-one evaporative crystallization into dual evaporation crystallizer, dual evaporation goes out The sodium chloride of 16.38kg/h is isolated in the vapor of 74.27kg/h, centrifugal filtration；
7. a pair sodium chloride product washs, dry；
8. dual evaporation salt extraction post mother liquor mass flow is that 65.04kg/h, wherein 26.02kg/h return system and charging are useless Water mixing circulation utilizes, remaining mother liquor goes to carnallite crystallizing evaporator.
Anhydrous sodium sulfate and sodium chloride product that this technique obtains carry out purity detecting, and (purity is anhydrous sodium sulfate 99.1%) up to the requirement of industrial anhydrous sodium sulfate national standard II class Grade A, sodium chloride (purity 99.2%) is up to work The rate of recovery of the requirement of industry salt national standard refining industrial salt first class product, sodium chloride and sodium sulphate reaches 90% or more, and a huge sum of money Belong to content and is lower than National Hazard waste judging standard.Two kinds of product purity height of sodium chloride and sodium sulphate, all can serve as Nacl It uses, realizes utilization of wastewater resource.
Embodiment 3:
The charging high-salt wastewater mass flow of certain coal chemical industry enterprises is 1000kg/h, and through analyzing, wherein sodium chloride quality is divided Number is 3.10%, and sodium sulfate quality score is 1.80%, COD value 600mg/L.
1. a pair high-salt wastewater pre-processes, decoloration pretreatment is carried out using active carbon, active carbon additional amount is useless for 9g/L Water, COD removal rate is 85%, while can remove insoluble impurities, Ca2+, Mg2+, the solable matters such as silicate；
2. pretreated high-salt wastewater charging waste water is first concentrated with electrodialysis, the water quality flow isolated is 750.00kg/h, then be concentrated with mechanical steam recompression (MVR) device, the water quality flow isolated is 50.00kg/h, dense Contracting afterchlorinate sodium mass fraction is 15.5%, and sodium sulfate quality score is 9.0%；
3. concentrate is sent into crystallizer, it is cooled to 0 DEG C, centrifugal filtration after constant temperature 3h, the saltcake for obtaining 37.96kg/h produces Product, sodium chloride mass fraction 19.13% in denitration mother liquor, sodium sulfate quality score 0.85%；
4. a pair saltcake product washs, dry, anhydrous sodium sulfate product 16.70kg/h is obtained；
5. 162.04kg/h denitration liquid is sent into level-one crystallizing evaporator, 65 DEG C of heat source heating temperature, absolute pressure Under the conditions of 0.06MPa, level-one evaporates the vapor of 92.27kg/h, and the sodium chloride of 17.66kg/h is isolated in centrifugal filtration；
6. sending level-one evaporative crystallization mother liquor 52.11kg/h into dual evaporation crystallizer, dual evaporation goes out 21.71kg/h Vapor, centrifugal filtration isolates the sodium chloride of 6.44kg/h；
7. a pair sodium chloride product washs, dry；
8. dual evaporation salt extraction post mother liquor mass flow is that 30.53kg/h, wherein 12.21kg/h return system and charging are useless Water mixing circulation utilizes, remaining mother liquor goes to carnallite crystallizing evaporator.
Anhydrous sodium sulfate and sodium chloride product that this technique obtains carry out purity detecting, and (purity is anhydrous sodium sulfate 98.9%) up to the requirement of industrial anhydrous sodium sulfate national standard II class Grade A, sodium chloride (purity 99.2%) is up to work The rate of recovery of the requirement of industry salt national standard refining industrial salt first class product, sodium chloride and sodium sulphate reaches 90% or more, and a huge sum of money Belong to content and is lower than National Hazard waste judging standard.Two kinds of product purity height of sodium chloride and sodium sulphate, all can serve as Nacl It uses, realizes utilization of wastewater resource.
Embodiment 4:
The charging high-salt wastewater mass flow of certain coal chemical industry enterprises is 1000kg/h, and through analyzing, wherein sodium chloride quality is divided Number is 1.5%, and sodium sulfate quality score is 1.5%, COD value 580mg/L.
1. a pair high-salt wastewater pre-processes, decoloration pretreatment is carried out using active carbon, active carbon additional amount is 8.5g/L Waste water, COD removal rate is 78%, while can remove insoluble impurities, Ca2+、Mg2+, the solable matters such as silicate；
2. pretreated high-salt wastewater charging waste water is concentrated with electrodialysis, the water quality flow isolated is 469.23kg/h, then be concentrated with mechanical steam recompression (MVR) device, the water quality flow isolated is 300.00kg/h, It is 6.5% that afterchlorinate sodium mass fraction, which is concentrated, and sodium sulfate quality score is 6.5%；
3. concentrate is sent into crystallizer, -5 DEG C are cooled to, the saltcake product of centrifugal filtration after constant temperature 3h, 30.45kg/h is de- Sodium chloride mass fraction 7.49% in nitre mother liquor, sodium sulfate quality score 1.0%；
4. a pair saltcake product washs, dry, anhydrous sodium sulfate product 13.40kg/h is obtained；
5. 200.32kg/h denitration mother liquor is sent into level-one crystallizing evaporator, 70 DEG C of heat source heating temperature, absolute pressure Under the conditions of 0.058MPa, level-one evaporates the vapor of 164.89kg/h, and the sodium chloride of 7.97kg/h is isolated in centrifugal filtration；
6. sending level-one evaporative crystallization mother liquor 27.46kg/h into dual evaporation crystallizer, dual evaporation goes out 1.08kg/h Vapor, centrifugal filtration isolates the sodium chloride of 1.38kg/h；
7. a pair sodium chloride product washs, dry；
8. evaporation salt extraction post mother liquor mass flow is 25.00kg/h, wherein 10.00kg/h return system and charging waste water are mixed Conjunction recycles, remaining mother liquor goes to carnallite crystallizing evaporator.
Anhydrous sodium sulfate and sodium chloride product that this technique obtains carry out purity detecting, and (purity is anhydrous sodium sulfate 99.3%) up to the requirement of industrial anhydrous sodium sulfate national standard II class Grade A, sodium chloride (purity 99.0%) is up to work The rate of recovery of the requirement of industry salt national standard refining industrial salt first class product, sodium chloride and sodium sulphate reaches 90% or more, and a huge sum of money Belong to content and is lower than National Hazard waste judging standard.Two kinds of product purity height of sodium chloride and sodium sulphate, all can serve as Nacl It uses, realizes utilization of wastewater resource.
Embodiment 5:
The charging high-salt wastewater mass flow of certain coal chemical industry enterprises is 1000kg/h, and through analyzing, wherein sodium chloride quality is divided Number is 5.0%, and sodium sulfate quality score is 5.0%, COD value 580mg/L.
1. a pair high-salt wastewater pre-processes, decoloration pretreatment is carried out using active carbon, active carbon additional amount is useless for 9g/L Water, COD removal rate is 78%, while can remove insoluble impurities, the solable matters such as Ca2+, Mg2+, silicate；
2. pretreated high-salt wastewater charging waste water is concentrated with electrodialysis plant, the water quality flow isolated is 230.77kg/h, concentration afterchlorinate sodium mass fraction are 6.5%, and sodium sulfate quality score is 6.5%；
3. concentrate is sent into crystallizer, -5 DEG C are cooled to, the saltcake product of centrifugal filtration after constant temperature 3h, 101.50kg/h is de- Sodium chloride mass fraction 7.49% in nitre mother liquor, sodium sulfate quality score 0.9%；
4. a pair saltcake product washs, dry, anhydrous sodium sulfate product 44.66kg/h is obtained；
5. 667.73kg/h denitration mother liquor is sent into level-one crystallizing evaporator, 67 DEG C of heat source heating temperature, absolute pressure Under the conditions of 0.053MPa, the vapor of 546.53kg/h is evaporated, centrifugal filtration separates the sodium chloride of 25.5kg/h；
6. sending level-one evaporative crystallization mother liquor 95.70kg/h into dual evaporation crystallizer, dual evaporation goes out 6.62kg/h Vapor, centrifugal filtration isolates the sodium chloride of 5.64kg/h；
7. a pair sodium chloride product washs, dry；
8. evaporation salt extraction post mother liquor mass flow is 83.44kg/h, wherein 33.37kg/h return system and charging waste water are mixed Conjunction recycles, remaining mother liquor goes to carnallite crystallizing evaporator.
Anhydrous sodium sulfate and sodium chloride product that this technique obtains carry out purity detecting, and (purity is anhydrous sodium sulfate 99.1%) up to the requirement of industrial anhydrous sodium sulfate national standard II class Grade A, sodium chloride (purity 98.8%) is up to work The rate of recovery of the requirement of industry salt national standard refining industrial salt first class product, sodium chloride and sodium sulphate reaches 90% or more, and a huge sum of money Belong to content and is lower than National Hazard waste judging standard.Two kinds of product purity height of sodium chloride and sodium sulphate, all can serve as Nacl It uses, realizes utilization of wastewater resource.
It can be seen from the above embodiments that, the anhydrous sodium sulfate and sodium chloride product purity that the method for the present invention obtains Reach technical grade national standard, and content of beary metal is lower than National Hazard waste judging standard, all can serve as Nacl use, Realize utilization of wastewater resource.
The present invention discloses a kind of recovery and treatment method of the high-salt wastewater of sulfur acid sodium and sodium chloride, those skilled in the art It can be by using for reference present disclosure, the links such as appropriate feed change, technological parameter are realized.Method of the invention and product by compared with Good examples of implementation are described, related technical personnel obviously can not depart from the content of present invention, in spirit and scope to herein The method and product is modified or appropriate changes and combinations, Lai Shixian the technology of the present invention.In particular, it should be pointed out that institute There are similar replacement and change apparent to those skilled in the art, they are considered as being included in the present invention In spirit, range and content.

Claims (9)

1. a kind of sub-prime method for crystallising for extracting sodium sulfate in high purity and sodium chloride that resourcebility utilizes from high-salt wastewater；Its It is characterized in including the following steps:
(1) charging high-salt wastewater carries out decoloration pretreatment using active carbon, removes insoluble impurities, Ca2+、Mg2+, silicate can Soluble substance；
(2) after pre-processing, electrodialysis and mechanical steam recompression device are successively sent into and is concentrated, according to waste water sodium sulphate and The initial composition of sodium chloride reaches sodium sulphate and sodium chloride content close to saturation by concentration；
(3) concentration waste water is sent into crystallizer, and crystallisation by cooling obtains saltcake, and saltcake directly produces, and washs, dry, obtains anhydrous sulphur Sour sodium product；
(4) concentrate of denitration mother liquor carries out double flash evaporation crystallization, and sodium chloride product directly produces, and washs, dry；
(5) the partial mother liquid return system after dual evaporation salt extraction and charging waste water mixing circulation utilize, remaining mother liquor is gone to miscellaneous Salt crystallizing evaporator；
The sodium chloride of charging high-salt wastewater and the total salt quality of sodium sulphate are in 3-10%, sodium chloride and sodium sulphate in the step (1) The ratio between mass fraction is in the range of 1:1~3.2；The temperature that crystallisation by cooling extracts saltcake in the step (3) is controlled at -5-0 DEG C In range；The quality of evaporation water accounts for crystallizer feedstock quality when level-one evaporative crystallization extracts sodium chloride in the step (4) 37%-83%；Evaporation water quality accounts for the 4.0%-48% of crystallizer feedstock quality when sodium chloride is extracted in dual evaporation crystallization；It is described It is 18-20% that charging waste water, which is first concentrated into total saliferous mass fraction with electrodialysis, in step (2), then uses mechanical steam recompression Device concentration, it is 6.5-20.58% that afterchlorinate sodium mass fraction range is concentrated twice, and sodium sulfate quality fraction range is 6.0- 9.0%.
2. the method as described in claim 1, it is characterized in that activated carbon dosage in active carbon decoloring pretreatment in the step (1) For 7-9g/L waste water.
3. the method as described in claim 1, it is characterized in that COD removal rate in active carbon decoloring pretreatment in the step (1) For 75-85%.
4. the method as described in claim 1, it is characterized in that crystallisation by cooling extracts the temperature control of saltcake in the step (3) At -5 DEG C.
5. the method as described in claim 1, it is characterized in that in the step (3) after crystallisation by cooling extraction saltcake in denitration mother liquor Sodium sulfate quality score is 0.8-1.0%.
6. the method as described in claim 1, it is characterized in that I and II evaporative crystallization extracts sodium chloride in the step (4) Condition is 65-70 DEG C of heating temperature, absolute pressure 0.05-0.06MPa.
7. the method as described in claim 1, it is characterized in that the sodium chloride product quality in the step (4) in two-stage crystallizer The ratio between flow and crystallizer feeding liquid mass flow range are 0.9-1.1.
8. the method as described in claim 1 is evaporated when it is characterized in that level-one evaporative crystallization extracting sodium chloride in the step (4) Water quality accounts for the 37.8%-82.3% of crystallizer feedstock quality；Evaporation water quality accounts for knot when sodium chloride is extracted in dual evaporation crystallization The 4.0%-47.7% of brilliant device feedstock quality.
9. the method as described in claim 1, it is characterized in that the desalting mother liquor in the method step (5) after dual evaporation crystallization Reclamation rate range is 38-42%.
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