CN110104815A - A kind of method and system from mine water recycling potassium - Google Patents
A kind of method and system from mine water recycling potassium Download PDFInfo
- Publication number
- CN110104815A CN110104815A CN201910448332.9A CN201910448332A CN110104815A CN 110104815 A CN110104815 A CN 110104815A CN 201910448332 A CN201910448332 A CN 201910448332A CN 110104815 A CN110104815 A CN 110104815A
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- China
- Prior art keywords
- potassium
- sulfate
- crystallization
- sodium
- potassium sulfate
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 62
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000011591 potassium Substances 0.000 title claims abstract description 27
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 27
- 238000004064 recycling Methods 0.000 title claims abstract description 15
- 238000002425 crystallisation Methods 0.000 claims abstract description 79
- 230000008025 crystallization Effects 0.000 claims abstract description 79
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 73
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 72
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 72
- 239000013078 crystal Substances 0.000 claims abstract description 70
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 49
- 238000000926 separation method Methods 0.000 claims abstract description 47
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 45
- 239000012452 mother liquor Substances 0.000 claims abstract description 33
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 29
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 239000011593 sulfur Substances 0.000 claims abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 25
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 24
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 15
- UOVHNSMBKKMHHP-UHFFFAOYSA-L potassium;sodium;sulfate Chemical compound [Na+].[K+].[O-]S([O-])(=O)=O UOVHNSMBKKMHHP-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000009938 salting Methods 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims description 34
- 150000003839 salts Chemical class 0.000 claims description 33
- 230000008020 evaporation Effects 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 5
- 238000000605 extraction Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 14
- 239000012141 concentrate Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000001223 reverse osmosis Methods 0.000 description 7
- 239000005416 organic matter Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000010612 desalination reaction Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 206010012735 Diarrhoea Diseases 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 240000005809 Prunus persica Species 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000005442 atmospheric precipitation Substances 0.000 description 1
- 235000019658 bitter taste Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 201000006549 dyspepsia Diseases 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 208000017169 kidney disease Diseases 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000012773 waffles Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/16—Purification
-
- 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
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
-
- 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
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
A method of potassium is recycled from mine water, comprising: which mine water is concentrated via the dilute salting liquid formed after pretreatment, then sulfate crystal processing is carried out, the dope obtained when by separating sodium sulfate crystallized product carries out the processing of sodium potassium sulphate crystal by control physical parameter.The sodium potassium composite sulfur hydrochlorate crystallized product that separation obtains adds after water and potassium sulfate crystal seed through evaporative crystallization progress potassium sulfate extraction.On the one hand method provided by the present invention realizes the recycling to potassium in mine water, on the other hand since separation mother liquor can recycle, therefore in addition to can effectively recycle potassium sulfate crystalline product, while the rate of recovery and purity of sulfate crystal (anhydrous sodium sulphate) also being substantially increased.Invention also provides the systems for the above method.
Description
Technical field
The present invention relates to environmentally friendly technical field of resource recovery more particularly to it is a kind of from mine water recycling potassium method and be
System.
Background technique
Deposit mining destroys the original occurrence status of underground water and produces crack, close Atmospheric precipitation, surface water,
It is lauched and domestic water, the hydraulic connection between each water-bearing layer makes various water penetrate into down-hole mining along original and new crack
Space forms mine water.Mine water is the waste water that discharge amount is most in coal production process.China is according to effect on environment at present
And the feasibility as Drinking Water water source, mine water is traditionally divided into clean mine water by water quality type feature, is contained
Suspended matter mine water, highly mineralized mine water, acid mine water and five class containing poisonous and harmful element or radioactive element mine water.
Highly mineralized mine water refers mainly to the mine water that salinity inorganic salts total content is greater than 1000mg/L.It mainly contains
S04 2-、Cl-、Ca2+、K+、Na+Plasma.Hardness is accordingly higher, and water quality majority is in neutrality or meta-alkali, and band bitter taste, minority has acid
Property.Highly mineralized mine water is unfavorable for plant growth, can make the soil salinization.As boiler feed water, it is easy fouling.Make for building
Water will affect concrete quality.People's long-term drinking will cause diarrhea and indigestion, especially to heart and Patients With Kidney Diseases
It influences more serious.The mine water in northern China water shortage mining area tends to belong to high mine degree mine water, it is necessary to by purifying and desalinating
Process becomes drinking water and industrial water.Current highly mineralized mine water uses following processing method.
Chemical method: ion-exchange is the main method of chemical decladding, and it is exactly benefit that this, which is a kind of fairly simple method,
The ion in water removal is removed with cation and anion exchange agent, to reduce the salt content of water.
Membrane separation process: reverse osmosis and electrodialysis desalination technology belongs to membrane separation technique, is the current bitter desalination in China
The main method of desalt processing.
(1) hyperfiltration.Hyperfiltration is the method for being carried out substance separation under pressure by means of semi-permeable membrane.Can have
Effect ground removal inorganic salts, low molecule organic matter, virus and bacterium etc., the desalination of the water suitable for salt content greater than 4000mg/L
Processing.
(2) electroosmose process.Choosing under DC electric field effect, using anions and canons exchange membrane to anions and canons in solution
Select permeability, and a kind of physical and chemical process for being separated from water the solute in solution.
Concentration and evaporation: the remaining water that processing keeps salt content high repeatedly is concentrated to very small volume, then deposits in suitable place
It puts.By natural evaporation, it is made to avoid being discharged into downstream.After water evaporation will there are salinities to crystallize, can its be concentrated into 200g/L with
It is transported when upper concentration, is used as industrial chemicals.
Dilution discharge: dilution discharge is to mix the water of low saline salinity, is discharged after reaching the standard for being discharged into water body.
Avoid the adverse effect to downstream.
Consumption utilizes: consumption is utilized for the place of less demanding to salt content, and water consumption is fallen, atmosphere is finally evaporated to
In, it avoids and downstream discharges.
In the existing treatment process to highly mineralized mine water, mainly sodium sulphate therein (anhydrous sodium sulphate) is carried out
Recycling, such as Nie Jiangfeng " sodium sulphate and the sodium chloride delivered in 2017 of Shijiazhuang ancient cooking vessel waffle construction equipment Engineering Co., Ltd
Sub-prime crystallize application in mine water " text, with the red celebrating river Technique of Coal Mine Drainage of Inner Mongol Yi Tai Guang Lian coalification Co., Ltd
For advanced treating project, the treatment process of mine water reuse and the crystallization of inorganic salts sub-prime is illustrated.In 2018
In state patent CN109336323A, such technology is had been further described.
Provided by the above-mentioned document it is representative in the prior art, do not consider the recycling to sylvite.Moreover, being
The purity for improving sodium sulphate (anhydrous sodium sulphate), needs to be discharged a large amount of mother liquors, mother liquor can carry high concentration sodium sulfate and high value
Potassium sulfate salt becomes abraum salt after being discharged together, solid is remained object landfill disposal after usually subsequent only evaporation, therefore lead to ring
It is high to protect disposal costs, while resulting in waste of resources again.
Summary of the invention
It is the technical problem to be solved in the present invention is to provide a kind of method from mine water recycling potassium and for this method
System, the problem of being formerly mentioned is reduced or avoided.
In order to solve the above technical problems, the invention proposes a kind of methods from mine water recycling potassium comprising:
Mine water is concentrated via the dilute salting liquid formed after pretreatment, the saline solution after concentration is then delivered to sulphur
Sour sodium crystalline element obtains sulfate crystal product,
The dope obtained when by separating sodium sulfate crystallized product is delivered to sodium potassium sulphate crystal unit, by controlling physics
Parameter is evaporated crystallization to dope, obtains sodium potassium sulphate crystal product.It is obtained when separating sodium potassium sulphate crystal product
Dope returns the sulfate crystal unit by Pipeline transport and recycles.
The sodium potassium composite sulfur hydrochlorate crystallized product that separation obtains is delivered to potassium sulfate crystalline element, adds water and potassium sulfate crystal seed
After form salting liquid, be evaporated crystallization by controlling physical parameter later, obtain potassium sulfate crystallized product, separation potassium sulfate knot
The dope obtained when brilliant product returns the sulfate crystal unit by Pipeline transport and recycles.
Preferably, obtain sodium potassium sulphate crystal product evaporation and crystal process in, do not need launch seed crystal material or
Person other be used for the material of ion exchange, it is only necessary to control evaporating temperature control at 0 to 110 °, pressure limit be -98kpaG extremely
40kpaG, while it is dense that reflux mother liquor of the concentration control of complex salt crystallization after 15%~70%, separation is maintained in crystallizer
Degree control is 10%~50%.
Preferably, in potassium sulfate crystalline element, potassium sulfate crystallization is carried out by control temperature and pressure, and sodium sulphate is not tied
Brilliant or only a small amount of crystallization, is then demultiplex out potassium product therein, and obtain the mother liquor of containing sulfate.Temperature control 0 to
90 °, pressure is controlled in -98kpa to 40kpa.
Preferably, in potassium sulfate crystalline element, 5% potassium sulfate crystal seed is launched.
Preferably, the pretreatment includes precipitating, filtering, pH adjusting, ion exchange or their combination.
Preferably, before saline solution enters sulfate crystal unit, organic matter removal is carried out.
The present invention also provides the systems for the above method comprising sequential connection, for sulfate crystal
One subsystem, the second subsystem for the crystallization of sodium potassium composite sulfur hydrochlorate and the third subsystem for potassium sulfate crystallization, wherein
First subsystem includes pretreatment unit, primary concentration unit, secondary concentration unit and the sulfate crystal being linked in sequence
Unit, second subsystem include the sodium potassium composite sulfur hydrochlorate crystalline element and complex salt Crystallization Separation device being linked in sequence,
The third subsystem includes the potassium sulfate crystalline element and potassium sulfate Crystallization Separation device being linked in sequence, the complex salt crystallization
Separator and the potassium sulfate Crystallization Separation device pass through pipeline respectively and connect with mother liquor collecting tank, and the mother liquor collecting tank is logical
Pipeline is crossed to connect with the sulfate crystal unit.
Preferably, the sodium potassium composite sulfur hydrochlorate crystalline element is evaporation continous way FC/OSLO/TDB type crystallizer, institute
Stating complex salt Crystallization Separation device is discharging centrifugation apparatus under two-level piston material pushing centrifugal machine or horizontal spiral.
Preferably, the potassium sulfate crystalline element include continuous evaporative crystallization tank, it is circulating pump, vacuum pump group, condenser, cold
Condensate tank, condensate pump, the potassium sulfate Crystallization Separation device be under two-level piston material pushing centrifugal machine or horizontal spiral discharging from
Scheming or flat centrifuge.
On the one hand method provided by the present invention realizes the recycling to potassium in mine water, on the other hand due to separating mother liquor energy
It recycles, therefore in addition to can effectively recycle potassium sulfate crystalline product, while it is (first bright also to substantially increase sulfate crystal
Powder) the rate of recovery and purity.Invention also provides the systems for the above method.
Detailed description of the invention
The following drawings are only intended to schematically illustrate and explain the present invention, not delimit the scope of the invention.Wherein,
A kind of method from mine water recycling potassium for a specific embodiment according to the present invention is shown in Fig. 1
The schematic illustration of system.
Specific embodiment
For a clearer understanding of the technical characteristics, objects and effects of the present invention, this hair of Detailed description of the invention is now compareed
Bright specific embodiment.Wherein, identical component uses identical label.
A kind of method from mine water recycling potassium for a specific embodiment according to the present invention is shown in Fig. 1
The schematic illustration of system.It is shown in Figure 1 with the arrows trend of material in figure, it is provided by the present invention it is a kind of from
The method of mine water recycling potassium comprising:
Firstly, mine water is concentrated via the dilute salting liquid formed after pretreatment, it is then that the saline solution after concentration is defeated
It send to sulfate crystal unit 14, obtains sulfate crystal product,
Present invention is generally directed to the mine waters of potassium content high (such as potassium content is on 60mg/L), in this way due to mine water
High sulfuric acid natrium potassium salt water initial stage concentration it is lower, it is therefore desirable to using concentration process improve raw water concentration, improve influent density
Afterwards, the water body after concentration can carry out sulfate crystal, that is, the process flow and equipment of evaporative crystallization can be used, first by water body
In a large amount of sodium sulphate products crystallize output.
Cut-off in the Chinese patent CN109336323A referred to such as background technique specifically can be used to " double-effect evaporation knot
Method and measure before crystalline substance " technique, can also be used as the advanced treatment system in Chinese patent CN107777803A is similar
Device is disposed to be concentrated,
This step is corresponded in the present invention, also can provide the pretreatment unit 11, primary concentration unit 12, softening of sequential connection
Unit and secondary concentration unit 13 realize the concentration to mine water, and the water body after concentration is delivered to the sulfate crystal unit
14。
Wherein, the pretreatment unit 11 may include a series of equipment for solid particle precipitating, filtering, pH value tune
The effects of section, ion exchange or their combination.
The primary concentration unit 12 and the secondary concentration unit 13 can be using reverse osmosis or high pressure it is reverse osmosis or
The equipment of evaporation technique.Such as Chinese patent 201810104936.7 (a kind of method for concentration and equipment of reverse osmosis concentrated salt water),
201820877364.1 (a kind of concentrations with high salt and penetration equipment), a kind of 201711076283.8 (two-part reverse osmosis membrane concentrations
Combination unit and technique), 201710902189.7 (a kind of MVR evaporation concentrators), a kind of 201811511085.4 (triple effect evaporations
Inspissator), similar enrichment facility, the concentration process such as 201710269064.5 (evaporation concentration systems) be mainly used for being promoted dense
Degree does not need crystallization and sodium element and potassium element is precipitated.
The pliable cell 15 can be further a series of equipment for solid particle precipitating, filtering, pH value tune
The effects of section, ion exchange or their combination.Such as Chinese patent 201711023488.X (pH regulating device),
201820491243.3 (pH adjusting towers), 201820269333.8 (a kind of PH conditioning tanks), 201810794591.2 (ion exchanges
Column) similar equipment.
If COD in water body content is still higher after the secondary concentration unit 13, then can also further be arranged
One organic matter removal unit 16 being connect with the secondary concentration unit 13, for example, by using Chinese patent 201811184706.2
Device, activated carbon adsorption device or the advanced oxidation of scheme provided by (a method of in haline water remove organic matter)
Or ozone equipment, organic matter can be eliminated as much as in this way.
The process flow and equipment of evaporative crystallization can be used in the sulfate crystal unit 14, and heat energy utilization can cover MVR
Evaporation, steam heat pump evaporate (such as the similar equipment such as Chinese patent 201710949247.1,201811310562.0), multiple-effect
Forms such as (such as the similar equipment such as Chinese patent 201520970132.7,201410240546.4) are evaporated, with the evaporation side MVR
Method is optimal selection, heat utilization efficiency can be greatly improved in this way, while can significantly reduce operating cost.For example, by using Chinese patent
The similar equipment of 201711064226.8 (MVR multi-effect evaporators), 201721444796.5 (MVR multi-effect evaporators).
It is maximum the difference lies in that in the prior art with the prior art that the above process can be implemented by using the prior art the present invention
In, usually after carrying out sulfate crystal, concentrate is used as solid-state castoff landfill disposal after will directly evaporating, and of the invention
Then further concentrate is handled, to obtain potassium product, therefore, this step is not features of the present invention place,
Details are not described herein.
The dope obtained when then, by separating sodium sulfate crystallized product is delivered to sodium potassium sulphate crystal unit 21, passes through
Control physical parameter is evaporated crystallization to dope, obtains sodium potassium sulphate crystal product.Separate sodium potassium sulphate crystal product
When the dope that obtains the sulfate crystal unit 14 returned by Pipeline transport recycle.
The concentrate obtained when by separating sodium sulfate crystallized product continues sodium potassium composite sulfur hydrochlorate Crystallization Procedure, obtains
Sodium potassium composite sulfur hydrochlorate crystalline solid, the mother liquor obtained after separation is back to sulfate crystal process and further recycles after collecting to be made
With.
In the present invention, this corresponding step can provide the sodium potassium composite sulfur hydrochlorate crystalline element 21, compound of sequential connection
Salt Crystallization Separation device 22.
Via the concentrate after sulfate crystal unit 14 output sulfate crystal (anhydrous sodium sulphate) product, pass through pipeline
It is delivered to the sodium potassium composite sulfur hydrochlorate crystalline element 21, it is continuous that evaporation can be used in the sodium potassium composite sulfur hydrochlorate crystalline element 21
Formula FC/OSLO/TDB type crystallizer or other crystallizers of same type and technology, such as Chinese patent 201820293994.4
(a kind of multistage continous way flow evaporation device), 201810174977.3 (a kind of multistage continous way flow evaporation devices),
The similar equipment of 201721742630.1 (linear evaporation source and continous way evaporated devices), mixture passes through Pipeline transport after crystallization
It is separated by solid-liquid separation to the complex salt Crystallization Separation device 22, the complex salt Crystallization Separation device 22 can be two-diameter piston
The centrifuge instruments such as discharging centrifugation apparatus are isolated as long as being able to carry out separation of solid and liquid under pusher centrifuge, horizontal spiral
Mother liquor need to by Pipeline transport to mother liquor collecting tank 4 collect after, by Pipeline transport return the sulfate crystal unit 14 into
The concentration of one step utilizes.
One of inventive point of the invention is, maintains by control evaporating temperature and pressure while in crystallizer multiple
The concentration (15%~70%) for closing salt crystallization crystallizes complex salt, obtains glaserite class compound crystal substance.
In above-mentioned technological parameter, evaporating temperature range is 0 to 110 °, and pressure limit is -98kpaG to 40kpaG, complex salt
The concentration of crystallization is controlled 15%~70%, in addition, in order to simultaneously can be effectively by the sodium sulphate further progress in concentrate
It extracts, after being handled by the sodium potassium composite sulfur hydrochlorate crystalline element, the mother liquor obtained after separation can control concentration 10%
~50%.
For the measurement of concetration of evaporation process concentrate and separation post mother liquor, it can be and set on the pipeline of corresponding device
Set the such dress using optical detection principle of similar Chinese patent 201710187360.0 (mixed concentration on-line measurement device)
It sets, the structure for being also possible on pipeline setting for sample extraction (such as is arranged similar on the connecting line of vaporising device
Faucet or the tee tube for being provided with valve etc. can extract the structure of sample), sample is extracted according to certain time interval
Carry out Concentration Testing.
In a preferred embodiment, when evaporating temperature is 50 DEG C, and pressure is -90kpa, keep complex salt in crystallizer dense
Degree control obtains the effect of complex salt crystallization by that will flow back mother liquid concentration control in 23%-30% in 20%~25% range
Rate highest, the sodium sulphate and potassium concn dissolved in mother liquor are lower.
In a further advantageous embodiment, when evaporating temperature is 95 DEG C, and pressure is -30kpa, make complex salt in crystallizer
Concentration control obtains the efficiency of complex salt crystallization by the control of reflux mother liquid concentration in 25%-30% in 30%~40% range
Also higher, the sodium sulphate and potassium concn dissolved in mother liquor is slightly higher.
In the prior art, usually after carrying out sulfate crystal, concentrate is discarded as solid-state after will directly evaporating
Object landfill disposal, and the present invention is led to then further to being crystallized by parameters such as control temperature, pressure and concentration to concentrate
Pervaporation crystallization obtains sodium potassium composite sulfur hydrochlorate, prepares for subsequent recycling potassium, moreover, the mother liquor after evaporative crystallization separation solid
Can be recycled repeatedly in the case where ensureing a certain concentration, thus greatly improve the rate of recovery of sulfate crystal (anhydrous sodium sulphate) with
Purity.
In this step, it is not required to additionally feed intake.This is also that the present invention is produced with other existing glaserite class compound crystals
The maximum difference of technology.
In this step, how to control temperature, pressure, how detectable concentration, have the aforementioned Patents documents referred to
The similar prior art is achievable, and key point of the invention is, in this step by these state modulators in particular range, this
Sample could on the one hand promoted sulfate crystal (anhydrous sodium sulphate) the rate of recovery and purity, on the other hand can subsequent completion potassium sulfate mention
It takes.
Finally, by separation obtain sodium potassium composite sulfur hydrochlorate crystallized product be delivered to potassium sulfate crystalline element 31, add water and
Salting liquid is formed after potassium sulfate crystal seed, is evaporated crystallization by controlling physical parameter later, obtains potassium sulfate crystallized product, point
The dope obtained when from potassium sulfate crystallized product returns the sulfate crystal unit 14 by Pipeline transport and recycles.
The sodium potassium composite sulfur hydrochlorate solid that aforementioned crystalline separation obtains is added water by this step, carries out potassium sulfate crystallization later,
Potassium product therein is then demultiplex out, and obtains the mother liquor of containing sulfate, the mother liquor of containing sulfate is back to sulphur after collecting
Sour sodium crystallization process further uses.
In the present invention, this corresponding step can provide potassium sulfate crystalline element 31, the potassium sulfate crystallization point of sequential connection
From device 32.
Previous step obtain sodium potassium composite sulfur hydrochlorate solid can by Pipeline transport to the potassium sulfate crystalline element 31,
The potassium sulfate crystalline element 31 may include continuous evaporative crystallization tank, circulating pump, vacuum pump group, condenser, condensate water pot, condensation
The devices such as water pump add water (can be the recycle-water that aforementioned upgrading unit generates), simultaneously in the potassium sulfate crystalline element 31
Control temperature (0 to 90 °) and pressure (- 98kpa to the parameters such as 40kpa), first in the continuous steaming for generating crystallization for potassium sulfate
Condition needed for sending out the crystallization of crystallizing tank internal control potassium sulfate making (temperature and pressure and dispensing crystal seed), forms potassium sulfate crystallization, together
When water be added if necessary under the conditions of this temperature, pressure allow to control sodium sulfate salt solubility and cannot reach saturation, in this way
Mother liquor is to convert the mother liquor for forming potassium sulfate crystallization and containing sulfate.
For example, can be about 35 DEG C working as running temperature in crystallizer, when pressure is 10kpa, by the way that 5% potassium sulfate is added
Crystal seed (5% herein can be the mass percent by calculating the opposite crystallization total amount obtained), forms potassium sulfate crystallization, together
The solubility of time control Sulphuric acid sodium salt is reduced to 20% hereinafter, obtaining potassium sulfate crystallization purity height.
It is about 10-15 DEG C when running temperature controls in crystallizer in another specific embodiment, pressure 5-10kpa
When, by the way that about 5% potassium sulfate crystal seed is added, potassium sulfate crystallization is formed, while the solubility for controlling sodium sulfate salt is reduced to 30%
Hereinafter, it is also higher to obtain potassium sulfate crystallization purity.
Later solidliquid mixture by pipeline enter the potassium sulfate Crystallization Separation device 32 (such as Double -stagepusher from
The equipment such as scheming, horizontal spiral lower discharging centrifuge, flat centrifuge, as long as being able to carry out separation of solid and liquid), realize sulphur
Sour potassium and the separation of sodium salt mother liquor, obtain potassium product.Mother liquor obtained after separation need to be collected by piping connection to mother liquor
Tank 4 is then refluxed for sulfate crystal unit 14 continuing with.
In this step, by putting into potassium sulfate crystal seed, the potassium sulfate crystalline product of purity is high is obtained, this is also the present invention
With the difference of other existing process for producing potassium sulfate.
The present invention also provides the systems for the above method comprising sequential connection, for sulfate crystal
One subsystem 1, the second subsystem 2 for the crystallization of sodium potassium composite sulfur hydrochlorate and the third subsystem 3 for potassium sulfate crystallization,
In, first subsystem 1 includes the pretreatment unit 11 being linked in sequence, primary concentration unit 12,13 and of secondary concentration unit
Sulfate crystal unit 14, second subsystem 2 include the sodium potassium composite sulfur hydrochlorate crystalline element 21 and compound being linked in sequence
Salt Crystallization Separation device 22, the third subsystem 3 include the potassium sulfate crystalline element 31 being linked in sequence and potassium sulfate crystallization point
From device 32, the complex salt Crystallization Separation device 22 and the potassium sulfate Crystallization Separation device 32 pass through pipeline and mother liquor respectively
Collecting tank 4 connects, and the mother liquor collecting tank 4 is connect by pipeline with the sulfate crystal unit 14.
The pretreatment unit 11 may include be linked in sequence sedimentation basin, filtering ponds (may include more medium filter, core
Peach shell filter and active carbon filter etc.), the pretreatment unit 11, which is used to for mine being discharged, carries out preliminary treatment, removal
Particulate matter therein.Certainly, after physical filtering, the pH value of water body can also be adjusted by dispensing.
The primary concentration unit 12 and the secondary concentration unit 13 can be using reverse osmosis or high pressure it is reverse osmosis or
The equipment of evaporation technique.Its effect is concentrated by two-stage, influent density is improved, so that subsequent can be more effectively in water
Sodium and kalium element extracts.
Between the primary concentration unit 12 and the secondary concentration unit 13, can connect the pliable cell
15, the pliable cell 15 can be used for the effects of solid particle is precipitated, filtered, PH is adjusted, ion exchange with a series of equipment,
Or their combination.The purpose is to solid particle is more in the water body after the primary concentration unit 12 concentration or impurity is more
In the case where water body is adjusted.
Between the secondary concentration unit 13 and the sulfate crystal unit 14, can also further connect one it is organic
Object removal unit 16, such as activated carbon adsorption device or advanced oxidation or ozone equipment, in this way can when needed, will be in water body
Organic matter be eliminated as much as.
The process flow and equipment of evaporative crystallization can be used in the sulfate crystal unit 14, and heat energy utilization can cover MVR
Heat utilization can be greatly improved using MVR method of evaporating as optimal selection in the forms such as evaporation, steam heat pump evaporation, multiple-effect evaporation in this way
Rate, while operating cost can be significantly reduced.
The Chinese patent referred to such as background technique can be used in first subsystem 1 for sulfate crystal
The method and measure before cut-off to " double-effect evaporation crystallization " technique in CN109336323A, the present invention and the prior art are maximum
The difference lies in that in the prior art, usually after carrying out sulfate crystal, concentrate will directly evaporate after as solid-state
Waste landfill disposal, and the present invention is then further handled concentrate, so that potassium product is obtained, it is therefore, described
First subsystem 1 is not features of the present invention place, and details are not described herein.
The concentrate of 14 outputs of sulfate crystal unit passes through Pipeline transport to the sodium potassium composite sulfur hydrochlorate knot
Brilliant unit 21, the sodium potassium composite sulfur hydrochlorate crystalline element 21 can be used evaporation continous way FC/OSLO/TDB type crystallizer or
Other crystallizers of same type and technology, after crystallization mixture by Pipeline transport to the complex salt Crystallization Separation device 22 into
Row is separated by solid-liquid separation, the complex salt Crystallization Separation device 22 can be under two-level piston material pushing centrifugal machine, horizontal spiral discharging from
The centrifuge instruments such as heart equipment, as long as being able to carry out separation of solid and liquid, the mother liquor isolated need to be by Pipeline transport to mother liquor
After collecting tank 4 is collected, returning the sulfate crystal unit 14 by Pipeline transport, further concentration is utilized.
The separated sodium potassium composite sulfur hydrochlorate solid out of the complex salt Crystallization Separation device 22 passes through Pipeline transport to institute
State potassium sulfate crystalline element 31, the potassium sulfate crystalline element 31 may include continuous evaporative crystallization tank, circulating pump, vacuum pump group,
The devices such as condenser, condensate water pot, condensate pump, in the potassium sulfate crystalline element 31 plus water keeps sodium potassium composite sulfur hydrochlorate molten
Solution, then by the control parameters such as temperature and pressure so that potassium sulfate crystallization and sodium sulphate does not crystallize.
Referring to shown in the dotted line for having arrow in Fig. 1, pipeline can use by the primary concentration unit 12, the second level
Upgrading unit 13 is connect with the potassium sulfate crystalline element 31, and it is compound to dissolve sodium potassium thus to can use concentration process production water
Sulfate solid improves environmental protection efficacy to save water.
The solidliquid mixture of 31 output of potassium sulfate crystalline element enters potassium sulfate crystallization point by pipeline later
From device 32, the potassium sulfate Crystallization Separation device 32 can be discharging under two-level piston material pushing centrifugal machine, horizontal spiral and be centrifuged
The equipment such as machine, flat centrifuge obtain potassium product as long as being able to achieve potassium sulfate and the separation of sodium salt mother liquor.Point
After the mother liquor obtained from after need to be collected by Pipeline transport to mother liquor collecting tank 4, the sulfate crystal is returned by Pipeline transport
Further concentration utilizes unit 14.
One aspect of the present invention realizes the recycling to potassium in mine water, on the other hand since separation mother liquor can recycle,
Therefore in addition to can effectively recycle potassium sulfate crystalline product, while the rate of recovery of sulfate crystal (anhydrous sodium sulphate) is also substantially increased
And purity.
It will be appreciated by those skilled in the art that although the present invention is described in the way of multiple embodiments,
It is that not each embodiment only contains an independent technical solution.So narration is used for the purpose of for the sake of understanding in specification,
The skilled in the art should refer to the specification as a whole is understood, and by technical solution involved in each embodiment
Regard as and can be combined with each other into the modes of different embodiments to understand protection scope of the present invention.
The foregoing is merely the schematical specific embodiment of the present invention, the range being not intended to limit the invention.It is any
Those skilled in the art, made equivalent variations, modification and combination under the premise of not departing from design and the principle of the present invention,
It should belong to the scope of protection of the invention.
Claims (10)
1. a kind of method from mine water recycling potassium, characterized in that it comprises:
Mine water is concentrated via the dilute salting liquid formed after pretreatment, the saline solution after concentration is then delivered to sodium sulphate
Crystalline element obtains sulfate crystal product,
The dope obtained when by separating sodium sulfate crystallized product is delivered to sodium potassium sulphate crystal unit, by controlling physical parameter
Crystallization is evaporated to dope, obtains sodium potassium sulphate crystal product.The dope obtained when separating sodium potassium sulphate crystal product
The sulfate crystal unit is returned by Pipeline transport to recycle.
The sodium potassium composite sulfur hydrochlorate crystallized product that separation obtains is delivered to potassium sulfate crystalline element, adds shape after water and potassium sulfate crystal seed
At salting liquid, it is evaporated crystallization by controlling physical parameter later, obtains potassium sulfate crystallized product, separation potassium sulfate crystallization produces
The dope obtained when object returns the sulfate crystal unit by Pipeline transport and recycles.
2. the method according to claim 1, wherein in the evaporative crystallization mistake for obtaining sodium potassium sulphate crystal product
Cheng Zhong, do not need launch seed crystal material or other be used for ion exchange material, it is only necessary to control evaporating temperature control 0 to
110 °, pressure limit is -98kpaG to 40kpaG.The concentration for maintaining complex salt crystallization in crystallizer simultaneously is controlled 15%
~70%, the reflux mother liquid concentration after separation is controlled 10%~50%.
3. the method according to claim 1, wherein in potassium sulfate crystalline element, by controlling temperature and pressure
Potassium sulfate crystallization is carried out, and sodium sulphate does not crystallize or only a small amount of crystallization, potassium product therein is then demultiplex out, and contained
The mother liquor of sulfate.At 0 to 90 °, pressure is controlled in -98kpa to 40kpa for temperature control.
4. according to the method described in claim 3, it is characterized in that, launching 5% potassium sulfate crystal seed in potassium sulfate crystalline element.
5. according to the method described in claim 4, it is characterized in that, temperature control exists in potassium sulfate crystallization process in step C
0 to 90 °, pressure is controlled in -98kpa to 40kpa.
6. the method according to claim 1, wherein the pretreatment includes precipitating, filtering, PH adjusting, ion
Exchange or their combination.
7. the method according to claim 1, wherein being carried out organic before saline solution enters sulfate crystal unit
Object removal.
8. a kind of system of the method for one of claim 1-7, which is characterized in that it includes being linked in sequence, and is used for sulphur
The first subsystem, the second subsystem for the crystallization of sodium potassium composite sulfur hydrochlorate and the third for potassium sulfate crystallization of sour sodium crystallization
Subsystem, wherein first subsystem includes the pretreatment unit being linked in sequence, primary concentration unit, secondary concentration unit
With sulfate crystal unit, second subsystem includes the sodium potassium composite sulfur hydrochlorate crystalline element and complex salt knot being linked in sequence
Brilliant separator, the third subsystem include the potassium sulfate crystalline element and potassium sulfate Crystallization Separation device being linked in sequence, institute
It states complex salt Crystallization Separation device and the potassium sulfate Crystallization Separation device passes through pipeline respectively and connect with mother liquor collecting tank, it is described
Mother liquor collecting tank is connect by pipeline with the sulfate crystal unit.
9. system according to claim 8, which is characterized in that the sodium potassium composite sulfur hydrochlorate crystalline element is that evaporation is continuous
Formula FC/OSLO/TDB type crystallizer, the complex salt Crystallization Separation device are two-level piston material pushing centrifugal machine or horizontal spiral
Lower discharging centrifugation apparatus.
10. system according to claim 8, which is characterized in that the potassium sulfate crystalline element includes continuous evaporative crystallization
Tank, circulating pump, vacuum pump group, condenser, condensate water pot, condensate pump, the potassium sulfate Crystallization Separation device are two-diameter piston
Pusher centrifuge or horizontal spiral lower discharging centrifuge or flat centrifuge.
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Effective date of registration: 20240204 Address after: 211899, 1st Floor, Research Building, No. 8 Yongjin Road, Jiangbei New District, Nanjing City, Jiangsu Province Patentee after: NANJING NANHUAN WATER TECHNOLOGY Co.,Ltd. Country or region after: China Patentee after: NANJING GUODIAN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Address before: 210061 1st floor, scientific research building, No.8, Yongjin Road, Jiangbei new district, Nanjing City, Jiangsu Province Patentee before: NANJING NANHUAN WATER TECHNOLOGY Co.,Ltd. Country or region before: China |