CN106006681B - A kind of method of high slat-containing wastewater recycling treatment - Google Patents

A kind of method of high slat-containing wastewater recycling treatment Download PDF

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CN106006681B
CN106006681B CN201610328533.1A CN201610328533A CN106006681B CN 106006681 B CN106006681 B CN 106006681B CN 201610328533 A CN201610328533 A CN 201610328533A CN 106006681 B CN106006681 B CN 106006681B
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containing wastewater
potassium sulfate
recycling treatment
sodium
potassium
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CN106006681A (en
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高文远
李昱昀
顾秋月
汤建良
吴开元
郑贤福
邹娟
杨三妹
罗稳
刘雨星
杨清
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China Bluestar Chonfar Engineering and Technology Co Ltd
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China Bluestar Changsha Design and Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • C—CHEMISTRY; METALLURGY
    • 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
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00—Fertilisers containing potassium
    • C05D1/02—Manufacture from potassium chloride or sulfate or double or mixed salts thereof
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

A kind of method of high slat-containing wastewater recycling treatment, comprises the following steps：（1）COD contents are made to be reduced to 30~50ppm through depth-type filtration and deep oxidation sodium sulfate type brine waste；（2）Deep oxidation water outlet is entered into vapo(u)rization system and carries out high power concentration；（3）By enriching slurry and potassium chloride mix, big particle diameter potassium product is made in conversion, crystallization；（4）Evaporative crystallization.The present invention realizes wastewater zero discharge substantially, and obtain a large amount of secondary recycle-waters of industry, wherein high value-added product is made in low yield value inorganic salts after secondary conversion, realizes the minimizing of high slat-containing wastewater, recycling and innoxious, promotes strategic structural adjustment and the optimization and upgrading of environmental protection industry.

Description

A kind of method of high slat-containing wastewater recycling treatment
Technical field
The present invention relates to a kind of method of high slat-containing wastewater recycling treatment, and in particular to a kind of water treatment industry and sulfuric acid Potassium industry organically combines, by high slat-containing wastewater after deep oxidation is degraded, the direct secondary conversion production potassium sulfate of enriching slurry, pair Sodium chloride is produced, and by energy and the method for the brine waste recycling treatment of fresh water reuse.
Background technology
High slat-containing wastewater, refer to the waste water of mass fraction sum >=3.5% of total dissolved solidss (TDS) and organic matter, it comes Source is extensive, is concentrated mainly on the industries such as electric power, oil refining, chemical industry, metallurgy, papermaking, agricultural chemicals.Such waste water characteristic is salt content height, Pollutant is based on inorganic salts, including NaCl, Na2SO4And NaNO3Deng the also organic matter containing difficult degradation in effluent part. In recent years, with social development and the raising of environmental consciousness, brine waste zero emission is gradually brought into schedule, especially quick in environment Sense and drought and water-scarce area are forbidden or limits to arrange outside waste water, and high slat-containing wastewater, which is handled, increasingly causes that enterprise and researcher's is wide General concern.
For the processing of brine waste, biological treatment is one of the most frequently used method of current wastewater treatment, and it has application The features such as scope is wide, strong adaptability, but the biological treatment of high slat-containing wastewater needs to be diluted, and is generally transported under low salt concn OK, the serious waste of water resource is caused, treatment facility is huge, investment increases, operating cost improves；Returned using evaporative crystallization technique Receive inorganic salts technique be also Recent study most extensively and the most common processing method of commercial Application, i.e., by pre-processing waste water In petroleum-type, suspension and organic matter be reduced to certain standard to meet the inflow requirement of film process unit, film process list Member concentrates and reclaims waste water, and condensed water enters evaporative crystallization processing unit, and according to the difference of solubility, fractional crystallization goes out difference Inorganic salt product.But pretreatment stage can not effective organics removal, the organic matter of difficult degradation is in evaporative concentration stage of saline It is more easy to be enriched with, causes fouling of heat exchangers and operating cost to raise, it is also possible to which entrainment influences properties of product in the product.This method With processing cost is high, energy consumption is big, the inorganic salt product of recovery is worth low shortcoming.CN105152443A discloses a kind of height and contained The method of salt wastewater zero discharge crystal salt resource reclaim, it is to be crystallized successively using pretreatment, film concentration and evaporative crystallization technique Na2SO4, NaCl and hybrid solid salt, can effectively reclaim the useful inorganic salts in brine waste, but generally existing cost recovery it is high, The shortcomings such as value of the product is low, do not carry out abundant secondary operation recycling.
Potassium sulfate has preferable economic well-being of workers and staff as a kind of market demand is big, the potash fertilizer products that have a extensive future.Using saltcake Conversion method production potassium sulfate technology possesses more rich research experience in China, also more meets the fundamental realities of the country in China.For a long time with Come, saltcake conversion method, which produces potassium sulfate technology, to be influenceed by energy consumption is higher, and industrialization device is constantly in dead state.It is and industrial Contain more rich sodium sulphate resource in brine waste, during brine waste recycling treatment is carried out, if being joined Conversion production is closed, can not only effective Resource recovery for brine waste recycling, moreover it is possible to realize that secondary operation recycles, Improve product income；For Production of Potassium Sulphate, the production cost of potassium sulfate has effectively also been married again into brine waste processing, It is a kind of comprehensive utilization treatment process combination of relatively tool market prospects.
Existing conversion production potassium sulfate technology, directly uses the raw material of industry or semi-finished product, such as saltcake or sodium sulphate mostly With potassium chloride, the purity of raw material is required, and General transformation device is influenceed uniformly mixing relatively difficult to achieve by material properties so that anti- Process charge less point is answered, grain size number is small, most of to be less than 120 μm, influences subsequent filter separating technology.And the saliferous of prior art Wastewater treatment is generally biological treatment, film process, evaporation and concentration etc., is discharged after general wastewater to reach standard, or chlorine is extracted from waste water Change sodium, sodium sulphate etc..But for high slat-containing wastewater, biological treatment is influenceed that making for microorganism can be suppressed by salt content With, wastewater biodegradability is deteriorated, the universal cost of film process is higher, be concentrated by evaporation extraction primary product sodium chloride or sodium sulphate production Product value is low, is influenceed by organic matter enrichment, the defects of product solubility property and commercial performance difference be present.
The content of the invention
The technical problem to be solved in the present invention is to overcome that existing brine waste processing product type is single, application value is low The defects of, there is provided a kind of production cost is low, the method for the high slat-containing wastewater recycling treatment of zero-emission.
It is a kind of method of high slat-containing wastewater recycling treatment that the present invention, which solves the technical scheme that its technical problem uses, Specifically include following steps：
（1）Deep oxidation：High slat-containing wastewater carries out deep oxidation, makes its COD after deep filter purifies（Chemistry needs Oxygen amount）Content is reduced to 30~50ppm, obtains deep oxidation water outlet；
Deep oxidation is mainly the hardly degraded organic substance and inorganic reduction contact scar thing for removing low concentration in waste water；
（2）High power concentrates：By step（1）The deep oxidation water outlet of gained is sent into vapo(u)rization system progress high power and is concentrated into sulfuric acid Na concn is 15~40wt%, obtains sodium sulphate slurry；
Sodium sulphate reacts one of primary raw material to participate in subsequent transformation, and the pulp density can ensure certain system material The transformation efficiency that concentration is formed and optimized；
（3）Potassium sulfate converts：By step（2）The sodium sulphate slurry of gained is sent into potassium sulfate conversion system, with potassium chloride the Mixed once dispensing, mixed once feed proportioning system each element total mass concentration are：K+：8.0~9.5wt%, Na+：7.0~ 9.0wt%, Cl-：13~16wt%, SO4 2-：4.5~8wt%, Yu Weishui（The mix concentration be in order to obtain preferable yield and The glaserite intermediate products of higher degree）；After 20~40 DEG C convert 0.5~1.5 hour, intermediate products are obtained through separation of solid and liquid Glaserite and high mother liquid of sodium；Glaserite again with potassium chloride, water in reaction crystalizer second of dispensing, second of mix system System each element total mass concentration be：K+：15~20wt%, Na+：1.0~3.0wt%, Cl-：8~10wt%, SO4 2-：10~15wt%, Yu Weishui（The mix concentration is to obtain the potassium product of preferable yield and higher degree）, in 30~50 DEG C of reactions 2.0~3.0 hours, potassium product is obtained after separation of solid and liquid, mother liquid obtained is potassium sulfate mother liquid；
Potassium sulfate conversion system reaction crystalizer preferably uses DTB type reaction crystalizers；
（4）Evaporative crystallization：Step（3）In, the high mother liquid of sodium of potassium sulfate conversion system discharge steams at 80~120 DEG C through forcing The moisture equivalent to high mother liquid of sodium weight 15%~30% is sent out, crystallizes and sodium chloride byproduct is made, it is mother liquid obtained for high temperature crystallization mother Liquid.
Further, step（1）In, the high slat-containing wastewater is COD（COD）Content ＜ 500ppm, SO4 2-/ Cl-Mass ratio ＞ 4.5 sodium sulfate type brine waste.Can be by raw wastewater by pre-processing so that its is up to standard, its preprocess method Can be calcium and magnesium chemical subtraction, high-enriched organics degraded etc..
Further, step（1）In, the deep filter is from bottom to top according to floor height 1：（2.5~3.5）：（1.2~ 2.0）Ratio, by the nothing of 0.5~1.0mm of particle diameter manganese sand, 1.0~1.2mm of particle diameter 1.0~2.0mm of quartz sand and particle diameter Three kinds of filtrate layering fillings of bituminous coal, total filler is highly 0.3~0.6 times of filter height.Because the filter is using compound Filtrate filler, can effectively remove particle, suspension, colloid and part organic matter in raw water, reduce influent turbidity to 5ppm with It is interior, ozone catalytic inflow requirement is complied fully with, and be not in backwash unrest layer.
Further, step（1）In, the deep oxidation, by ozone oxidation under catalyst action, the catalyst by CN102872884A（A kind for the treatment of catalyst and its production method and application）Public technology obtains, and the catalyst amount is The 5~10% of waste water gross mass；The ozone catalytic, ozone usage/COD mass ratio are 2.0~4.5.Ozone is being urged The lower generation hydroxyl radical free radical of agent effect, oxidation rate is extremely strong, rapidly, unconditionality can decompose and go difficult degradation in water removal Most organic pollutants, so as to reach the purpose that depth removes COD and reduction effluent color dilution, the ozone usage can maximum limit Degree removes COD and realizes the purpose of waste water advanced degraded.
Further, step（2）The vapo(u)rization system can use MED multiple-effect evaporations, MVR function of mechanical steam recompression evaporation or Two kinds of evaporation mode combinations, the selection of evaporation mode can be according to enterprise's location energy advantages and enterprises characteristicses, prioritizing selection energy The cheap evaporation mode of source cost.
Further, step（3）In second of dispensing, the water of dispensing is fresh water or step（1）The depth oxygen of gained Water is dissolved, preferable liquid phase reactor crystalline environment is provided as reaction medium, substituting fresh water using deep oxidation water outlet can be one Determine to save system fresh water dosage in degree, reduce evaporation energy consumption.
Further, step（3）The potassium sulfate mother liquid and step（4）The high temperature crystallization mother liquor can return to step （3）Potassium sulfate conversion system substitutes partial oxidation potassium and participates in the conversion of first time mix；Mother liquor all returns to dispensing both one Determine to realize wastewater zero discharge in degree, also can fully recycle mother liquor K+And SO4 2-Resource, improve system potassium yield.
Further, step（2）And step（4）Involved vapo(u)rization system can use tubular type or plate type heat exchanger to carry out heat Recycle, steam condensate (SC) is used as industrial reuse water secondary use after cooling.Energy regenerating utilization is carried out by heat exchanger, Energy reasonable energy utilization, condensing hot air furnace energy fresh-water-saving, break away from the dependence to fresh water as recycle-water is produced, while Meet the environmental requirement of national energy-saving consumption reduction and recycling economy.
The beneficial effects of the present invention are, the method for the high slat-containing wastewater recycling treatment employed in the present invention, mainly It is related to sodium sulfate type brine waste, wherein contain hardly degraded organic substance, using ozone catalytic advanced oxidation processes, in Decomposition Wastewater Hardly degraded organic substance and inorganic reduction contact scar thing, can reduce influence of the organic matter to subsequent product quality to greatest extent；Utilize High power condensing mode obtains the slurry of sulfur acid sodium, dispensing conversion direct with potassium chloride, big particle diameter potassium product can be made, 80% potassium sulfate granularity reaches more than 300 μm, can overcome limitation of the process for producing potassium sulfate to conversion raw material, realize product quality Lifting and Business Economic Benefit leap；The combination of water treatment industry and process for producing potassium sulfate, can overcome the disadvantages that mirabilite method Produce the technological deficiency of potassium sulfate high energy consumption；Mother liquor all recycles, and can improve system potassium yield, is arranged outside without any mother liquor, Comprehensive utilization of resources and wastewater zero discharge can be realized；Energy and steam water are reclaimed simultaneously, resource, the energy can be realized again Utilize, reduce enterprise to the dependence of fresh water, local environment can be improved, promote strategic structural adjustment and the optimization of environmental protection industry Upgrading.
Brine waste advanced treating of the present invention is organically combined with process for producing potassium sulfate, and existing brine waste can be overcome to handle The market flaw that product type is single, application value is low, with reference to the process characteristic and shortcoming of saltcake conversion method production potassium sulfate, fill Divide and utilize the useful sodium sulphate resource of brine waste, production cost is low, zero-emission.
Embodiment
Technical scheme is described further with reference to specific embodiment.
High slat-containing wastewater used in the embodiment of the present invention 1 and 2 derives from Shanxi coal chemical industry production waste water, and COD contains Measure 350ppm, SO4 2/ Cl-Mass ratio 6.8；High slat-containing wastewater used in embodiment 3 and 4 derives from the life of Inner Mongol power plant Produce waste water, COD contents 220ppm, SO4 2/ Cl-Mass ratio 260；Chemical reagent used in other is unless otherwise specified, logical Cross the acquisition of routine business approach.
Embodiment 1
A kind of method of high slat-containing wastewater recycling treatment, comprises the following steps：
（1）Deep oxidation：High slat-containing wastewater carries out deep oxidation, makes its COD after deep filter purifies（Chemistry needs Oxygen amount）Content is reduced to 28ppm, obtains deep oxidation water outlet；
Wherein, the deep filter packed height is 0.4 times of filter height, from bottom to top according to floor height 1：2.5： 1.8 ratio, by 0.5~1.0mm of particle diameter manganese sand, 1.0~1.2mm of particle diameter 1.0~2.0mm of quartz sand and particle diameter it is smokeless Coal layering filling.
The deep oxidation, by ozone oxidation under catalyst action, the catalyst is by CN102872884A（A kind of water Handle catalyst and its production method and application）Public technology obtains（Catalyst by 21% manganese dioxide, 15% alundum (Al2O3), 15% titanium dioxide, 3% cobaltosic oxide, 7% carbon dust and 39% clay are made, and the dosage of catalyst is brine waste quality 8%, is urged Agent is reusable）, the ozone catalytic, ozone usage/COD mass ratio is 2.3.
（2）High power concentrates：By step（1）Vapo(u)rization system is sent into the deep oxidation water outlet of gained, utilizes MED multiple-effect evaporation sides It is 25% that formula, which is concentrated into sodium sulfate quality concentration, obtains sodium sulphate slurry；
（3）Potassium sulfate converts：By step（2）Gained sodium sulphate slurry is sent into potassium sulfate conversion system, with potassium chloride first Secondary mix to system each element total mass concentration is：K+：8.84wt%, Na+：7.94wt%, Cl-：14.7wt%, SO4 2-： 5.7wt%, Yu Weishui, separation of solid and liquid after 1.5h is converted under the conditions of 25 DEG C of normal temperature；Intermediate products glaserite is obtained through separation of solid and liquid With high mother liquid of sodium；Glaserite again with potassium chloride, water in reaction crystalizer second of dispensing, second of dispensing to system each element Total mass concentration is：K+：17.37wt%, Na+：1.91wt%, Cl-：8.94wt%, SO4 2-：13.09wt%, Yu Weishui, in DTB types In reaction crystalizer under the conditions of 50 DEG C after reactive crystallization 2h, separation of solid and liquid, you can obtain 80% potassium sulfate granularity reach 250 μm with On big particle diameter potassium sulfate, K in the big particle diameter potassium sulfate of gained2O content 50.8%, reach GB20406-2006 potassium sulfate for agricultural uses Grade A requirement, mother liquid obtained is potassium sulfate mother liquid；
（4）Evaporative crystallization：Step（3）In, the high mother liquid of sodium of potassium sulfate conversion system discharge is forced to steam at 110 DEG C through multiple-effect The moisture equivalent to high mother liquid of sodium weight 28% is sent out, crystallization can obtain sodium chloride, NaCl contents 98.6%, reach GB/T 5462-2003 The requirement of refining industrial salt primes；Mother liquid obtained is high temperature crystallization mother liquor.
Wherein, step（2）And step（4）Involved vapo(u)rization system carries out heat recovery and utilization using pipe heat exchanger, steams Vapour condensed water is used as industrial reuse water secondary use after cooling.
Embodiment 2
A kind of method of high slat-containing wastewater recycling treatment, comprises the following steps：
（1）Deep oxidation：High slat-containing wastewater carries out deep oxidation, makes its COD after deep filter purifies（Chemistry needs Oxygen amount）Content is reduced to 23ppm, obtains deep oxidation water outlet；
Wherein, deep filter packed height is 0.6 times of filter height, from bottom to top according to floor height 1：2.6：2.0 Ratio is layered by 0.5~1.0mm of particle diameter manganese sand, 1.0~1.2mm of particle diameter 1.0~2.0mm of quartz sand and particle diameter anthracite Filling.
The deep oxidation, by ozone oxidation under catalyst action, the catalyst is by CN102872884A（A kind of water Handle catalyst and its production method and application）Public technology obtains（Catalyst by 15% manganese dioxide, 10% alundum (Al2O3), 15% titanium dioxide, 10% cobaltosic oxide, 6% carbon dust and 44% clay are made；The dosage of catalyst is the 5% of brine waste quality, Catalyst is reusable）, the ozone catalytic, ozone usage/COD mass ratio is 4.5.
（2）High power concentrates：By step（1）Vapo(u)rization system is sent into the deep oxidation water outlet of gained, utilizes MED multiple-effect evaporation sides It is 22% that formula, which is concentrated into sodium sulfate quality concentration, obtains sodium sulphate slurry；
（3）Potassium sulfate converts：By step（2）Gained sodium sulphate slurry is sent into potassium sulfate conversion system, with potassium chloride, implementation Step in example 1（3）Step in gained potassium sulfate mother liquid and embodiment 1（4）Gained high temperature crystallization mother liquor first time mix is extremely System each element total mass concentration is：K+：8.5wt%, Na+：7.0wt%, Cl-：13.5wt%, SO4 2-：4.8wt%, Yu Weishui, often Separation of solid and liquid after conversion 0.5h under the conditions of 30 DEG C of temperature；Intermediate products glaserite and high mother liquid of sodium are obtained through separation of solid and liquid；Gained is filtered Expect glaserite and potassium chloride, step（1）Second of dispensing of gained deep oxidation water outlet to system each element total mass concentration is：K+：16.5wt%, Na+：1.5wt%, Cl-：8.2wt%, SO4 2-：15.5wt%, Yu Weishui, in DTB type crystallizers under the conditions of 45 DEG C Separation of solid and liquid after reactive crystallization 1.5h, you can obtain the big particle diameter potassium sulfate that 80% potassium sulfate granularity reaches more than 230 μm, K2O contains Amount 50.6%, reaches GB20406-2006 potassium sulfate for agricultural use Grade A requirements, mother liquid obtained is potassium sulfate mother liquid；
（4）Evaporative crystallization：Step（3）In, the high mother liquid of sodium of potassium sulfate conversion system discharge is suitable through multiple-effect forced evaporation In the moisture of high mother liquid of sodium weight 16%, crystallization can obtain sodium chloride, NaCl contents 98.5%, reach GB/T 5462-2003 and refine work The requirement of industry salt primes；Mother liquid obtained is high temperature crystallization mother liquor.
Wherein, step（2）And step（4）Involved vapo(u)rization system carries out heat recovery and utilization using plate type heat exchanger, steams Vapour condensed water is used as industrial reuse water secondary use after cooling.
Embodiment 3
A kind of method of high slat-containing wastewater recycling treatment, comprises the following steps：
（1）Deep oxidation：High slat-containing wastewater carries out deep oxidation, makes its COD after deep filter purifies（Chemistry needs Oxygen amount）Content is reduced to 42ppm, obtains deep oxidation water outlet；
Wherein, deep filter packed height is 0.3 times of filter height, from bottom to top according to floor height 1：3.5：1.6 Ratio by 0.5~1.0mm of particle diameter manganese sand, 1.0~1.2mm of particle diameter 1.0~2.0mm of quartz sand and particle diameter anthracite point Layer filling.
The deep oxidation, by ozone oxidation under catalyst action, the catalyst is by CN102872884A（A kind of water Handle catalyst and its production method and application）Public technology obtains（Catalyst by 10% manganese dioxide, 20% alundum (Al2O3), 18% titanium dioxide, 12% cobaltosic oxide, 4% carbon dust and 36% clay are made, and the dosage of catalyst is the 9% of brine waste quality, Catalyst is reusable）, the ozone catalytic, ozone usage/COD mass ratio is 3.5.
（2）High power concentrates：By step（1）Vapo(u)rization system is sent into the deep oxidation water outlet of gained, using MVR mechanical vapors again It is 30% that Compression Evaporation mode, which is concentrated into sodium sulfate quality concentration, obtains sodium sulphate slurry；
（3）Potassium sulfate converts：By step（2）Gained sodium sulphate slurry is sent into potassium sulfate conversion system, first with potassium chloride the Mixed once dispensing to system each element total mass concentration is：K+：9.3wt%, Na+：8.7wt%, Cl-：13.2wt%, SO4 2-： 6.9wt%, Yu Weishui, separation of solid and liquid after 1h is converted under the conditions of 32 DEG C of normal temperature；Intermediate products glaserite and height are obtained through separation of solid and liquid Mother liquid of sodium；Gained glaserite and potassium chloride, step（1）Second of dispensing of gained deep oxidation water outlet is to system each element gross mass Concentration is：K+：18.2wt%, Na+：2.6wt%, Cl-：8.2wt%, SO4 2-：14.8wt%, Yu Weishui, 42 in DTB type crystallizers Separation of solid and liquid after reactive crystallization 2.5h under the conditions of DEG C, you can obtain the big particle diameter sulfuric acid that 80% potassium sulfate granularity reaches more than 280 μm Potassium, K2O content 51.3%, reach GB20406-2006 potassium sulfate for agricultural use Grade A requirements, mother liquid obtained is potassium sulfate mother liquid；
（4）Evaporative crystallization：Potassium sulfate conversion system discharge high mother liquid of sodium 120 DEG C through multiple-effect forced evaporation equivalent to height The moisture of mother liquid of sodium weight 22%, crystallization can obtain sodium chloride, NaCl contents 98.8%, reach GB/T 5462-2003 refining industrial salts Primes requirement, mother liquid obtained is high temperature crystallization mother liquor.
Wherein, step（2）And step（4）Involved vapo(u)rization system carries out heat recovery and utilization using pipe heat exchanger, steams Vapour condensed water is used as industrial reuse water secondary use after cooling.
Embodiment 4
A kind of method of high slat-containing wastewater recycling treatment, comprises the following steps：
（1）Deep oxidation：High slat-containing wastewater carries out deep oxidation, makes its COD after deep filter purifies（Chemistry needs Oxygen amount）Content is reduced to 35ppm, obtains deep oxidation water outlet；
Wherein, deep filter packed height is 0.5 times of filter height, from bottom to top according to floor height 1：3.0：1.5 Ratio by 0.5~1.0mm of particle diameter manganese sand, 1.0~1.2mm of particle diameter 1.0~2.0mm of quartz sand and particle diameter anthracite point Layer filling.
The deep oxidation, by ozone oxidation under catalyst action, the catalyst is by CN102872884A（A kind of water Handle catalyst and its production method and application）Public technology obtains（Catalyst by 18% manganese dioxide, 5% alundum (Al2O3), 25% titanium dioxide, 8% cobaltosic oxide, 3.5% carbon dust and 40.5% clay are made, and the dosage of catalyst is brine waste quality 9%, catalyst is reusable）, the ozone catalytic, ozone usage/COD mass ratio is 3.0.
（2）High power concentrates：By step（1）Vapo(u)rization system is sent into the deep oxidation water outlet of gained, using MED multiple-effect evaporations with MVR mechanical vapors recompression evaporation combination carries out high power concentration, is 24% to sodium sulfate quality concentration, obtains sodium sulphate slurry；
（3）Potassium sulfate converts：By step（2）The sodium sulphate slurry feeding potassium sulfate conversion system of gained, first and potassium chloride, Step in embodiment 3（3）Step in gained potassium sulfate mother liquid and embodiment 3（4）Gained high temperature crystallization mother liquor for the first time match somebody with somebody by mixing Material is to system each element total mass concentration：K+：8.6wt%, Na+：7.3wt%, Cl-：15.8wt%, SO4 2-：7.2wt%, Yu Wei Water, separation of solid and liquid after 0.5h is converted under the conditions of 35 DEG C of normal temperature, intermediate products glaserite and high mother liquid of sodium are obtained through separation of solid and liquid；Institute Obtain glaserite and potassium chloride, step（1）Second of dispensing of gained deep oxidation water outlet to system each element total mass concentration is：K+：16.4wt%, Na+：1.5wt%, Cl-：9.1wt%, SO4 2-：11.9wt%, Yu Weishui, in DTB type crystallizers under the conditions of 47 DEG C Separation of solid and liquid after reactive crystallization 1.5h, you can obtain the big particle diameter potassium sulfate that 80wt% potassium sulfate granularities reach more than 300 μm, K2O Content 51.5%, reach GB20406-2006 potassium sulfate for agricultural use Grade A requirements, mother liquid obtained is potassium sulfate mother liquid；
（4）Evaporative crystallization：Potassium sulfate conversion system discharge high mother liquid of sodium 100 DEG C through multiple-effect forced evaporation equivalent to height The moisture of mother liquid of sodium weight 24%, crystallization can obtain sodium chloride, NaCl contents 98.6%, reach GB/T 5462-2003 refining industrial salts Primes requirement；Mother liquid obtained is high temperature crystallization mother liquor.
Wherein, step（2）And step（4）Involved vapo(u)rization system carries out heat recovery and utilization using plate type heat exchanger, steams Vapour condensed water is used as industrial reuse water secondary use after cooling.

Claims (8)

  1. A kind of 1. method of high slat-containing wastewater recycling treatment, it is characterised in that comprise the following steps：
    （1）Deep oxidation：High slat-containing wastewater carries out deep oxidation, its COD content is reduced to 30 after deep filter purifies ~50ppm, obtain deep oxidation water outlet；
    Step（1）In, the high slat-containing wastewater is COD content ＜ 500ppm, SO4 2-/ Cl-Mass ratio ＞ 4.5 sulphur Sour sodium form brine waste；
    （2）High power concentrates：By step（1）It is dense that the deep oxidation water outlet feeding vapo(u)rization system progress high power of gained is concentrated into sodium sulphate Spend for 15~40wt%, obtain sodium sulphate slurry；
    （3）Potassium sulfate converts：By step（2）The sodium sulphate slurry of gained is sent into potassium sulfate conversion system, with potassium chloride for the first time Mix, mixed once feed proportioning system each element total mass concentration are：K+：8.0~9.5wt%, Na+：7.0~9.0wt%, Cl-：13~16wt%, SO4 2-：4.5~8wt%, Yu Weishui；After 20~40 DEG C convert 0.5~1.5 hour, obtained through separation of solid and liquid To intermediate products glaserite and high mother liquid of sodium；Glaserite again with potassium chloride, water in reaction crystalizer second of dispensing, second Mix system each element total mass concentration is：K+：15~20wt%, Na+：1.0~3.0wt%, Cl-：8~10wt%, SO4 2-： 10~15wt%, Yu Weishui, reacted 2.0~3.0 hours at 30~50 DEG C, potassium product is obtained after separation of solid and liquid, it is mother liquid obtained For potassium sulfate mother liquid；
    （4）Evaporative crystallization：Step（3）In, the high mother liquid of sodium that potassium sulfate conversion system is discharged is at 80~120 DEG C through forced evaporation phase When sodium chloride byproduct is made in the moisture of high mother liquid of sodium weight 15%~30%, crystallization, mother liquid obtained is high temperature crystallization mother liquor.
  2. 2. the method for high slat-containing wastewater recycling treatment according to claim 1, it is characterised in that step（1）In, institute Deep filter is stated from bottom to top according to floor height 1：（2.5~3.5）：（1.2~2.0）Ratio, by 0.5~1.0mm's of particle diameter 1.0~2.0mm of manganese sand, 1.0~1.2mm of particle diameter quartz sand and particle diameter three kinds of filtrate layering fillings of anthracite, total filler are high Spend for 0.3~0.6 times of filter height.
  3. 3. the method for high slat-containing wastewater recycling treatment according to claim 1 or 2, it is characterised in that step（1）In, The deep oxidation, by ozone oxidation under catalyst action, ozone usage/COD mass ratio is 2.0~4.5.
  4. 4. the method for high slat-containing wastewater recycling treatment according to claim 1 or 2, it is characterised in that step（2）It is described Vapo(u)rization system is MED multiple-effect evaporations, the evaporation of MVR function of mechanical steam recompression or two kinds of evaporation mode combinations.
  5. 5. the method for high slat-containing wastewater recycling treatment according to claim 1 or 2, it is characterised in that step（3）It is described In second of dispensing, the water of dispensing is fresh water or step（1）The deep oxidation water outlet of gained.
  6. 6. the method for high slat-containing wastewater recycling treatment according to claim 1 or 2, it is characterised in that step（3）It is described Potassium sulfate mother liquid and step（4）The high temperature crystallization mother liquor return to step（3）Potassium sulfate conversion system substitutes partial oxidation potassium ginseng Converted with first time mix.
  7. 7. the method for high slat-containing wastewater recycling treatment according to claim 1 or 2, it is characterised in that step（2）And step Suddenly（4）Involved vapo(u)rization system carries out heat recovery and utilization using tubular type or plate type heat exchanger, and steam condensate (SC) is made after cooling For industrial reuse water secondary use.
  8. 8. the method for high slat-containing wastewater recycling treatment according to claim 1 or 2, it is characterised in that step（3）In, Potassium sulfate conversion system reaction crystalizer uses DTB type reaction crystalizers.
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