CN106315991A - Industrial wastewater salt separation technology and industrialized application thereof - Google Patents

Abstract

The invention relates to an industrial wastewater salt separation technology and industrialized application thereof, belonging to the field of water management. In allusion to coal chemical industry wastewater and coal mine drainage water, reduced high concentration saline water is further concentrated and is subjected to evaporative crystallization for salt separation treatment through double membrane process reduction treatment in the step one and a 'zero release' system in the step two, thereby realizing the goals of the zero release of wastewater and resource utilization of crystal salt and carnallite reduction. Anhydrous sodium sulfate produced according to the technical scheme conforms to the standards of first-grade products in GB/T 6009-2014 Industrial Anhydrous Sodium Sulfate Type I, and sodium sulfate reaches the standards of first-grade refined industrial salt and drying salt in GB/T 5462-2015 Industrial Salt. The technical scheme is simple and practicable, and the operation is convenient, so that the technical scheme is suitable for large-scale popularization and application.

Description

A kind of Industry Waste moisture salt technology and industrial applications thereof

Technical field

The invention belongs to high-salt wastewater process field, the process relating to a kind of industrial wastewater divides salt technology and industrialization thereof to answer With, particularly relate to point salt technology and the industrial applications thereof of coal chemical industrial waste water and colliery drainage water.

Background technology

In recent years, along with development and the raising of cities and towns living standards of the people of industrial and agricultural production, industrial wastewater, municipal sewage Discharge capacity is increasing, the environmental pollution thus caused, and has badly influenced environmental ecology and human health, especially high salt high The emission problem of concentration organic wastewater is on the rise, and is one of the major reason of water environment pollution.High-salt-content organic wastewater contains Some leading ions are Cl^-、SO₄ ^2-、Na⁺、Ca²⁺Deng salts substances.High concentration ion can produce suppression and poison work microorganism With, mainly performance: salinity is high, osmotic pressure is high, microbial cell dehydration causes cellular plasm to separate；Salting out makes dehydrogenation Enzymatic activity reduces；The high effect toxic to antibacterial of chloride ion；Salinity is high, and the density of waste water increases, and activated sludge easily floats stream Lose, thus have a strong impact on the clean-up effect of biological treatment system.How to process high-salt wastewater thus ensure that the cleaning of water resource is Problem demanding prompt solution at present.

China's Coal Chemical Industry is flourish through " 12 ", and technique and equipment technology all achieve huge progress, coal gas Change technology, methanol-to-olefins technological project are in full flourish in the Northwest, but coal resources and water resource are more in contrary distribution.Make For Xinjiang of Development of Coal Chemical Industry main body, the Inner Mongol, Shanxi, Shaanxi, ratio of water to coal is only 1: 22,1: 30,1: 45 and 1: 7, water resource Become the primary binding target of Development of Coal Chemical Industry.

Concentrated Halite water total dissolved solidss (TDS) are usually 4000～50000mg/L, if directly discharge can cause River and underground water pollution, can cause the serious ecological problems such as region water level decreasing, vegetation degeneration, desertification of land what is more.With Enforcement and the proposition of " ten, water " of the new environmental law of country in 2015, in order to survive, each coal chemical industry enterprises realizes waste water " zero-emission Put " become the only way which must be passed, by specific " zero-emission " technique, high slat-containing wastewater is concentrated, salt-pepper noise is solid, produces water whole For reuse, reach the target of sewage/wastewater " zero-emission ".

In industry, discharge technology flow process is as follows at present:

Although this technology can realize the target of sewage/wastewater " zero-emission ", but the shortcoming of its maximum is crystal salt is mixing Carnallite, carnallite comprises multiple inorganic matter, and large amount of organic, and carnallite has extremely strong solubility, and its stability is with solid The property changed is poor, can ooze out along with drenching with rain, in turn results in secondary pollution.Additionally carnallite belongs to danger wastes, and processing cost is high, mesh The processing cost of front dangerous solid waste is about 3000 yuan/ton, considerably increases the operating cost of enterprise.

In view of industrial wastewater crystal salt intractability greatly, costly, and high environment permit standard, for realizing " zero-emission " And the stabilisation of the crystal salt produced, innoxious and recycling will be the research sides that process further of industrial wastewater crystal salt To.

Summary of the invention

For the defect of prior art, the present invention is directed to coal chemical industrial waste water and/or colliery drainage water, the first step is by double films Method minimizing processes, and second step is " zero-emission " system, the further concentration of high strong brine of minimizing, evaporative crystallization is divided at salt Reason, it is achieved waste water zero emission, crystal salt recycling, the target of carnallite minimizing, it is achieved that high salt concentration moisture salt skill The industrial applications of art

Specifically, the concrete scheme of the present invention is achieved in that and includes following process step:

(1) pretreatment of industrial wastewater；

(2) desalting processing；

(3) " zero-emission " point salt technology pretreatment；

(4) dense water concentrates；

(5) evaporative crystallization divides salt；

(6) residue mother solution drying and other treatment.

In the present invention, minimizing system inflow scope is 1000-1800m³/h.It is preferably 1200m³/h。

The industrial wastewater of described step () can be coal chemical industrial waste water, colliery drainage water one or both.

Preferably, the industrial wastewater of described step () is coal chemical industrial waste water and colliery drainage water.

Wherein, coal chemical industrial waste water inflow scope is 100-500m³/ h, preferably 200m³/h；Colliery drainage water inflow Scope is 700-1300m³/ h, preferably 1000m³/h。

The method of the pretreatment of step (one) industrial wastewater includes high dense settling pond, immersion ultrafiltration or high density clarification Pond, filter tank, ultrafiltration two ways.

Wherein: the method for the pretreatment of step (one) industrial wastewater includes high dense settling pond, immersion ultrafiltration pretreatment Step includes:

1, coal chemical industrial waste water pretreatment

(1) TDS >=5560mg/L coal chemical industrial waste water of appropriate flow velocity is introduced high dense settling pond, and add quality and compare body Long-pending, with kg/m³Calculate, add 2-8kg/m³Bodied ferric sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, polyacrylamide Mixture, filtering precipitate, waste water processes further；

(2) the pending waste water of step (1) leads to ozone 1-3 hour, then measures B/C value.

(3) waste water after ozone oxidation of step (2) reacts 12-24 hour from flowing to biochemistry pool；

(4) in the case of oxygen-supplying amount is 95-100%, the waste water of step (3) is carried out in MBR membrane biological reaction pond Filtration and adsorption treatment；Then the water of filtration is delivered to ion exchanger and carry out degree of depth sofening treatment, after softening, deliver to next Step desalting processing；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, and regenerative wastewater is delivered to " zero-emission " system and processed；

Wherein, the bodied ferric sulfate in step (1) mixture, sodium carbonate, calcium hydroxide, sodium hydroxide, polyacrylamide Weight consumption ratio be: 50-300:20-100:10-50:5-25:5-20.

Step (2) B/C value is in the range of 1.0-3.5.

2, colliery drainage water pretreatment

(1) TDS >=9280mg/L colliery drainage water of appropriate flow velocity is introduced high dense settling pond, and add quality and compare body Long-pending, with kg/m³Calculate, add 2-8kg/m³Bodied ferric sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, polyacrylamide Mixture, filtering precipitate, water demineralization；

(2) waste water of step (1) is carried out filtration treatment through immersion ultrafiltration；Then the water of filtration is delivered to ion exchange Device carries out degree of depth sofening treatment, delivers to next step desalting processing after softening；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, regeneration Waste water is delivered to " zero-emission " system and is processed；

Wherein, step (1) bodied ferric sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, the weight consumption of polyacrylamide Ratio is: 50-300:20-100:10-50:5-25:5-20.

Described acid includes hydrochloric acid.Described alkali include sodium hydroxide, potassium hydroxide one or both.It is preferably hydrogen-oxygen Change sodium.

3, step (two) desalting processing step includes:

(1) desalination includes single stage desalting--middle pressure reverse osmosis, the former water softened through the degree of depth is delivered to middle pressure reverse osmosis and is taken off Salt, obtains product water and recycles, and dense water processes again；

(2) two grades of desalination-high pressure reverse osmosiss.The dense water of above-mentioned steps is delivered to high pressure reverse osmosis and carries out desalination, produced Product Water Sproading utilizes, and dense water is delivered to " zero-emission " system and processed.

Wherein；After the described dense water in step (1) obtains concentrating for the first time, TDS scope is 30000-60000mg/L.

Wherein；It is 60000-100000mg/L that the described dense water in step (2) obtains TDS scope after second time concentrates.

4, step (three) " zero-emission " system pre-treatment step includes:

In dense water, add appropriate sodium carbonate, sodium hydroxide, remove the calcium in strong brine, magnesium ion, through ozone catalytic Oxidation, activated carbon adsorption organics removal, obtain pretreatment water outlet after chelating resin softens；

5, step (four) dense water concentration step includes:

Use enrichment facility to the further minimizing of dense water of step (three), improve dense water salinity.

Described enrichment facility can be just permeating, vibrating diaphragm, STRO/DTRO, electric drive film device or MVR falling film evaporation Device；The TDS of dense water reaches 100000-200000mg/L.

6, step (five) evaporative crystallization divides salt to use step to include:

(1) feed liquid after step (four) concentration initially enters IV effect of four-effect countercurrent extraction crystallizing evaporator, is depended on by guide pump Secondary entrance III, II, I imitate, heating with steam then with feed liquid flow to contrary, give birth to steam initially enter I effect, then enter back into II effect, III effect, IV effect, anhydrous sodium sulfate crystal salt is from I effect, II effect extraction, by washing, be dehydrated, be dried, weigh, packing, simultaneously IV Imitate after secondary vapour is condensed by surface condenser as product water reuse；

(2) I single-effect evaporator concentrated solutions deliver to cooler crystallizer, separate out sal glauberi crystallization, sal glauberi when 0 DEG C Crystallization is delivered to IV effect feed end and is continued through quadruple effect crystallizer output anhydrous sodium sulfate；

(3) concentrated solution after crystallisation by cooling delivers to salt crystallizing evaporator extraction sodium chloride, and sodium chloride is by being dehydrated, being dried also Weighing, pack, residue mother solution is standby；

7, the mother solution mummification of step (six) residue uses step to include:

Above-mentioned residue mother solution is by being spray-dried drying and other treatment, output carnallite, it is achieved waste water zero emission.

The present invention compared with prior art, has prominent advantage and is mainly reflected in the following aspects:

(1), during this point of salt technology is applied to industrial wastewater " zero-emission " process by the present invention, waste water " zero-emission is finally realized Put "；The water, the anhydrous sodium sulfate that reclaim, sodium chloride can industrialized utilization again.Residue mother solution is by being spray-dried at mummification Reason, output carnallite amount is the 0-10% of total salt amount, it is achieved carnallite minimizing, significantly reduces expense and pressure that carnallite processes.

(2) anhydrous sodium sulfate of Industry Waste moisture salt technology final production is met GB/ by technical scheme T6009-2014 " industrial anhydrous sodium sulfate " I class Grade A standard, sodium chloride reaches GB/T 5462-2015 " Nacl " and refines Nacl dry salt primes standard, it is achieved crystal salt recycling, reduces the discharge capacity of solid waste.

(3) it is used alternatingly by cold and hot crystallization process, a point salt can not only be realized, and can guarantee that crystal salt quality, be to realize The guarantee of crystal salt recycling.

(4) this method uses vacuum band-type filter machine to wash anhydrous sodium sulfate crystal salt, and final product quality meets Related request.

(5) this point of salt technology commercialization is applied by the present invention, widelys popularize for industry and provides reliability service foundation.This skill Art scheme simple possible, easy to operate applicable large-scale application.

Accompanying drawing 1: technical solution of the present invention workflow graph.

Specific embodiment

In order to absolutely prove the technique of patent of the present invention, Technology of the present invention is described in the following embodiments, These embodiments are intended for illustrating, and should not be construed or be interpreted as the restriction to present invention protection.

Embodiment 1:

1, coal chemical industrial waste water pretreatment

(1) by 100m³The TDS of/h is that 5560mg/L coal chemical industrial waste water introduces high dense settling pond, and adds 2kg/m³Suitable Amount bodied ferric sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, polyacrylamide mixture (bodied ferric sulfate, sodium carbonate, Calcium hydroxide, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 50:20:10:5:5), filtering precipitate, water demineralization；

(2) the pending water of step (1) leads to ozone 1 hour, then measures B/C value in the range of 1.0；

(3) waste water after ozone oxidation of step (2) reacts 12 hours from flowing to biochemistry pool；

(4) in the case of oxygen-supplying amount is 95%, the waste water of step (3) is filtered in MBR membrane biological reaction pond Adsorption treatment；Then the water of filtration is delivered to ion exchanger and carry out degree of depth sofening treatment, after softening, deliver to next step Desalting processing；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, and regenerative wastewater is delivered to " zero-emission " system and processed；

2, colliery drainage water pretreatment

(1) by 700m³The colliery drainage water that the TDS of/h is introduces high dense settling pond, and adds 2kg/m³Polyaluminum sulfate Ferrum, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, sodium carbonate, calcium hydroxide, the hydrogen of polyacrylamide Sodium oxide, the weight consumption ratio of polyacrylamide be: 50:20:10:5:5), filtering precipitate, water demineralization；

(2) waste water of step (1) is carried out filtration treatment through immersion ultrafiltration；Then the water of filtration is delivered to ion exchange Device carries out degree of depth sofening treatment, delivers to next step desalting processing after softening；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, regeneration Waste water is delivered to " zero-emission " system and is processed；

3, step (two) desalting processing step includes:

(1) desalination includes single stage desalting--middle pressure reverse osmosis, the former water softened through the degree of depth is delivered to middle pressure reverse osmosis and is taken off Salt, obtains product water and recycles, and dense water processes again, and after dense water obtains concentrating for the first time, TDS reaches 35000mg/L；

(2) two grades of desalination-high pressure reverse osmosiss.The dense water of above-mentioned steps is delivered to high pressure reverse osmosis and carries out desalination, produced Product Water Sproading utilizes, and dense water is delivered to " zero-emission " system and processed, and dense water obtains TDS after second time concentrates and reaches 62000mg/L；

4, step (three) " zero-emission " system pre-treatment step includes:

In dense water, add appropriate sodium carbonate, sodium hydroxide, remove the calcium in strong brine, magnesium ion, through ozone catalytic Oxidation, activated carbon adsorption organics removal, obtain pretreatment water outlet after chelating resin softens；

5, step (four) dense water concentration step includes:

Electric drive film device and MVR falling film evaporator to the further minimizing of dense water of step (three), improve dense water saliferous Amount, the TDS of dense water is 100000mg/L.

6, step (five) evaporative crystallization divides salt step to include:

(1) feed liquid after step (four) concentration initially enters IV effect of four-effect countercurrent extraction crystallizing evaporator, is depended on by guide pump Secondary entrance III, II, I imitate, heating with steam then with feed liquid flow to contrary, give birth to steam initially enter I effect, then enter back into II effect, III effect, IV effect, anhydrous sodium sulfate crystal salt, from I effect, II effect extraction, by washing, being dehydrated, is dried and weighs, simultaneously IV effect secondary Vapour condensed by surface condenser after as product water reuse；

(2) I single-effect evaporator concentrated solutions deliver to cooler crystallizer, separate out sal glauberi crystallization, sal glauberi when 0 DEG C Crystallization is delivered to IV effect feed end and is continued through quadruple effect crystallizer output anhydrous sodium sulfate；

(3) concentrated solution after crystallisation by cooling delivers to salt crystallizing evaporator extraction sodium chloride, and sodium chloride is by being dehydrated, being dried also Weighing, residue mother solution is standby；

7, the mother solution mummification of step (six) residue uses step to include:

Above-mentioned residue mother solution is by being spray-dried drying and other treatment, output carnallite, it is achieved waste water zero emission.Through calculating: Minimizing system inflow is 800m³/ h, wherein Coal Chemical Industry strong brine is 100m³/ h, colliery drainage water is 700m³/ h, " zero-emission Put " system inflow is 133m³/ h, the final products water yield is 741.0m³/ h, anhydrous sodium sulfate 7.1t/h, sodium chloride 0.49t/h, Carnallite 0.31t/h.

Embodiment 2:

1, coal chemical industrial waste water pretreatment

(1) by 200m³The TDS of/h is that 5560mg/L coal chemical industrial waste water introduces high dense settling pond, and adds 5kg/m³Poly- Close iron sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, sodium carbonate, the hydroxide of polyacrylamide Calcium, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15:12), filtering precipitate, water demineralization；

(2) the pending water of step (1) leads to ozone 2 hours, then measure B/C value for 2.2；

(3) waste water after ozone oxidation of step (2) reacts 18 hours from flowing to biochemistry pool；

(4) in the case of oxygen-supplying amount is 100%, the waste water of step (3) is filtered in MBR membrane biological reaction pond Adsorption treatment；Then the water of filtration is delivered to ion exchanger and carry out degree of depth sofening treatment, after softening, deliver to next step Desalting processing；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, and regenerative wastewater is delivered to " zero-emission " system and processed.

2, colliery drainage water pretreatment

(1) by 1000m³The colliery drainage water that the TDS of/h is appropriate for 9280mg/L introduces high dense settling pond, and adds 5kg/m³Bodied ferric sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, the carbonic acid of polyacrylamide Sodium, calcium hydroxide, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15:12), filtering precipitate, water Matter softens；

(2) waste water of step (1) is carried out filtration treatment through immersion ultrafiltration；Then the water of filtration is delivered to ion exchange Device carries out degree of depth sofening treatment, delivers to next step desalting processing after softening；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, regeneration Waste water is delivered to " zero-emission " system and is processed.

3, step (two) desalting processing step includes:

(1) desalination includes single stage desalting--middle pressure reverse osmosis, the former water softened through the degree of depth is delivered to middle pressure reverse osmosis and is taken off Salt, obtains product water and recycles, and dense water processes again；After dense water obtains concentrating for the first time, TDS reaches 30000mg/L

(2) two grades of desalination-high pressure reverse osmosiss.The dense water of above-mentioned steps is delivered to high pressure reverse osmosis and carries out desalination, produced Product Water Sproading utilizes, and dense water is delivered to " zero-emission " system and processed；Dense water obtains TDS after second time concentrates and reaches 60000mg/L.

4, step (three) " zero-emission " system pre-treatment step includes:

In dense water, add appropriate sodium carbonate, sodium hydroxide, remove the calcium in strong brine, magnesium ion, through ozone catalytic Oxidation, activated carbon adsorption organics removal, obtain pretreatment water outlet after chelating resin softens；6, step (four) dense water concentration step Including:

The further minimizing of dense water to step (three) of the electric drive film device, improves dense water salinity, and the TDS of dense water is 150000mg/L。

6, step (five) evaporative crystallization divides salt step to include:

(1) feed liquid after step (four) concentration initially enters IV effect of four-effect countercurrent extraction crystallizing evaporator, is depended on by guide pump Secondary entrance III, II, I imitate, heating with steam then with feed liquid flow to contrary, give birth to steam initially enter I effect, then enter back into II effect, III effect, IV effect, anhydrous sodium sulfate crystal salt, from I effect, II effect extraction, by washing, being dehydrated, is dried and weighs, simultaneously IV effect secondary Vapour condensed by surface condenser after as product water reuse；

(2) I single-effect evaporator concentrated solutions deliver to cooler crystallizer, separate out sal glauberi crystallization, sal glauberi when 0 DEG C Crystallization is delivered to IV effect feed end and is continued through quadruple effect crystallizer output anhydrous sodium sulfate；

(3) concentrated solution after crystallisation by cooling delivers to salt crystallizing evaporator extraction sodium chloride, and sodium chloride is by being dehydrated, being dried also Weighing, residue mother solution is standby；

7, the mother solution mummification of step (six) residue uses step to include:

Above-mentioned residue mother solution is by being spray-dried drying and other treatment, output carnallite, it is achieved waste water zero emission.Through calculating: Minimizing system inflow is 1200m³/ h, wherein Coal Chemical Industry strong brine is 200m³/ h, colliery drainage water is 1000m³/ h, " zero Discharge " system inflow is 200m³/ h, the final products water yield is 1138.3.0m³/ h, anhydrous sodium sulfate 11.1t/h, sodium chloride 0.84t/h, carnallite 0.37t/h.

Embodiment 3:

1, coal chemical industrial waste water pretreatment

(1) by 300m³The TDS of/h is that 7280mg/L coal chemical industrial waste water introduces high dense settling pond, and adds 8kg/m³Polymerization Iron sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, sodium carbonate, the hydroxide of polyacrylamide Calcium, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 300:100:50:25:20), filtering precipitate, water demineralization；

(2) the pending water of step (1) leads to ozone 1-3 hour, then measure B/C value for 4.5；

(3) waste water after ozone oxidation of step (2) reacts 24 hours from flowing to biochemistry pool；

(4) in the case of oxygen-supplying amount is 100%, the waste water of step (3) is filtered in MBR membrane biological reaction pond Adsorption treatment；Then the water of filtration is delivered to ion exchanger and carry out degree of depth sofening treatment, after softening, deliver to next step Desalting processing；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, and regenerative wastewater is delivered to " zero-emission " system and processed.

2, colliery drainage water pretreatment

(1) by 1500m³The colliery drainage water that the TDS of/h is appropriate for 10320mg/L introduces high dense settling pond, and adds 8kg/m³Bodied ferric sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, the carbonic acid of polyacrylamide Sodium, calcium hydroxide, sodium hydroxide, the amount ratio of polyacrylamide be: 300:100:50:25:20), filtering precipitate, water quality is soft Change；

(2) waste water of step (1) is carried out filtration treatment through immersion ultrafiltration；Then the water of filtration is delivered to ion exchange Device carries out degree of depth sofening treatment, delivers to next step desalting processing after softening；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, regeneration Waste water is delivered to " zero-emission " system and is processed.

3, step (two) desalting processing step includes:

(1) desalination includes single stage desalting--middle pressure reverse osmosis, the former water softened through the degree of depth is delivered to middle pressure reverse osmosis and is taken off Salt, obtains product water and recycles, and dense water processes again；After dense water obtains concentrating for the first time, TDS reaches 60000mg/L

(2) two grades of desalination-high pressure reverse osmosiss.The dense water of above-mentioned steps is delivered to high pressure reverse osmosis and carries out desalination, produced Product Water Sproading utilizes, and dense water is delivered to " zero-emission " system and processed；Dense water obtains TDS after second time concentrates and reaches 100000mg/L.

4, step (three) " zero-emission " system pre-treatment step includes:

In dense water, add appropriate sodium carbonate, sodium hydroxide, remove the calcium in strong brine, magnesium ion, through ozone catalytic Oxidation, activated carbon adsorption organics removal, obtain pretreatment water outlet after chelating resin softens；

5, step (four) dense water concentration step includes:

Use enrichment facility to the further minimizing of dense water of step (two), improve dense water salinity.

Described enrichment facility can be just permeating, vibrating diaphragm, STRO/DTRO, electric drive film device or MVR falling film evaporation Device；The TDS of dense water reaches 200000mg/L.

6, step (five) evaporative crystallization divides salt step to include:

(1) feed liquid after step (four) concentration initially enters IV effect of four-effect countercurrent extraction crystallizing evaporator, is depended on by guide pump Secondary entrance III, II, I imitate, heating with steam then with feed liquid flow to contrary, give birth to steam initially enter I effect, then enter back into II effect, III effect, IV effect, anhydrous sodium sulfate crystal salt, from I effect, II effect extraction, by washing, being dehydrated, is dried and weighs, simultaneously IV effect secondary Vapour condensed by surface condenser after as product water reuse；

(2) I single-effect evaporator concentrated solutions deliver to cooler crystallizer, separate out sal glauberi crystallization, sal glauberi when 0 DEG C Crystallization is delivered to IV effect feed end and is continued through quadruple effect crystallizer output anhydrous sodium sulfate；

(3) concentrated solution after crystallisation by cooling delivers to salt crystallizing evaporator extraction sodium chloride, and sodium chloride is by being dehydrated, being dried also Weighing, residue mother solution is standby；

7, the mother solution mummification of step (six) residue uses step to include:

Above-mentioned residue mother solution is by being spray-dried drying and other treatment, output carnallite, it is achieved waste water zero emission.

Through calculating: minimizing system inflow is 1800m³/ h, wherein Coal Chemical Industry strong brine is 300m³/ h, colliery drainage Water is 1500m³/ h, " zero-emission " system inflow is 300m³/ h, the final products water yield is 1044.5m³/ h, anhydrous sodium sulfate 10.8t/h, sodium chloride 0.55t/h, carnallite 1.01t/h.

Embodiment 4:

1, coal chemical industrial waste water pretreatment

(1) by 250m³The TDS of/h is that 5560mg/L coal chemical industrial waste water introduces high dense settling pond, and adds 5kg/m³Polymerization Iron sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, sodium carbonate, the hydroxide of polyacrylamide Calcium, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15:12), filtering precipitate, water demineralization；

(2) the pending water of step (1) leads to ozone 1-3 hour, then measure B/C value for 2.0；

(3) waste water after ozone oxidation of step (2) reacts 18 hours from flowing to biochemistry pool；

(4) in the case of oxygen-supplying amount is 100%, the waste water of step (3) is filtered in MBR membrane biological reaction pond Adsorption treatment；Then the water of filtration is delivered to ion exchanger and carry out degree of depth sofening treatment, after softening, deliver to next step Desalting processing；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, and regenerative wastewater is delivered to " zero-emission " system and processed.

2, colliery drainage water pretreatment

(1) by 1250m³The colliery drainage water that the TDS of/h is appropriate for 9280mg/L introduces high dense settling pond, and adds 5kg/m³Bodied ferric sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, the carbonic acid of polyacrylamide Sodium, calcium hydroxide, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15:12), filtering precipitate, water Matter softens；

(2) waste water of step (1) is carried out filtration treatment through immersion ultrafiltration；Then the water of filtration is delivered to ion exchange Device carries out degree of depth sofening treatment, delivers to next step desalting processing after softening；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, regeneration Waste water is delivered to " zero-emission " system and is processed.

3, step (two) desalting processing step includes:

(1) desalination includes single stage desalting--middle pressure reverse osmosis, the former water softened through the degree of depth is delivered to middle pressure reverse osmosis and is taken off Salt, obtains product water and recycles, and dense water processes again；After dense water obtains concentrating for the first time, TDS reaches 44000mg/L

(2) two grades of desalination-high pressure reverse osmosiss.The dense water of above-mentioned steps is delivered to high pressure reverse osmosis and carries out desalination, produced Product Water Sproading utilizes, and dense water is delivered to " zero-emission " system and processed；Dense water obtains TDS after second time concentrates and reaches 77000mg/L.

4, step (three) " zero-emission " system pre-treatment step includes:

In dense water, add appropriate sodium carbonate, sodium hydroxide, remove the calcium in strong brine, magnesium ion, through ozone catalytic Oxidation, activated carbon adsorption organics removal, obtain pretreatment water outlet after chelating resin softens；

5, step (four) dense water concentration step includes:

The further minimizing of dense water to step (three) of the electric drive film device, improves dense water salinity, and the TDS of dense water is 150000mg/L。

6, step (five) evaporative crystallization divides salt step to include:

(1) feed liquid after step (four) concentration initially enters IV effect of four-effect countercurrent extraction crystallizing evaporator, is depended on by guide pump Secondary entrance III, II, I imitate, heating with steam then with feed liquid flow to contrary, give birth to steam initially enter I effect, then enter back into II effect, III effect, IV effect, anhydrous sodium sulfate crystal salt, from I effect, II effect extraction, by washing, being dehydrated, is dried and weighs, simultaneously IV effect secondary Vapour condensed by surface condenser after as product water reuse；

(2) I single-effect evaporator concentrated solutions deliver to cooler crystallizer, separate out sal glauberi crystallization, sal glauberi when 0 DEG C Crystallization is delivered to IV effect feed end and is continued through quadruple effect crystallizer output anhydrous sodium sulfate；

(3) concentrated solution after crystallisation by cooling delivers to salt crystallizing evaporator extraction sodium chloride, and sodium chloride is by being dehydrated, being dried also Weighing, residue mother solution is standby；

7, the mother solution mummification of step (six) residue uses step to include:

Above-mentioned residue mother solution is by being spray-dried drying and other treatment, output carnallite, it is achieved waste water zero emission.

Through calculating: minimizing system inflow is 1500m³/ h, wherein Coal Chemical Industry strong brine is 250m³/ h, colliery drainage Water is 1250m³/ h, " zero-emission " system inflow is 250m³/ h, the final products water yield is 1038.5m³/ h, anhydrous sodium sulfate 10.1t/h, sodium chloride 0.80t/h, carnallite 0.77t/h.

Embodiment 5:

1, coal chemical industrial waste water pretreatment

(1) by 200m³The TDS of/h is that 6130mg/L coal chemical industrial waste water introduces high dense settling pond, and adds 5kg/m³Polymerization Iron sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, sodium carbonate, the hydroxide of polyacrylamide Calcium, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15:12), filtering precipitate, water demineralization；

(2) the pending water of step (1) leads to ozone 2 hours, then measure B/C value for 2.3；

(3) waste water after ozone oxidation of step (2) reacts 18 hours from flowing to biochemistry pool；

(4) in the case of oxygen-supplying amount is 100%, the waste water of step (3) is filtered in MBR membrane biological reaction pond Adsorption treatment；Then the water of filtration is delivered to ion exchanger and carry out degree of depth sofening treatment, after softening, deliver to next step Desalting processing；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, and regenerative wastewater is delivered to " zero-emission " system and processed.

2, colliery drainage water pretreatment

(1) by 1000m³The colliery drainage water that the TDS of/h is appropriate for 9822mg/L introduces high dense settling pond, and adds 5kg/m³Bodied ferric sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, the carbonic acid of polyacrylamide Sodium, calcium hydroxide, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15:12), filtering precipitate, water Matter softens；

(2) waste water of step (1) is carried out filtration treatment through immersion ultrafiltration；Then the water of filtration is delivered to ion exchange Device carries out degree of depth sofening treatment, delivers to next step desalting processing after softening；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, regeneration Waste water is delivered to " zero-emission " system and is processed.

3, step (two) desalting processing step includes:

(1) desalination includes single stage desalting--middle pressure reverse osmosis, the former water softened through the degree of depth is delivered to middle pressure reverse osmosis and is taken off Salt, obtains product water and recycles, and dense water processes again；After dense water obtains concentrating for the first time, TDS reaches 47000mg/L

(2) two grades of desalination-high pressure reverse osmosiss.The dense water of above-mentioned steps is delivered to high pressure reverse osmosis and carries out desalination, produced Product Water Sproading utilizes, and dense water is delivered to " zero-emission " system and processed；Dense water obtains TDS after second time concentrates and reaches 82000mg/L.

4, step (three) " zero-emission " system pre-treatment step includes:

In dense water, add appropriate sodium carbonate, sodium hydroxide, remove the calcium in strong brine, magnesium ion, through ozone catalytic Oxidation, activated carbon adsorption organics removal, obtain pretreatment water outlet after chelating resin softens；

5, step (four) dense water concentration step includes:

The further minimizing of dense water to step (three) of the electric drive film device, improves dense water salinity, and the TDS of dense water is 160000mg/L。

6, step (five) evaporative crystallization divides salt step to include:

(1) feed liquid after step (four) concentration initially enters IV effect of four-effect countercurrent extraction crystallizing evaporator, is depended on by guide pump Secondary entrance III, II, I imitate, heating with steam then with feed liquid flow to contrary, give birth to steam initially enter I effect, then enter back into II effect, III effect, IV effect, anhydrous sodium sulfate crystal salt, from I effect, II effect extraction, by washing, being dehydrated, is dried and weighs, simultaneously IV effect secondary Vapour condensed by surface condenser after as product water reuse；

(2) I single-effect evaporator concentrated solutions deliver to cooler crystallizer, separate out sal glauberi crystallization, sal glauberi when 0 DEG C Crystallization is delivered to IV effect feed end and is continued through quadruple effect crystallizer output anhydrous sodium sulfate；

(3) concentrated solution after crystallisation by cooling delivers to salt crystallizing evaporator extraction sodium chloride, and sodium chloride is by being dehydrated, being dried also Weighing, residue mother solution is standby；

7, the mother solution mummification of step (six) residue uses step to include:

Above-mentioned residue mother solution is by being spray-dried drying and other treatment, output carnallite, it is achieved waste water zero emission.

Through calculating: minimizing system inflow is 1200m³/ h, wherein Coal Chemical Industry strong brine is 200m³/ h, colliery drainage Water is 1000m³/ h, " zero-emission " system inflow is 200m³/ h, the final products water yield is 1144.3.0m³/ h, anhydrous sodium sulfate 11.7t/h, sodium chloride 0.91t/h, carnallite 0.42t/h.

Embodiment 6:

1, coal chemical industrial waste water pretreatment

(1) by 200m³The TDS of/h is that 6130mg/L coal chemical industrial waste water introduces high dense settling pond, and adds 5kg/m³Polymerization Iron sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, sodium carbonate, the hydroxide of polyacrylamide Calcium, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15:12), filtering precipitate, water demineralization；

(2) the pending water of step (1) leads to ozone 2 hours, then measure B/C value for 2.3；

(3) waste water after ozone oxidation of step (2) reacts 18 hours from flowing to biochemistry pool；

(4) in the case of oxygen-supplying amount is 100%, the waste water of step (3) is filtered in MBR membrane biological reaction pond Adsorption treatment；Then the water of filtration is delivered to ion exchanger and carry out degree of depth sofening treatment, after softening, deliver to next step Desalting processing；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, and regenerative wastewater is delivered to " zero-emission " system and processed.

2, colliery drainage water pretreatment

(1) by 1000m³The colliery drainage water that the TDS of/h is appropriate for 9822mg/L introduces high dense settling pond, and adds 5kg/m³Bodied ferric sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, the carbonic acid of polyacrylamide Sodium, calcium hydroxide, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15:12), filtering precipitate, water Matter softens；

(2) waste water of step (1) gained is led to ozone 2 through the pending water of filtering ponds, hyperfiltration treatment (2) step (1) little Time, then measure B/C value for 2.3；

(3) waste water after ozone oxidation of step (2) reacts 18 hours from flowing to biochemistry pool；

(4) in the case of oxygen-supplying amount is 100%, the waste water of step (3) is filtered in MBR membrane biological reaction pond Adsorption treatment；Then the water of filtration is delivered to ion exchanger and carry out degree of depth sofening treatment, after softening, deliver to next step Desalting processing；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, and regenerative wastewater is delivered to " zero-emission " system and processed.

3, step (two) desalting processing step includes:

(1) desalination includes single stage desalting--middle pressure reverse osmosis, the former water softened through the degree of depth is delivered to middle pressure reverse osmosis and is taken off Salt, obtains product water and recycles, and dense water processes again；After dense water obtains concentrating for the first time, TDS reaches 35000mg/L

(2) two grades of desalination-high pressure reverse osmosiss.The dense water of above-mentioned steps is delivered to high pressure reverse osmosis and carries out desalination, produced Product Water Sproading utilizes, and dense water is delivered to " zero-emission " system and processed；Dense water obtains TDS after second time concentrates and reaches 59000mg/L.

4, step (three) " zero-emission " system pre-treatment step includes:

In dense water, add appropriate sodium carbonate, sodium hydroxide, remove the calcium in strong brine, magnesium ion, through ozone catalytic Oxidation, activated carbon adsorption organics removal, obtain pretreatment water outlet after chelating resin softens；

5, step (four) dense water concentration step includes:

The further minimizing of dense water to step (three) of the electric drive film device, improves dense water salinity, and the TDS of dense water is 130000mg/L。

6, step (five) evaporative crystallization divides salt step to include:

(1) feed liquid after step (four) concentration initially enters IV effect of four-effect countercurrent extraction crystallizing evaporator, is depended on by guide pump Secondary entrance III, II, I imitate, heating with steam then with feed liquid flow to contrary, give birth to steam initially enter I effect, then enter back into II effect, III effect, IV effect, anhydrous sodium sulfate crystal salt, from I effect, II effect extraction, by washing, being dehydrated, is dried and weighs, simultaneously IV effect secondary Vapour condensed by surface condenser after as product water reuse；

(2) I single-effect evaporator concentrated solutions deliver to cooler crystallizer, separate out sal glauberi crystallization, sal glauberi when 0 DEG C Crystallization is delivered to IV effect feed end and is continued through quadruple effect crystallizer output anhydrous sodium sulfate；

(3) concentrated solution after crystallisation by cooling delivers to salt crystallizing evaporator extraction sodium chloride, and sodium chloride is by being dehydrated, being dried also Weighing, residue mother solution is standby；

7, the mother solution mummification of step (six) residue uses step to include:

Above-mentioned residue mother solution is by being spray-dried drying and other treatment, output carnallite, it is achieved waste water zero emission.

Through calculating: minimizing system inflow is 1200m³/ h, wherein Coal Chemical Industry strong brine is 200m³/ h, colliery drainage Water is 1000m³/ h, " zero-emission " system inflow is 200m³/ h, the final products water yield is 958.3.0m³/ h, anhydrous sodium sulfate 6.7t/h, sodium chloride 0.51t/h, carnallite 1.96t/h.

Embodiment 7:

1, coal chemical industrial waste water pretreatment

(1) by 200m³The TDS of/h is that 6130mg/L coal chemical industrial waste water introduces high dense settling pond, and adds 5kg/m³Polymerization Iron sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, sodium carbonate, the hydroxide of polyacrylamide Calcium, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15:12), filtering precipitate, water demineralization；

(2) the pending water of step (1) leads to ozone 2 hours, then measure B/C value for 2.3；

(3) waste water after ozone oxidation of step (2) reacts 18 hours from flowing to biochemistry pool；

(4) in the case of oxygen-supplying amount is 100%, the waste water of step (3) is filtered in MBR membrane biological reaction pond Adsorption treatment；Then the water of filtration is delivered to ion exchanger and carry out degree of depth sofening treatment, after softening, deliver to next step Desalting processing；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, and regenerative wastewater is delivered to " zero-emission " system and processed.

2, colliery drainage water pretreatment

(1) by 1000m³The colliery drainage water that the TDS of/h is appropriate for 9822mg/L introduces high dense settling pond, and adds 5kg/m³Bodied ferric sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, the carbonic acid of polyacrylamide Sodium, calcium hydroxide, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15:12), filtering precipitate, water Matter softens；

(2) waste water of step (1) is carried out filtration treatment through immersion ultrafiltration；Then the water of filtration is delivered to ion exchange Device carries out degree of depth sofening treatment, delivers to next step desalting processing after softening；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, regeneration Waste water is delivered to " zero-emission " system and is processed.

3, step (two) desalting processing step includes:

(1) desalination includes single stage desalting--middle pressure reverse osmosis, the former water softened through the degree of depth is delivered to middle pressure reverse osmosis and is taken off Salt, obtains product water and recycles, and dense water processes again；After dense water obtains concentrating for the first time, TDS reaches 47000mg/L

(2) two grades of desalination-high pressure reverse osmosiss.The dense water of above-mentioned steps is delivered to high pressure reverse osmosis and carries out desalination, produced Product Water Sproading utilizes, and dense water is delivered to " zero-emission " system and processed；Dense water obtains TDS after second time concentrates and reaches 82000mg/L.

4, step (three) " zero-emission " system pre-treatment step includes:

In dense water, add appropriate sodium carbonate, sodium hydroxide, remove the calcium in strong brine, magnesium ion, through ozone catalytic Oxidation, activated carbon adsorption organics removal, obtain pretreatment water outlet after chelating resin softens；

5, step (four) dense water concentration step includes:

The further minimizing of dense water to step (three) of the MVR falling film evaporator, improves dense water salinity, and the TDS of dense water is 200000mg/L。

6, step (five) evaporative crystallization divides salt step to include:

(1) feed liquid after step (four) concentration initially enters IV effect of four-effect countercurrent extraction crystallizing evaporator, is depended on by guide pump Secondary entrance III, II, I imitate, heating with steam then with feed liquid flow to contrary, give birth to steam initially enter I effect, then enter back into II effect, III effect, IV effect, anhydrous sodium sulfate crystal salt, from I effect, II effect extraction, by washing, being dehydrated, is dried and weighs, simultaneously IV effect secondary Vapour condensed by surface condenser after as product water reuse；

(2) I single-effect evaporator concentrated solutions deliver to cooler crystallizer, separate out sal glauberi crystallization, sal glauberi when 0 DEG C Crystallization is delivered to IV effect feed end and is continued through quadruple effect crystallizer output anhydrous sodium sulfate；

(3) concentrated solution after crystallisation by cooling delivers to salt crystallizing evaporator extraction sodium chloride, and sodium chloride is by being dehydrated, being dried also Weighing, residue mother solution is standby；

7, the mother solution mummification of step (six) residue uses step to include:

Above-mentioned residue mother solution is by being spray-dried drying and other treatment, output carnallite, it is achieved waste water zero emission.

Through calculating: minimizing system inflow is 1200m³/ h, wherein Coal Chemical Industry strong brine is 200m³/ h, colliery drainage Water is 1000m³/ h, " zero-emission " system inflow is 200m³/ h, the final products water yield is 1134.0m³/ h, anhydrous sodium sulfate 11.5t/h, sodium chloride 0.89t/h, carnallite 0.44t/h.

Embodiment 8:

1, coal chemical industrial waste water pretreatment

(1) by 200m³The TDS of/h is that 6130mg/L coal chemical industrial waste water introduces high dense settling pond, and adds 5kg/m³Polymerization Iron sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, sodium carbonate, the hydroxide of polyacrylamide Calcium, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15:12), filtering precipitate, water demineralization；

(2) the pending water of step (1) leads to ozone 2 hours, then measure B/C value for 2.3；

(3) waste water after ozone oxidation of step (2) reacts 18 hours from flowing to biochemistry pool；

(4) in the case of oxygen-supplying amount is 100%, the waste water of step (3) is filtered in MBR membrane biological reaction pond Adsorption treatment；Then the water of filtration is delivered to ion exchanger and carry out degree of depth sofening treatment, after softening, deliver to next step Desalting processing；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, and regenerative wastewater is delivered to " zero-emission " system and processed.

2, colliery drainage water pretreatment

(1) by 1000m³The colliery drainage water that the TDS of/h is appropriate for 9822mg/L introduces high dense settling pond, and adds poly- Close iron sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, sodium carbonate, the hydroxide of polyacrylamide Calcium, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15:12), filtering precipitate, water demineralization；

(2) waste water of step (1) is carried out filtration treatment through immersion ultrafiltration；Then the water of filtration is delivered to ion exchange Device carries out degree of depth sofening treatment, delivers to next step desalting processing after softening；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, regeneration Waste water is delivered to " zero-emission " system and is processed.

3, step (two) desalting processing step includes:

(1) desalination includes single stage desalting--middle pressure reverse osmosis, the former water softened through the degree of depth is delivered to middle pressure reverse osmosis and is taken off Salt, obtains product water and recycles, and dense water processes again；After dense water obtains concentrating for the first time, TDS reaches 47000mg/L

(2) two grades of desalination-high pressure reverse osmosiss.The dense water of above-mentioned steps is delivered to high pressure reverse osmosis and carries out desalination, produced Product Water Sproading utilizes, and dense water is delivered to " zero-emission " system and processed；Dense water obtains TDS after second time concentrates and reaches 82000mg/L.

4, step (three) " zero-emission " system pre-treatment step includes:

In dense water, add appropriate sodium carbonate, sodium hydroxide, remove the calcium in strong brine, magnesium ion, through ozone catalytic Oxidation, activated carbon adsorption organics removal, obtain pretreatment water outlet after chelating resin softens；

5, step (four) dense water concentration step includes:

Just permeating the further minimizing of dense water to step (three), improving dense water salinity, the TDS of dense water is 200000mg/L。

6, step (five) evaporative crystallization divides salt step to include:

(1) feed liquid after step (four) concentration initially enters IV effect of four-effect countercurrent extraction crystallizing evaporator, is depended on by guide pump Secondary entrance III, II, I is imitated, and heating steam then flows to contrary with feed liquid, and raw steam initially enters I effect, then enters back into II, imitate, III effect, IV effect, anhydrous sodium sulfate crystal salt, from I effect, II effect extraction, by washing, being dehydrated, is dried and weighs, simultaneously IV effect secondary Vapour condensed by surface condenser after as product water reuse；

(2) I single-effect evaporator concentrated solutions deliver to cooler crystallizer, separate out sal glauberi crystallization, sal glauberi when 0 DEG C Crystallization is delivered to IV effect feed end and is continued through quadruple effect crystallizer output anhydrous sodium sulfate；

(3) concentrated solution after crystallisation by cooling delivers to salt crystallizing evaporator extraction sodium chloride, and sodium chloride is by being dehydrated, being dried also Weighing, residue mother solution is standby；

7, the mother solution mummification of step (six) residue uses step to include:

Above-mentioned residue mother solution is by being spray-dried drying and other treatment, output carnallite, it is achieved waste water zero emission.

Through calculating: minimizing system inflow is 1200m³/ h, wherein Coal Chemical Industry strong brine is 200m³/ h, colliery drainage Water is 1000m³/ h, " zero-emission " system inflow is 200m³/ h, the final products water yield is 1114.0m³/ h, anhydrous sodium sulfate 11.0t/h, sodium chloride 0.81t/h, carnallite 0.54t/h.

Embodiment 9:

1, coal chemical industrial waste water pretreatment

(1) by 200m³The TDS of/h is that 6130mg/L coal chemical industrial waste water introduces high dense settling pond, and adds 5kg/m³Polymerization Iron sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, sodium carbonate, the hydroxide of polyacrylamide Calcium, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15:12), filtering precipitate, water demineralization；

(2) the pending water of step (1) leads to ozone 2 hours, then measure B/C value for 2.3；

(3) waste water after ozone oxidation of step (2) reacts 18 hours from flowing to biochemistry pool；

(4) in the case of oxygen-supplying amount is 100%, the waste water of step (3) is filtered in MBR membrane biological reaction pond Adsorption treatment；Then the water of filtration is delivered to ion exchanger and carry out degree of depth sofening treatment, after softening, deliver to next step Desalting processing；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, and regenerative wastewater is delivered to " zero-emission " system and processed.

2, colliery drainage water pretreatment

(1) by 1000m³The colliery drainage water that the TDS of/h is appropriate for 9822mg/L introduces high dense settling pond, and adds 5kg/m³Bodied ferric sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, the carbonic acid of polyacrylamide Sodium, calcium hydroxide, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15:12), filtering precipitate, water Matter softens；

(2) waste water of step (1) is carried out filtration treatment through immersion ultrafiltration；Then the water of filtration is delivered to ion exchange Device carries out degree of depth sofening treatment, delivers to next step desalting processing after softening；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, regeneration Waste water is delivered to " zero-emission " system and is processed.

3, step (two) desalting processing step includes:

(1) desalination includes single stage desalting--middle pressure reverse osmosis, the former water softened through the degree of depth is delivered to middle pressure reverse osmosis and is taken off Salt, obtains product water and recycles, and dense water processes again；After dense water obtains concentrating for the first time, TDS reaches 47000mg/L

(2) two grades of desalination-high pressure reverse osmosiss.The dense water of above-mentioned steps is delivered to high pressure reverse osmosis and carries out desalination, produced Product Water Sproading utilizes, and dense water is delivered to " zero-emission " system and processed；Dense water obtains TDS after second time concentrates and reaches 82000mg/L.

4, step (three) " zero-emission " system pre-treatment step includes:

In dense water, add appropriate sodium carbonate, sodium hydroxide, remove the calcium in strong brine, magnesium ion, through ozone catalytic Oxidation, activated carbon adsorption organics removal, obtain pretreatment water outlet after chelating resin softens；

5, step (four) dense water concentration step includes:

Just permeating the further minimizing of dense water to step (three), improving dense water salinity, the TDS of dense water is 200000mg/L。

6, step (five) evaporative crystallization divides salt step to include:

(1) feed liquid after step (four) concentration initially enters IV effect of four-effect countercurrent extraction crystallizing evaporator, is depended on by guide pump Secondary entrance III, II, I imitate, heating with steam then with feed liquid flow to contrary, give birth to steam initially enter I effect, then enter back into II effect, III effect, IV effect, anhydrous sodium sulfate crystal salt, from I effect, II effect extraction, by washing, being dehydrated, is dried and weighs, simultaneously IV effect secondary Vapour condensed by surface condenser after as product water reuse；

(2) I single-effect evaporator concentrated solutions deliver to cooler crystallizer, separate out sal glauberi crystallization, sal glauberi when 0 DEG C Crystallization is delivered to IV effect feed end and is continued through quadruple effect crystallizer output anhydrous sodium sulfate；

(3) concentrated solution after crystallisation by cooling delivers to salt crystallizing evaporator extraction sodium chloride, and sodium chloride is by being dehydrated, being dried also Weighing, residue mother solution is standby；

7, the mother solution mummification of step (six) residue uses step to include:

Above-mentioned residue mother solution is by being spray-dried drying and other treatment, output carnallite, it is achieved waste water zero emission.

Through calculating: minimizing system inflow is 1200m³/ h, wherein Coal Chemical Industry strong brine is 200m³/ h, colliery drainage Water is 1000m³/ h, " zero-emission " system inflow is 200m³/ h, the final products water yield is 1135.0m³/ h, anhydrous sodium sulfate 11.5t/h, sodium chloride 0.81t/h, carnallite 0.57t/h.

Embodiment 10:

1, colliery drainage water pretreatment

(1) by 1200m³The colliery drainage water that the TDS of/h is appropriate for 9280mg/L introduces high dense settling pond, and adds 5kg/m³Bodied ferric sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, the carbonic acid of polyacrylamide Sodium, calcium hydroxide, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15:12), filtering precipitate, water Matter softens；Then the water of filtration is delivered to ion exchanger and carry out degree of depth sofening treatment, deliver to next step after softening and take off Salt treatment；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, and regenerative wastewater is delivered to " zero-emission " system and processed.

(2) waste water of step (1) is carried out filtration treatment through immersion ultrafiltration；

3, step (two) desalting processing step includes:

(1) desalination includes single stage desalting--middle pressure reverse osmosis, the former water softened through the degree of depth is delivered to middle pressure reverse osmosis and is taken off Salt, obtains product water and recycles, and dense water processes again；After dense water obtains concentrating for the first time, TDS reaches 45000mg/L

(2) two grades of desalination-high pressure reverse osmosiss.The dense water of above-mentioned steps is delivered to high pressure reverse osmosis and carries out desalination, produced Product Water Sproading utilizes, and dense water is delivered to " zero-emission " system and processed；Dense water obtains TDS after second time concentrates and reaches 80000mg/L.

4, step (three) " zero-emission " system pre-treatment step includes:

In dense water, add appropriate sodium carbonate, sodium hydroxide, remove the calcium in strong brine, magnesium ion, through ozone catalytic Oxidation, activated carbon adsorption organics removal, obtain pretreatment water outlet after chelating resin softens；

5, step (four) dense water concentration step includes:

The further minimizing of dense water to step (two) of the electric drive film device, improves dense water salinity, and the TDS of dense water is 190000mg/L。

6, step (five) evaporative crystallization divides salt step to include:

(1) feed liquid after step (four) concentration initially enters IV effect of four-effect countercurrent extraction crystallizing evaporator, is depended on by guide pump Secondary entrance III, II, I is imitated, and heating steam then flows to contrary with feed liquid, and raw steam initially enters I effect, then enters back into II, imitate, III effect, IV effect, anhydrous sodium sulfate crystal salt, from I effect, II effect extraction, by washing, being dehydrated, is dried and weighs, simultaneously IV effect secondary Vapour condensed by surface condenser after as product water reuse；

(2) I single-effect evaporator concentrated solutions deliver to cooler crystallizer, separate out sal glauberi crystallization, sal glauberi when 0 DEG C Crystallization is delivered to IV effect feed end and is continued through quadruple effect crystallizer output anhydrous sodium sulfate；

(3) concentrated solution after crystallisation by cooling delivers to salt crystallizing evaporator extraction sodium chloride, and sodium chloride is by being dehydrated, being dried also Weighing, residue mother solution is standby；

7, the mother solution mummification of step (six) residue uses step to include:

Above-mentioned residue mother solution is by being spray-dried drying and other treatment, output carnallite, it is achieved waste water zero emission.

Through calculating: minimizing system inflow is 1200m³/ h, " zero-emission " system inflow is 200m³/ h, finally produces The product water yield is 1128.3.0m³/ h, anhydrous sodium sulfate 10.1t/h, sodium chloride 0.64t/h, carnallite 0.77t/h.

Embodiment 11:

1, coal chemical industrial waste water pretreatment

(1) by 200m³The TDS of/h is that 5560mg/L coal chemical industrial waste water introduces high dense settling pond, and adds 5kg/m³Poly- Close iron sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, sodium carbonate, the hydroxide of polyacrylamide Calcium, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15:12), filtering precipitate, water demineralization；

(2) the pending water of step (1) leads to ozone 2 hours, then measure B/C value for 2.2；

(3) waste water after ozone oxidation of step (2) reacts 18 hours from flowing to biochemistry pool；

(4) in the case of oxygen-supplying amount is 100%, the waste water of step (3) is filtered in MBR membrane biological reaction pond Adsorption treatment；Then the water of filtration is delivered to ion exchanger and carry out degree of depth sofening treatment, after softening, deliver to next step Desalting processing；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, and regenerative wastewater is delivered to " zero-emission " system and processed.

2, colliery drainage water pretreatment

(1) by 1000m³The colliery drainage water that the TDS of/h is appropriate for 9280mg/L introduces high dense settling pond, and adds 5kg/m³Bodied ferric sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, mixture (bodied ferric sulfate, the carbonic acid of polyacrylamide Sodium, calcium hydroxide, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15:12), filtering precipitate, water Matter softens；

(2) waste water of step (1) is carried out filtration treatment through immersion ultrafiltration；Then the water of filtration is delivered to ion exchange Device carries out degree of depth sofening treatment, delivers to next step desalting processing after softening；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, regeneration Waste water is delivered to " zero-emission " system and is processed.

3, product water is obtained, at gained concentrated solution continuation after being processed by MVP falling film evaporator by the former water of step 3 Reason；

5, the concentrated solution in step 4 processes through crystallizing evaporator, separates out calcium carbonate crystal and product water recycles, Carnallite centrifuge dehydration.

Through calculating: minimizing system inflow is 1200m³/ h, wherein Coal Chemical Industry strong brine is 200m³/ h, colliery drainage Water is 1000m³/ h, " zero-emission " system inflow is 200m³/ h, the final products water yield is 890.3.0m³/ h, calcium carbonate crystal 0.84t/h, carnallite 14.37t/h.

Claims (10)

1. point salt technology for industrial wastewater, it is characterised in that: include following process step:

(1) pretreatment of industrial wastewater；

(2) desalting processing；

(3) " zero-emission " point salt technology pretreatment；

(4) dense water concentrates；

(5) evaporative crystallization divides salt；

(6) residue mother solution drying and other treatment.

The most according to claim 1 point of salt technology, it is characterised in that described industrial wastewater inflow scope is 1000- 1800m³/ h, preferably 1200m³/h。

The most according to claim 1 point of salt technology, it is characterised in that described industrial wastewater is coal chemical industrial waste water, colliery Drainage water one or both.

The most according to claim 3 point of salt technology, it is characterised in that described coal chemical industrial waste water inflow scope is 100- 500m³/ h, preferably 200m³/h；Colliery drainage water inflow scope is 700-1300m³/ h, preferably 1000m³/h。

The most according to claim 1 point of salt technology, it is characterised in that the method for the pretreatment of described industrial wastewater includes High dense settling pond, immersion ultrafiltration or high dense settling pond, filter tank, ultrafiltration two ways.

The most according to claim 1 point of salt technology, it is characterised in that described step includes:

1, coal chemical industrial waste water pretreatment

(1) TDS >=5560mg/L coal chemical industrial waste water of appropriate flow velocity is introduced high dense settling pond, and adds quality than volume, With kg/m³Calculate, add 2-8kg/m³Bodied ferric sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, the mixing of polyacrylamide Thing, filtering precipitate, waste water processes further；

(2) the pending waste water of step (1) leads to ozone 1-3 hour, then measures B/C value；

(3) waste water after ozone oxidation of step (2) reacts 12-24 hour from flowing to biochemistry pool；

(4) in the case of oxygen-supplying amount is 95-100%, the waste water of step (3) is filtered in MBR membrane biological reaction pond Adsorption treatment；Then the water of filtration is delivered to ion exchanger and carry out degree of depth sofening treatment, after softening, deliver to next step Desalting processing；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, and regenerative wastewater is delivered to " zero-emission " system and processed；

2, colliery drainage water pretreatment

(1) TDS >=9280mg/L colliery drainage water of appropriate flow velocity is introduced high dense settling pond, and adds quality than volume, With kg/m³Calculate, add 2-8kg/m³Bodied ferric sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, the mixing of polyacrylamide Thing, filtering precipitate, water demineralization；

(2) waste water of step (1) is carried out filtration treatment through immersion ultrafiltration；Then the water of filtration is delivered to ion exchanger enter Row carries out degree of depth sofening treatment, delivers to next step desalting processing after softening；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, regenerative wastewater " zero-emission " system of delivering to processes；

3, step (two) desalting processing step includes:

(1) desalination includes single stage desalting--middle pressure reverse osmosis, and the water outlet softened through the degree of depth delivers to middle pressure reverse osmosis and carries out desalination, Recycling to product water, dense water processes again；

(2) two grades of desalination-high pressure reverse osmosiss, deliver to high pressure reverse osmosis by the dense water of above-mentioned steps and carry out desalination, obtain product water Recycling, dense water delivers to " zero-emission " point salt technical finesse；

4, step (three) " zero-emission " point salt technology pre-treatment step includes:

In dense water, add appropriate sodium carbonate, sodium hydroxide, remove the calcium in strong brine, magnesium ion, through catalytic ozonation, Activated carbon adsorption organics removal, obtains dense water after chelating resin softens；

5, step (four) dense water concentration step includes:

Use enrichment facility to the further minimizing of dense water of step (three), improve dense water salinity；The TDS of dense water reaches 10-20 Ten thousand mg/L；

6, step (five) evaporative crystallization divides salt to use step to include:

(1) feed liquid after step (four) concentration initially enters IV effect of four-effect countercurrent extraction crystallizing evaporator, is entered successively by guide pump Entering III, II, I effect, heating steam then flows to contrary with feed liquid, and raw steam initially enters I effect, then enter back into II effect, III imitate, IV effect, anhydrous sodium sulfate crystal salt is from I effect, II effect extraction, by washing, be dehydrated, be dried, weigh, packing, IV effect secondary simultaneously Vapour condensed by surface condenser after as product water reuse；

(2) I single-effect evaporator concentrated solutions deliver to cooler crystallizer, separate out sal glauberi crystallization when 0 DEG C, and sal glauberi crystallizes Deliver to IV effect feed end and continue through quadruple effect crystallizer output anhydrous sodium sulfate；

(3) concentrated solution after crystallisation by cooling delivers to salt crystallizing evaporator extraction sodium chloride, and sodium chloride is by being dehydrated, being dried and claim Weight, residue mother solution is standby；

7, the mother solution mummification of step (six) residue uses step to include:

Above-mentioned residue mother solution is by being spray-dried drying and other treatment, output carnallite, it is achieved waste water zero emission.

The most according to claim 6 point of salt technology, it is characterised in that polyaluminum sulfate in described coal chemical industrial waste water pretreatment Ferrum, sodium carbonate, calcium hydroxide, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 50-300:20-100:10-50:5- 25:5-20；Described acid is hydrochloric acid；Described alkali be sodium hydroxide, potassium hydroxide one or both；Described step (two) After once concentration, TDS scope is 30000-60000mg/L, and after second time concentrates, TDS scope is 60000-100000mg/L；Described Step (three) in enrichment facility can be just permeating, vibrating diaphragm, STRO/DTRO, electric drive film device or MVR falling film evaporator One or both.

The most according to claim 6 point of salt technology, it is characterised in that polyaluminum sulfate in described coal chemical industrial waste water pretreatment Ferrum, sodium carbonate, calcium hydroxide, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15:12；Described alkali For sodium hydroxide；After described step (two) concentrates for the first time, TDS scope is 30000mg/L, and after second time concentrates, TDS scope is 60000mg/L；During described step (three) dense water concentrates, enrichment facility can be in electric drive film device or MVR falling film evaporator One or both.

The most according to claim 6 point of salt technology, it is characterised in that this point of salt technical operation step includes

1, coal chemical industrial waste water pretreatment

(1) by 100-500m³The TDS of/h is that 5560-7280mg/L coal chemical industrial waste water introduces high dense settling pond, and adds 5kg/ m³Bodied ferric sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 50-300:20- The mixture of 100:10-50:5-25:5-20, filtering precipitate, water demineralization；

(2) the pending water of step (1) leads to ozone 1-3 hour, then measure B/C value for 1.0-3.5；

(3) waste water after ozone oxidation of step (2) reacts 12-24 hour from flowing to biochemistry pool；

(4) in the case of oxygen-supplying amount is 95-100%, the waste water of step (3) is filtered in MBR membrane biological reaction pond Adsorption treatment；Then the water of filtration is delivered to ion exchanger and carry out degree of depth sofening treatment, after softening, deliver to next step Desalting processing；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, and regenerative wastewater is delivered to " zero-emission " system and processed；

2, colliery drainage water pretreatment

(1) by 700-1300m³The TDS of/h is that the colliery drainage water of 9280-10320mg/L introduces high dense settling pond, and adds 5kg/m³Bodied ferric sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 50-300: The mixture of 20-100:10-50:5-25:5-20, filtering precipitate, water demineralization；

(2) waste water of step (1) is carried out filtration treatment through immersion ultrafiltration；Then the water of filtration is delivered to ion exchanger enter Row carries out degree of depth sofening treatment, delivers to next step desalting processing after softening；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, regenerative wastewater " zero-emission " system of delivering to processes；

3, step (two) desalting processing step includes:

(1) desalination includes single stage desalting--middle pressure reverse osmosis, and the former water softened through the degree of depth delivers to middle pressure reverse osmosis and carries out desalination, Recycling to product water, dense water processes again；After dense water obtains concentrating for the first time, TDS reaches 30000-6000mg/L；

(2) two grades of desalination-high pressure reverse osmosiss；The dense water of above-mentioned steps is delivered to high pressure reverse osmosis and carries out desalination, obtain product water Recycling, dense water delivers to " zero-emission " point salt technical finesse；Dense water obtains TDS after second time concentrates and reaches 60000- 100000mg/L；

4, step (three) " zero-emission " point salt technology pre-treatment step includes:

In dense water, add appropriate sodium carbonate, sodium hydroxide, remove the calcium in strong brine, magnesium ion, through catalytic ozonation, Activated carbon adsorption organics removal, obtains pretreatment water outlet after chelating resin softens；

5, step (four) dense water concentration step includes:

The further minimizing of dense water to step (three) of the electric drive film device, improves dense water salinity, and the TDS of dense water is 100000-200000mg/L；

6, step (five) evaporative crystallization divides salt step to include:

(1) feed liquid after step (four) concentration initially enters IV effect of four-effect countercurrent extraction crystallizing evaporator, is entered successively by guide pump Entering III, II, I effect, heating steam then flows to contrary with feed liquid, and raw steam initially enters I effect, then enter back into II effect, III imitate, IV effect, anhydrous sodium sulfate crystal salt is from I effect, II effect extraction, by washing, be dehydrated, be dried, weigh, packing, IV effect secondary simultaneously Vapour condensed by surface condenser after as product water reuse；

(2) I single-effect evaporator concentrated solutions deliver to cooler crystallizer, separate out sal glauberi crystallization when 0 DEG C, and sal glauberi crystallizes Deliver to IV effect feed end and continue through quadruple effect crystallizer output anhydrous sodium sulfate；

(3) concentrated solution after crystallisation by cooling delivers to salt crystallizing evaporator extraction sodium chloride, and sodium chloride is by being dehydrated, being dried and claim Weight, residue mother solution is standby；

7, the mother solution mummification of step (six) residue uses step to include:

Above-mentioned residue mother solution is by being spray-dried drying and other treatment, output carnallite, it is achieved waste water zero emission.

The most according to claim 6 point of salt technology, it is characterised in that this point of salt technical operation step includes

1, coal chemical industrial waste water pretreatment

(1) by 200m³The TDS of/h is that 5560mg/L coal chemical industrial waste water introduces high dense settling pond, and adds 5kg/m³Polymerised sulphur Acid ferrum, sodium carbonate, calcium hydroxide, sodium hydroxide, the weight consumption ratio of polyacrylamide be: the mixing of 175:60:30:15:12 Thing, filtering precipitate, water demineralization；

(2) the pending water of step (1) leads to ozone 2 hours, then measure B/C value for 2.2；

(3) waste water after ozone oxidation of step (2) reacts 18 hours from flowing to biochemistry pool；

(4) in the case of oxygen-supplying amount is 100%, the waste water of step (3) is carried out Filtration Adsorption in MBR membrane biological reaction pond Process；Then the water of filtration is delivered to ion exchanger and carry out degree of depth sofening treatment, after softening, deliver to next step desalination Process；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, and regenerative wastewater is delivered to " zero-emission " system and processed；

2, colliery drainage water pretreatment

(1) by 1000m³The colliery drainage water that the TDS of/h is appropriate for 9280mg/L introduces high dense settling pond, and adds 5kg/m³ Bodied ferric sulfate, sodium carbonate, calcium hydroxide, sodium hydroxide, the weight consumption ratio of polyacrylamide be: 175:60:30:15: The mixture of 12, filtering precipitate, water demineralization；

(2) waste water of step (1) is carried out filtration treatment through immersion ultrafiltration, then the water of filtration is delivered to ion exchanger and enter Row carries out degree of depth sofening treatment, delivers to next step desalting processing after softening；Ion exchanger bronsted lowry acids and bases bronsted lowry regenerates, regenerative wastewater " zero-emission " system of delivering to processes；

3, step (three) desalting processing step includes:

(1) desalination includes single stage desalting--middle pressure reverse osmosis, and the former water softened through the degree of depth delivers to middle pressure reverse osmosis and carries out desalination, Recycling to product water, dense water processes again；After dense water obtains concentrating for the first time, TDS reaches 30000mg/L；

(2) two grades of desalination-high pressure reverse osmosiss；The dense water of above-mentioned steps is delivered to high pressure reverse osmosis and carries out desalination, obtain product water Recycling, dense water delivers to " zero-emission " point salt technical finesse；Dense water obtains TDS after second time concentrates and reaches 60000mg/L；

4, step (three) " zero-emission " point salt technology pre-treatment step includes:

In dense water, add appropriate sodium carbonate, sodium hydroxide, remove the calcium in strong brine, magnesium ion, through catalytic ozonation, Activated carbon adsorption organics removal, obtains pretreatment water outlet after chelating resin softens；

5, step (four) dense water concentration step includes:

The further minimizing of dense water to step (three) of the electric drive film device, improves dense water salinity, and the TDS of dense water is 200000mg/L；

6, step (five) evaporative crystallization divides salt step to include:

(1) feed liquid after step (four) concentration initially enters IV effect of four-effect countercurrent extraction crystallizing evaporator, is entered successively by guide pump Entering III, II, I effect, heating steam then flows to contrary with feed liquid, and raw steam initially enters I effect, then enters back into II, imitates, III Effect, IV effect, anhydrous sodium sulfate crystal salt is from I effect, II effect extraction, by washing, be dehydrated, be dried, weigh, packing, IV effect simultaneously Secondary vapour condensed by surface condenser after as product water reuse；

(2) I single-effect evaporator concentrated solutions deliver to cooler crystallizer, separate out sal glauberi crystallization when 0 DEG C, and sal glauberi crystallizes Deliver to IV effect feed end and continue through quadruple effect crystallizer output anhydrous sodium sulfate；

(3) concentrated solution after crystallisation by cooling delivers to salt crystallizing evaporator extraction sodium chloride, and sodium chloride is by being dehydrated, being dried and claim Weight, residue mother solution is standby；

7, the mother solution mummification of step (six) residue uses step to include:

Above-mentioned residue mother solution is by being spray-dried drying and other treatment, output carnallite, it is achieved waste water zero emission.