CN106396227A - Recycling method for waste acid generated during preparation of graphite oxide through liquid-phase chemical method - Google Patents
Recycling method for waste acid generated during preparation of graphite oxide through liquid-phase chemical method Download PDFInfo
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- CN106396227A CN106396227A CN201610809999.3A CN201610809999A CN106396227A CN 106396227 A CN106396227 A CN 106396227A CN 201610809999 A CN201610809999 A CN 201610809999A CN 106396227 A CN106396227 A CN 106396227A
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- Prior art keywords
- acid
- spent acid
- alkene
- graphite oxide
- resource
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- 238000000034 method Methods 0.000 title claims abstract description 143
- 239000002253 acid Substances 0.000 title claims abstract description 115
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 56
- 239000010439 graphite Substances 0.000 title claims abstract description 56
- 239000000126 substance Substances 0.000 title claims abstract description 39
- 239000002699 waste material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 238000004064 recycling Methods 0.000 title abstract 8
- 239000007791 liquid phase Substances 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 97
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 42
- 238000000926 separation method Methods 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 25
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims abstract 5
- 239000007788 liquid Substances 0.000 claims description 86
- 150000001336 alkenes Chemical class 0.000 claims description 53
- 239000013049 sediment Substances 0.000 claims description 34
- 239000006228 supernatant Substances 0.000 claims description 34
- 239000000706 filtrate Substances 0.000 claims description 33
- 239000011572 manganese Substances 0.000 claims description 33
- 238000001556 precipitation Methods 0.000 claims description 32
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- -1 manganese, inorganic base Chemical class 0.000 claims description 5
- 239000013064 chemical raw material Substances 0.000 claims description 4
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 4
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 4
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004035 construction material Substances 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 238000000108 ultra-filtration Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910003174 MnOOH Inorganic materials 0.000 claims description 2
- 230000004308 accommodation Effects 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical class ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 229910021389 graphene Inorganic materials 0.000 abstract description 5
- 229910052925 anhydrite Inorganic materials 0.000 abstract description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000000053 physical method Methods 0.000 abstract description 3
- 238000000713 high-energy ball milling Methods 0.000 abstract description 2
- 238000000265 homogenisation Methods 0.000 abstract 2
- 238000007796 conventional method Methods 0.000 abstract 1
- 239000010440 gypsum Substances 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 238000011403 purification operation Methods 0.000 abstract 1
- 239000012065 filter cake Substances 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 15
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 6
- 150000001805 chlorine compounds Chemical group 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- 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
- C02F1/44—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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Geology (AREA)
- Removal Of Specific Substances (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention provides a recycling method for waste acid generated during the preparation of graphite oxide through the liquid-phase chemical method. The method comprises the steps of homogenizing the waste acid: pumping the waste acid into a homogenization tank by an acid-resistant pump to homogenize the waste acid; recycling sulfate: adding a precipitant in the homogenization tank according to the molar weight of sulfate ions in the waste acid, conducting the stirring reaction and recycling gypsum (CaSO4*2H2O); recycling manganese ions: adding an inorganic base to adjust the pH value so as to form a manganese hydroxide, then adding an oxidant to react with the manganese hydroxide so as to form a manganese oxide, recycling the manganese hydroxide/manganese oxide or the mixture of the manganese hydroxide and the manganese oxide; conducting the separation and purification operation; recycling chloride ions; and recycling the water. Conventional methods for preparing graphene are mainly divided into physical methods and chemical methods. The physical methods are composed of a micro-mechanical stripping method, a high-energy ball milling method and the like. The above methods are low in yield and are not suitable for large scale production. The method of the present invention is applied to the clean production of graphite oxide and the comprehensive utilization of waste acid resources.
Description
Technical field：
The present invention relates to a kind of liquid chemical method prepares the method for resource of the produced spent acid of graphite oxide (alkene).
Background technology：
Graphene is a kind of carbon nanomaterial with two-dimension plane structure, shows because it has special monoatomic layer structure
Many unique physicochemical properties, are widely used in fields such as the energy, environment, electronics, biology, medical science, chemistry,
Basic and applied research about Graphene has become one of current focus advanced subject.The preparation method of Graphene is mainly divided
For physical method and chemical method, Physical mainly includes micromechanics stripping method, high-energy ball milling method etc., and the method low yield is uncomfortable
In large-scale production.Chemical method mainly includes chemical vapour deposition technique, crystal epitaxy method, oxidation-reduction method.Wherein, aoxidize
Reducing process is also referred to as liquid chemical method, is to aoxidize graphite strong acid to generate graphite oxide (alkene), then carries out reduction and generate stone
Black alkene.What liquid chemical method application at present was more is Hummers method, is the main of graphite oxide (alkene) large-scale production preparation
Form.But, liquid chemical method can produce substantial amounts of spent acid during graphite oxide (alkene) is prepared in production, with Hummers method
As a example, often produce the acid pickle that 1 ton of graphite oxide (alkene) can produce 5-20 ton, and acid content is high, ecological environment is caused can not
The pollution problem reversing, therefore, seriously constrains the scale of mass production of graphite oxide (alkene).
Environmental pollution and shortage of resources are the top-priority key subjects of China's the Implement of sustainable development strategy, are also 21
Century the significant challenge that faced of human society.As a kind of important environomental pollution source, its comprehensive control recycles draws spent acid
Play the extensive concern of people.At present, waste acid resource treatment technology mainly has one-step calcinations, evaporation, membrane separation process, extraction
Follow the example of and chemical transformation.These methods respectively have pluses and minuses in actual application, and single technical process is difficult to meet practicality
Require, especially liquid chemical method prepares produced acid pickle during graphite oxide (alkene), not only acid content is high, but also
Containing substantial amounts of metal ion, if appropriate integrated treatment not carried out to it, not only result in serious environmental pollution, but also
The significant wastage of resource can be caused.It is directed to liquid chemical method and prepare spent acid produced by graphite oxide (alkene), still without row
Effectively comprehensive resource treatment technology, still belongs to blank in China.
Taking Hummers method as a example, liquid chemical method prepares the main component of produced spent acid during graphite oxide (alkene)
Be main component be water, sulphuric acid, hydrochloric acid, nitric acid, manganese ion, potassium ion, several in sodium ion.Materialization according to these components
Characteristic, the present invention develops a set of simple combined technical method it is achieved that the resource of spent acid, reclaims Gypsum Fibrosum and contains
Chlorine complex salt；Achieve the resource of manganese ion, reclaim hydroxide or the oxide of manganese；Achieve the cycling and reutilization of water.
The product that this process reclaims can be permissible as electrode material, construction material, ornament materials and other chemical raw material, water
Cycling and reutilization achieves closed circulation in graphite oxide (alkene) production line, whole technical process, meets the basic of clean manufacturing
Require.In addition, the method is simple to operate, process intensification, easily controllable, with low cost, technical process environmental protection, there is popularization
The realistic meaning of application.
Content of the invention：
It is an object of the invention to provide a kind of liquid chemical method prepares the method for resource of the produced spent acid of graphite oxide (alkene).
Above-mentioned purpose is realized by following technical scheme：
A kind of liquid chemical method prepares the method for resource of the produced spent acid of graphite oxide (alkene) it is characterised in that including following work
Skill step：
（1）Spent acid homogenizing：With acid-proof pump, spent acid is injected homogenizing in balancing reservoir；
（2）Sulfate radical resource：Reclaim Gypsum Fibrosum（CaSO4·2H2O）, the spent acid after homogenizing is pumped to reaction settling basin A
In, add precipitant by the mole of sulfate ion in spent acid, stirring reaction forms Gypsum Fibrosum, precipitation, and supernatant is pumped to
Reaction settling basin B, sediment pump delivers to filter plant, solid-liquid separation, and filtrate enters reaction settling basin B, gained after filtration cakes torrefaction
Gypsum Fibrosum export trade, as construction material or ornament materials.
（3）Manganese ion resource：Reclaim hydroxide or oxide or the two mixture of manganese, inorganic base is added to instead
Answer in sedimentation tank B, adjust pH value, stirring, form the hydroxide of manganese, add oxidant, reaction forms the oxide of manganese, sinks
Form sediment, supernatant is pumped to next procedure, and sediment pump delivers to filter plant, solid-liquid separation, and filtrate delivers to next procedure, filter cake is done
Dry rear gained recovery product export trade, as electrode material or other chemical raw material.
（4）Chloride ion resource：Water circulation recycles, step（3）The separated purification of produced waste liquid, obtains chloride compound
Salt and water, chloride complex salt export trade after being dried is used as other chemical raw materials, and water circulation is reused in oxidation-reduction method and prepares oxygen
Graphite alkene technique.
Described liquid chemical method prepares the method for resource of the produced spent acid of graphite oxide (alkene), according to institute in step 1
The spent acid stated prepares graphite oxide (alkene) technique from chemical method production, main component be water, sulphuric acid, hydrochloric acid, nitric acid, manganese from
One or more of son, potassium ion, sodium ion.
Described liquid chemical method prepares the method for resource of the produced spent acid of graphite oxide (alkene), according to institute in step 2
The recovery product stated is Gypsum Fibrosum（CaSO4·2H2O）.
Described liquid chemical method prepares the method for resource of the produced spent acid of graphite oxide (alkene), according to institute in step 2
The precipitant stated is CaO, Ca (OH) 2 or combinations thereof.
Described liquid chemical method prepares the method for resource of the produced spent acid of graphite oxide (alkene), according to institute in step 3
The recovery product stated is hydroxide or oxide or the two mixture of manganese, and the hydroxide of manganese includes Mn (OH) 2, Mn (OH)
4 and MnOOH and its variant of different crystal forms, the oxide of manganese includes MnO, MnO2, Mn2O3 and Mn3O4 and its different crystal forms
Variant.
Described liquid chemical method prepares the method for resource of the produced spent acid of graphite oxide (alkene), according to institute in step 3
The inorganic base adding stated is one or more of NaOH, KOH, Ca (OH) 2, Mg (OH) 2.
Described liquid chemical method prepares the method for resource of the produced spent acid of graphite oxide (alkene), according to institute in step 3
The pH value range of accommodation stated is 8 ~ 14.
Described liquid chemical method prepares the method for resource of the produced spent acid of graphite oxide (alkene), according to institute in step 3
The oxidant stated be permanganate, manganate, perchlorate, hypochlorite, persulfate, thiosulfate, O3, H2O2,
One or more of ClO2.
Described liquid chemical method prepares the method for resource of the produced spent acid of graphite oxide (alkene), according to institute in step 4
The chloride complex salt of recovery stated, water circulation recycle.
Described liquid chemical method prepares the method for resource of the produced spent acid of graphite oxide (alkene), according to institute in step 4
The method for purifying and separating stated is one or more of ultrafiltration, nano filtering process, electroosmose process, hyperfiltration, crystallization and evaporation method.
Beneficial effects of the present invention：
1. the present invention selects green general-purpose, the chemical agent of environment-protecting asepsis and easily operated, the simple method of program, recovery
Product can be used as electrode material, construction material, ornament materials and other chemical raw material, and water can be with cycling and reutilization in oxidation
Graphite (alkene) production line, whole technical process achieves closed circulation, no pollution, zero-emission.In addition, the method simple to operate,
Process intensification, easily controllable, operating cost are cheap, have the realistic meaning of popularization and application, are graphite oxide (alkene) scale amount
Product has paved road.
The enforcement of the present invention can significantly reduce the production cost of enterprise, substantially improves Business Economic Benefit.Due to money
Source recovery product can make the operation cost of spent acid integrated treatment be reduced to zero with export trade profit or extension industry chain.With year
As a example producing the enterprise of 500 tons of Graphenes, it is expected every year to produce spent acid 5000-10000 ton, if entrusting third party to process,
Per kilogram bargain price is about 80 yuan, and annual enterprise will pay the processing cost of hundred million yuan of 4-8 for this, considerably increases the life of enterprise
Produce cost, damage Business Economic Benefit.Using the Technology of the present invention, the production that can save hundred million yuan of 4-8 for enterprise every year becomes
This, and this method invests little instant effect.
Brief description：
The method of resource process chart of accompanying drawing 1 present invention.
Specific embodiment：
Embodiment 1
With acid-proof pump, spent acid is injected homogenizing in balancing reservoir, the spent acid after homogenizing is pumped in reaction settling basin A, by sulfur in spent acid
The mole of acid ion adds the mixture of precipitant CaO and Ca (OH) 2, and stirring reaction forms Gypsum Fibrosum（CaSO4·
2H2O）, supernatants after precipitation is pumped to reaction settling basin B, and sediment pump delivers to filter plant.Solid-liquid separation, filtrate enters instead
Answer sedimentation tank B, filter cake is Gypsum Fibrosum.KOH is added in reaction settling basin B, adjusts pH value to 9, stir and form Mn (OH)
4, add potassium permanganate, reaction forms Mn3O4, and supernatants after precipitation is pumped to next procedure, and sediment pump is delivered to filtration and set
Standby.Solid-liquid separation, filtrate delivers to next procedure, obtains Mn3O4 after filtration cakes torrefaction.Collected waste liquid is returned using evaporative crystallization method
Receive chloride double salt, water circulation is reused in graphite oxide (alkene) production line.
Embodiment 2
With acid-proof pump, spent acid is injected homogenizing in balancing reservoir, the spent acid after homogenizing is pumped in reaction settling basin A, by sulfur in spent acid
The mole of acid ion adds precipitant CaO, and stirring reaction forms Gypsum Fibrosum（CaSO4·2H2O）, supernatants after precipitation pump
Deliver to reaction settling basin B, sediment pump delivers to filter plant.Solid-liquid separation, filtrate enters reaction settling basin B, and filter cake is made a living
Gypsum Fibrosum.NaOH is added in reaction settling basin B, adjusts pH value to 10, stir and form Mn (OH) 2, add potassium permanganate, instead
MnO should be formed, supernatants after precipitation is pumped to next procedure, sediment pump delivers to filter plant.Solid-liquid separation, filtrate is delivered to down
Procedure, obtains MnO after filtration cakes torrefaction.Collected waste liquid adopts evaporative crystallization method to reclaim chloride double salt, and water circulation recycles
In graphite oxide (alkene) production line.
Embodiment 3
With acid-proof pump, spent acid is injected homogenizing in balancing reservoir, the spent acid after homogenizing is pumped in reaction settling basin A, by sulfur in spent acid
The mole of acid ion adds the mixture of precipitant CaO and Ca (OH) 2, and stirring reaction forms Gypsum Fibrosum（CaSO4·
2H2O）, supernatants after precipitation is pumped to reaction settling basin B, and sediment pump delivers to filter plant.Solid-liquid separation, filtrate enters instead
Answer sedimentation tank B, filter cake is Gypsum Fibrosum.KOH and NaOH is added in reaction settling basin B, adjusts pH value to 9.5, stir shape
Become Mn (OH) 2, add sodium hypochlorite and potassium permanganate, reaction forms MnO2, and supernatants after precipitation is pumped to next procedure, sinks
Long-pending thing is pumped to filter plant.Solid-liquid separation, filtrate delivers to next procedure, obtains MnO2 after filtration cakes torrefaction.Collected waste liquid
Chloride double salt is reclaimed using electroosmose process, water circulation is reused in graphite oxide (alkene) production line.
Embodiment 4
With acid-proof pump, spent acid is injected homogenizing in balancing reservoir, the spent acid after homogenizing is pumped in reaction settling basin A, by sulfur in spent acid
The mole of acid ion adds precipitant Ca (OH) 2, and stirring reaction forms Gypsum Fibrosum（CaSO4·2H2O）, supernatant after precipitation
Reaction settling basin B delivered to by liquid pump, and sediment pump delivers to filter plant.Solid-liquid separation, filtrate enters reaction settling basin B, and filter cake is
For Gypsum Fibrosum.KOH is added in reaction settling basin B, adjusts pH value to 9, stir and form Mn (OH) 4, add potassium hyperchlorate,
Reaction forms Mn3O4 and MnO, and supernatants after precipitation is pumped to next procedure, and sediment pump delivers to filter plant.Solid-liquid separation,
Filtrate delivers to next procedure, obtains Mn3O4, MnO and Mn (OH) 4 mixture after filtration cakes torrefaction.Collected waste liquid adopts nanofiltration
Method reclaims chloride double salt, and water circulation is reused in graphite oxide (alkene) production line.
Embodiment 5
With acid-proof pump, spent acid is injected homogenizing in balancing reservoir, the spent acid after homogenizing is pumped in reaction settling basin A, by sulfur in spent acid
The mole of acid ion adds precipitant CaO, and stirring reaction forms Gypsum Fibrosum（CaSO4·2H2O）, supernatants after precipitation pump
Deliver to reaction settling basin B, sediment pump delivers to filter plant.Solid-liquid separation, filtrate enters reaction settling basin B, and filter cake is made a living
Gypsum Fibrosum.Ca (OH) 2 is added in reaction settling basin B, adjusts pH value to 14, stir and form Mn (OH) 2, add O3, reaction
Form MnO2 and MnO, supernatants after precipitation is pumped to next procedure, and sediment pump delivers to filter plant.Solid-liquid separation, filtrate is sent
To next procedure, after filtration cakes torrefaction, obtain MnO2, MnO and Mn (OH) 2 mixture.Collected waste liquid adopts hyperfiltration to reclaim
Chloride double salt, water circulation is reused in graphite oxide (alkene) production line.
Embodiment 6
With acid-proof pump, spent acid is injected homogenizing in balancing reservoir, the spent acid after homogenizing is pumped in reaction settling basin A, by sulfur in spent acid
The mole of acid ion adds precipitant CaO, and stirring reaction forms Gypsum Fibrosum（CaSO4·2H2O）, supernatants after precipitation pump
Deliver to reaction settling basin B, sediment pump delivers to filter plant.Solid-liquid separation, filtrate enters reaction settling basin B, and filter cake is made a living
Gypsum Fibrosum.Ca (OH) 2 is added in reaction settling basin B, adjusts pH value to 11.5, stir and form Mn (OH) 2, add H2O2,
Reaction forms MnO2 and MnO, and supernatants after precipitation is pumped to next procedure, and sediment pump delivers to filter plant.Solid-liquid separation, filter
Liquid delivers to next procedure, obtains MnO2, MnO mixture after filtration cakes torrefaction.It is chloride multiple that collected waste liquid adopts ultrafiltration to reclaim
Salt, water circulation is reused in graphite oxide (alkene) production line.
Embodiment 7
With acid-proof pump, spent acid is injected homogenizing in balancing reservoir, the spent acid after homogenizing is pumped in reaction settling basin A, by sulfur in spent acid
The mole of acid ion adds precipitant Ca (OH) 2, and stirring reaction forms Gypsum Fibrosum（CaSO4·2H2O）, supernatant after precipitation
Reaction settling basin B delivered to by liquid pump, and sediment pump delivers to filter plant.Solid-liquid separation, filtrate enters reaction settling basin B, and filter cake is
For Gypsum Fibrosum.Mg (OH) 2 is added in reaction settling basin B, adjusts pH value to 13.5, stir and form Mn (OH) 4, add
O3, reaction forms MnO2, and supernatants after precipitation is pumped to next procedure, and sediment pump delivers to filter plant.Solid-liquid separation, filtrate
Deliver to next procedure, after filtration cakes torrefaction, obtain MnO2, Mn (OH) 4 mixture.It is chloride that collected waste liquid adopts nano filtering process to reclaim
Double salt, water circulation is reused in graphite oxide (alkene) production line.
Embodiment 8
With acid-proof pump, spent acid is injected homogenizing in balancing reservoir, the spent acid after homogenizing is pumped in reaction settling basin A, by sulfur in spent acid
The mole of acid ion adds precipitant CaO, and stirring reaction forms Gypsum Fibrosum（CaSO4·2H2O）, supernatants after precipitation pump
Deliver to reaction settling basin B, sediment pump delivers to filter plant.Solid-liquid separation, filtrate enters reaction settling basin B, and filter cake is made a living
Gypsum Fibrosum.NaOH is added in reaction settling basin B, adjusts pH value to 10.5, stir and form Mn (OH) 2, add H2O2, reaction
Form MnO2, supernatants after precipitation is pumped to next procedure, and sediment pump delivers to filter plant.Solid-liquid separation, filtrate is delivered to down
Procedure, obtains MnO2 after filtration cakes torrefaction.Collected waste liquid adopts evaporative crystallization method to reclaim chloride double salt, and water circulation recycles
In graphite oxide (alkene) production line.
Embodiment 9
With acid-proof pump, spent acid is injected homogenizing in balancing reservoir, the spent acid after homogenizing is pumped in reaction settling basin A, by sulfur in spent acid
The mole of acid ion adds precipitant Ca (OH) 2, and stirring reaction forms Gypsum Fibrosum（CaSO4·2H2O）, supernatant after precipitation
Reaction settling basin B delivered to by liquid pump, and sediment pump delivers to filter plant.Solid-liquid separation, filtrate enters reaction settling basin B, and filter cake is
For Gypsum Fibrosum.NaOH and Ca (OH) 2 is added in reaction settling basin B, adjusts pH value to 12.5, stir and form Mn (OH) 2 He
Mn (OH) 4, adds persulfate, and reaction forms Mn3O4, and supernatants after precipitation is pumped to next procedure, and sediment pump is delivered to
Filter plant.Solid-liquid separation, filtrate delivers to next procedure, obtains Mn3O4, Mn (OH) 4 mixture after filtration cakes torrefaction.Collected
Waste liquid adopts nano filtering process to reclaim chloride double salt, and water circulation is reused in graphite oxide (alkene) production line.
Embodiment 10
With acid-proof pump, spent acid is injected homogenizing in balancing reservoir, the spent acid after homogenizing is pumped in reaction settling basin A, by sulfur in spent acid
The mole of acid ion adds precipitant Ca (OH) 2, and stirring reaction forms Gypsum Fibrosum（CaSO4·2H2O）, supernatant after precipitation
Reaction settling basin B delivered to by liquid pump, and sediment pump delivers to filter plant.Solid-liquid separation, filtrate enters reaction settling basin B, and filter cake is
For Gypsum Fibrosum.Ca (OH) 2 is added in reaction settling basin B, adjusts pH value to 14, stir and form Mn (OH) 2 and Mn (OH) 4,
Add thiosulfate, reaction forms Mn3O4, and supernatants after precipitation is pumped to next procedure, and sediment pump is delivered to filtration and set
Standby.Solid-liquid separation, filtrate delivers to next procedure, obtains Mn3O4, Mn (OH) 4 mixture after filtration cakes torrefaction.Collected waste liquid is adopted
Reclaim chloride double salt with ultrafiltration, water circulation is reused in graphite oxide (alkene) production line.
Embodiment 11
With acid-proof pump, spent acid is injected homogenizing in balancing reservoir, the spent acid after homogenizing is pumped in reaction settling basin A, by sulfur in spent acid
The mole of acid ion adds precipitant CaO, and stirring reaction forms Gypsum Fibrosum（CaSO4·2H2O）, supernatants after precipitation pump
Deliver to reaction settling basin B, sediment pump delivers to filter plant.Solid-liquid separation, filtrate enters reaction settling basin B, and filter cake is made a living
Gypsum Fibrosum.KOH is added in reaction settling basin B, adjusts pH value to 13, stir and form Mn (OH) 2, add hypochlorite, instead
Mn3O4 should be formed, supernatants after precipitation is pumped to next procedure, sediment pump delivers to filter plant.Solid-liquid separation, filtrate is delivered to
Next procedure, obtains Mn3O4, Mn (OH) 2 mixture after filtration cakes torrefaction.It is chloride multiple that collected waste liquid adopts hyperfiltration to reclaim
Salt, water circulation is reused in graphite oxide (alkene) production line.
Embodiment 12
With acid-proof pump, spent acid is injected homogenizing in balancing reservoir, the spent acid after homogenizing is pumped in reaction settling basin A, by sulfur in spent acid
The mole of acid ion adds precipitant CaO and Ca (OH) 2, and stirring reaction forms Gypsum Fibrosum（CaSO4·2H2O）, after precipitation
Supernatant is pumped to reaction settling basin B, and sediment pump delivers to filter plant.Solid-liquid separation, filtrate enters reaction settling basin B, filter
Cake is Gypsum Fibrosum.KOH and Ca (OH) 2 is added in reaction settling basin B, adjusts pH value to 9.5, stir and form Mn (OH) 2,
Add ClO2, reaction forms Mn3O4, and supernatants after precipitation is pumped to next procedure, and sediment pump delivers to filter plant.Solid-liquid
Separate, filtrate is delivered to next procedure, obtained Mn3O4 after filtration cakes torrefaction.It is chloride multiple that collected waste liquid adopts electroosmose process to reclaim
Salt, water circulation is reused in graphite oxide (alkene) production line.
Embodiment 13
With acid-proof pump, spent acid is injected homogenizing in balancing reservoir, the spent acid after homogenizing is pumped in reaction settling basin A, by sulfur in spent acid
The mole of acid ion adds precipitant CaO, and stirring reaction forms Gypsum Fibrosum（CaSO4·2H2O）, supernatants after precipitation pump
Deliver to reaction settling basin B, sediment pump delivers to filter plant.Solid-liquid separation, filtrate enters reaction settling basin B, and filter cake is made a living
Gypsum Fibrosum.KOH is added in reaction settling basin B, adjusts pH value to 10, stir and form Mn (OH) 2, add hypochlorite, instead
MnO should be formed, supernatants after precipitation is pumped to next procedure, sediment pump delivers to filter plant.Solid-liquid separation, filtrate is delivered to down
Procedure, obtains MnO, Mn (OH) 2 mixture after filtration cakes torrefaction.It is chloride multiple that collected waste liquid adopts evaporative crystallization method to reclaim
Salt, water circulation is reused in graphite oxide (alkene) production line.
Embodiment 14
With acid-proof pump, spent acid is injected homogenizing in balancing reservoir, the spent acid after homogenizing is pumped in reaction settling basin A, by sulfur in spent acid
The mole of acid ion adds precipitant CaO, and stirring reaction forms Gypsum Fibrosum（CaSO4·2H2O）, supernatants after precipitation pump
Deliver to reaction settling basin B, sediment pump delivers to filter plant.Solid-liquid separation, filtrate enters reaction settling basin B, and filter cake is made a living
Gypsum Fibrosum.KOH is added in reaction settling basin B, adjusts pH value to 10, stir and form Mn (OH) 2, add persulfate, instead
MnO2 should be formed, supernatants after precipitation is pumped to next procedure, sediment pump delivers to filter plant.Solid-liquid separation, filtrate is delivered to
Next procedure, obtains MnO2 after filtration cakes torrefaction.Collected waste liquid adopts electroosmose process to reclaim chloride double salt, and water circulation recycles
In graphite oxide (alkene) production line.
Embodiment 15
With acid-proof pump, spent acid is injected homogenizing in balancing reservoir, the spent acid after homogenizing is pumped in reaction settling basin A, by sulfur in spent acid
The mole of acid ion adds precipitant CaO, and stirring reaction forms Gypsum Fibrosum（CaSO4·2H2O）, supernatants after precipitation pump
Deliver to reaction settling basin B, sediment pump delivers to filter plant.Solid-liquid separation, filtrate enters reaction settling basin B, and filter cake is made a living
Gypsum Fibrosum.Ca (OH) 2 is added in reaction settling basin B, adjusts pH value to 10.5, stir and form Mn (OH) 2, add ClO2,
Reaction forms Mn3O4, and supernatants after precipitation is pumped to next procedure, and sediment pump delivers to filter plant.Solid-liquid separation, filtrate is sent
To next procedure, after filtration cakes torrefaction, obtain Mn3O4.Collected waste liquid adopts hyperfiltration to reclaim chloride double salt, and water circulation is again
It is used in graphite oxide (alkene) production line.
Claims (10)
1. a kind of liquid chemical method prepares the method for resource of the produced spent acid of graphite oxide (alkene) it is characterised in that including following
Processing step：
（1）Spent acid homogenizing：With acid-proof pump, spent acid is injected homogenizing in balancing reservoir；
（2）Sulfate radical resource：Reclaim Gypsum Fibrosum（CaSO4·2H2O）, the spent acid after homogenizing is pumped to reaction settling basin A
In, add precipitant by the mole of sulfate ion in spent acid, stirring reaction forms Gypsum Fibrosum, precipitation, and supernatant is pumped to
Reaction settling basin B, sediment pump delivers to filter plant, solid-liquid separation, and filtrate enters reaction settling basin B, gained after filtration cakes torrefaction
Gypsum Fibrosum export trade, as construction material or ornament materials；
（3）Manganese ion resource：Reclaim hydroxide or oxide or the two mixture of manganese, inorganic base is added to reaction heavy
In the B of shallow lake pond, regulation pH value, stirring, form the hydroxide of manganese, add oxidant, reaction forms the oxide of manganese, precipitates,
Supernatant is pumped to next procedure, and sediment pump delivers to filter plant, solid-liquid separation, and filtrate delivers to next procedure, filtration cakes torrefaction
Gained recovery product export trade afterwards, as electrode material or other chemical raw material；
（4）Chloride ion resource：Water circulation recycles, step（3）The separated purification of produced waste liquid, obtain chloride complex salt and
Water, chloride complex salt export trade after being dried is used as other chemical raw materials, and water circulation is reused in liquid chemical method preparation oxidation stone
Black (alkene) technique.
2. the liquid chemical method according to right 1 prepares the method for resource of the produced spent acid of graphite oxide (alkene), its feature
It is：Spent acid according to step 1 prepares graphite oxide (alkene) technique from chemical method production, and main component is water, sulfur
One or more of acid, hydrochloric acid, nitric acid, manganese ion, potassium ion, sodium ion.
3. the liquid chemical method according to right 1 or 2 prepares the method for resource of the produced spent acid of graphite oxide (alkene), and it is special
Levying is：Recovery product according to step 2 is Gypsum Fibrosum（CaSO4·2H2O）.
4. the liquid chemical method according to right 1 or 2 or 3 prepares the method for resource of the produced spent acid of graphite oxide (alkene),
It is characterized in that：Precipitant according to step 2 is CaO, Ca (OH) 2 or combinations thereof.
5. the liquid chemical method according to right 1 or 2 or 3 or 4 prepares the resource side of the produced spent acid of graphite oxide (alkene)
Method, is characterized in that：Recovery product according to step 3 is hydroxide or oxide or the two mixture of manganese, manganese
Hydroxide includes the variant of Mn (OH) 2, Mn (OH) 4 and MnOOH and its different crystal forms, the oxide of manganese include MnO, MnO2,
Mn2O3 and Mn3O4 and its variant of different crystal forms.
6. the liquid chemical method according to right 1 or 2 or 3 or 4 or 5 prepares the resource of the produced spent acid of graphite oxide (alkene)
Method, is characterized in that：The inorganic base adding according to step 3 is one of NaOH, KOH, Ca (OH) 2, Mg (OH) 2
Or it is several.
7. the liquid chemical method according to right 1 or 2 or 3 or 4 or 5 or 6 prepares the money of the produced spent acid of graphite oxide (alkene)
Source method, is characterized in that：PH value range of accommodation according to step 3 is 8 ~ 14.
8. the liquid chemical method according to right 1 or 2 or 3 or 4 or 5 or 6 or 7 prepares the produced spent acid of graphite oxide (alkene)
Method of resource, is characterized in that：Oxidant according to step 3 is permanganate, manganate, perchlorate, hypochlorous acid
Salt, persulfate, thiosulfate, one or more of O3, H2O2, ClO2.
9. the liquid chemical method according to right 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 prepare graphite oxide (alkene) produced useless
The method of resource of acid, is characterized in that：The chloride complex salt of recovery according to step 4, water circulation recycle.
10. the liquid chemical method according to right 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 is prepared graphite oxide (alkene) and is produced
The method of resource of raw spent acid, is characterized in that：Method for purifying and separating according to step 4 is ultrafiltration, nano filtering process, electric osmose
One or more of analysis method, hyperfiltration, crystallization and evaporation method.
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