CN112299591A - Method for recovering chlorine and preparing chlorine salt based on solvent extraction and salting-out effect integrated technology - Google Patents
Method for recovering chlorine and preparing chlorine salt based on solvent extraction and salting-out effect integrated technology Download PDFInfo
- Publication number
- CN112299591A CN112299591A CN202011012507.0A CN202011012507A CN112299591A CN 112299591 A CN112299591 A CN 112299591A CN 202011012507 A CN202011012507 A CN 202011012507A CN 112299591 A CN112299591 A CN 112299591A
- Authority
- CN
- China
- Prior art keywords
- extraction
- salting
- chlorine
- organic phase
- back extraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 69
- 238000005185 salting out Methods 0.000 title claims abstract description 66
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000000460 chlorine Substances 0.000 title claims abstract description 55
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 55
- 230000000694 effects Effects 0.000 title claims abstract description 35
- 238000000638 solvent extraction Methods 0.000 title claims abstract description 29
- 150000001804 chlorine Chemical class 0.000 title claims abstract description 26
- 238000005516 engineering process Methods 0.000 title claims abstract description 25
- 238000000605 extraction Methods 0.000 claims abstract description 137
- 239000002351 wastewater Substances 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 230000020477 pH reduction Effects 0.000 claims abstract description 34
- 239000003607 modifier Substances 0.000 claims abstract description 19
- 239000012074 organic phase Substances 0.000 claims description 68
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 60
- 239000012071 phase Substances 0.000 claims description 41
- 239000003153 chemical reaction reagent Substances 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 239000003085 diluting agent Substances 0.000 claims description 16
- 239000010842 industrial wastewater Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 239000003350 kerosene Substances 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 235000017550 sodium carbonate Nutrition 0.000 claims description 8
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010977 unit operation Methods 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 229910001422 barium ion Inorganic materials 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 229940057995 liquid paraffin Drugs 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 235000015096 spirit Nutrition 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 26
- 239000000243 solution Substances 0.000 description 24
- 238000005191 phase separation Methods 0.000 description 14
- 239000011780 sodium chloride Substances 0.000 description 13
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- 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
-
- 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)
- 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)
- Physical Water Treatments (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention belongs to the technical field of wastewater treatment, and particularly relates to a method for recovering chlorine and preparing chlorine salt based on a solvent extraction and salting-out effect integrated technology. By adopting a solvent extraction method and combining the process steps of wastewater pretreatment, acidification, extraction, back extraction and salting out in the method, the method has an obvious extraction effect on the ultra-high concentration chlorine-containing wastewater, and provides a feasible scheme for the treatment of the ultra-high concentration industrial chlorine-containing wastewater. In the whole process flow, the cost is reduced to the lowest, the extraction agent is recycled, the purity of the product obtained by salting out is high, and the filtered solution returns to the back extraction process without secondary pollution. The problems of low extraction rate, layering of the extracting agent and the like caused by high viscosity of the extracting agent are solved by adding the phase modifier, and the extracting agent is easy to obtain, high in phase splitting speed, low in investment, low in cost, convenient to use, safe, reliable and convenient to industrialize.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a method for recovering chlorine and preparing chlorine salt based on a solvent extraction and salting-out effect integrated technology.
Background
With the continuous development of the industrial society, water resources are increasingly in short supply, the discharge standard of waste acid is severer year by year, people are dedicated to the recycling of industrial wastewater, and the utilization efficiency of water is improved. The industrial chlorine-containing wastewater is mainly derived from industrial raw materials and chemical reagents added in industrial operation. In recent years, due to continuous mining of mineral resources, ores tend to be poor, fine and impure, so that the concentrate grade is low, the impurity content is high, and high-concentration chlorides are brought in a wet smelting process. The waste water generated in the rare earth industry every year exceeds 2 hundred million tons, wherein the chlorine-containing waste water generated by dissolving rare earth ore with hydrochloric acid and extracting rare earth with a hydrochloric acid system has the characteristics of large volume, high chloride concentration (about 0.45-1.13 mol/L) and the like, and has attracted wide attention. China, one of the largest chlorine-containing product producing countries in the world, can discharge a part of sewage containing organic chloride to nearby rivers and lakes during production and use, so that the chloride content is over-standard. In daily life, the chlorine byproducts are the most common chlorine byproducts used for disinfecting drinking water and sewage and a large amount of chlorine-containing substances brought by burning garbage.
Industrial waste water contains a large amount of chloride ions, and if the industrial waste water is directly discharged without treatment, a plurality of environmental problems are caused, for example, when the content of chloride in animals and plants exceeds a certain value, a poisoning phenomenon is caused; chloride ions in the hydrometallurgical process not only accelerate corrosion and fracture of equipment such as a pump, a stirrer and the like to cause corrosion and dissolution of parts such as a pump shell, a shaft sleeve and the like, but also corrode an anode plate in the electrolytic process and cause corrosion products to deposit on a cathode to influence the product quality; the chlorine-containing waste water is discharged into soil, so that the soil is salinized. Chloride not only damages the passive film of stainless steel to cause pitting corrosion, but also promotes the development of pitting corrosion, affecting the service life of concrete steel bridges. The sodium chloride content of the solution is limited in most areas of china. The sewage discharge reaching the standard is only the minimum standard of industrial wastewater treatment, and the sewage is discharged at the minimum limit value through standard management, equipment maintenance and optimized operation when a society with resource saving, environment friendliness and harmony between people and nature is constructed. The great amount of chloride entering the environment causes serious harm to the environment and organisms, so that the research on the technology for removing the chloride ions is of great significance. In addition, many metallurgical enterprises have technical requirements on efficient dechlorination of wet systems.
At present, chlorine-containing wastewater produced in rare earth production is treated by a plurality of methods, such as a salt precipitation method, a separation and interception method, an ion exchange method, an oxidation-reduction method and the like. However, these methods have certain disadvantages, such as the salt precipitation method, most of the precipitating agents are expensive, and the obtained precipitates are difficult to recycle, resulting in secondary pollution, while the lime aluminum salt precipitation method has a large amount of slag and high cost. The ion exchange method has great limitation aiming at high-concentration chlorine-containing wastewater. The application of the separation and interception method mostly stays in a laboratory stage, and industrial application is difficult to realize. Therefore, in view of the above technical problems, it is necessary to develop a chloride removal process with high extraction efficiency and low energy consumption, i.e., it is urgently required to develop a process for recovering chlorine and preparing a chlorine salt based on an integrated technique of solvent extraction and salting-out effect.
Disclosure of Invention
The invention aims to provide a method for recovering chlorine and preparing chlorine salt based on solvent extraction and salting-out effect integrated technology.
The first of the invention is realized by the following steps: the method comprises the following steps:
(1) and wastewater pretreatment: adding salt substances into industrial wastewater containing 1-90 g/L chloride ions, removing calcium and barium ion impurities in the industrial wastewater, and filtering to remove precipitates and suspended particles;
(2) and acidification: preparing an extracting agent, a diluent and a phase modifier into an organic phase according to a volume ratio, mixing the organic phase with an acid, wherein the ratio is 1: 1-3: 1 at normal temperature, and the acidification time is as follows: 30-60 min; standing, phase separating, and using oil phase as extractant;
(3) and (3) extracting: contacting the acidified organic phase with the pretreated industrial chlorine-containing wastewater according to the volume ratio of 1: 1-4: 1 for 5-60 min, carrying out 1-5-stage countercurrent extraction at normal temperature, standing and splitting phases; if the raffinate is discharged after reaching the standard, continuing the extraction operation if the raffinate is not discharged after reaching the standard, and collecting an organic phase to perform a back extraction unit operation;
(4) and back extraction: selecting alkali liquor as a back extraction reagent, mixing a loaded organic phase with the back extraction reagent, carrying out 1-5-stage counter-current or cross-current back extraction at normal temperature, concentrating chloride ions in the solution to 100-200 g/L, wherein the volume ratio of the organic phase to the back extraction reagent is 1-7: 7-1, the concentration of the back extraction reagent is 1-10 mol/L, and the back extraction time is 1-30 min;
(5) salting out: salting out the chloride ion concentrated solution after back extraction, and precipitating crystals from the concentrated solution by adding a salting-out agent, wherein the amount of the salting-out agent added is determined according to Ksp.
The invention provides a method for recovering chlorine and preparing chlorine salt based on solvent extraction and salting-out effect integrated technology, which has obvious extraction effect on ultra-high concentration chlorine-containing wastewater by adopting a solvent extraction method and combining wastewater pretreatment, acidification, extraction, back extraction and salting-out in the method, and provides a feasible scheme for the treatment of the ultra-high concentration industrial chlorine-containing wastewater. In the whole process flow, the cost is reduced to the lowest, the extraction agent is recycled, the purity of the product obtained by salting out is high, and the filtered solution returns to the back extraction process without secondary pollution. By adding the phase modifier, the problems of low extraction rate, extraction agent layering and the like caused by high viscosity of the extraction agent are solved. The invention has the advantages of easy obtaining of the extracting agent, fast phase separation, less investment, low cost, convenient use, safety, reliability and convenient industrialization.
Drawings
FIG. 1 is a schematic diagram of the process flow of the method for recovering chlorine and preparing chlorine salt based on the solvent extraction and salting-out effect integrated technology;
FIG. 2 is a schematic diagram of XRD of crystals obtained by sodium hydroxide salt precipitation in a method for recovering chlorine and preparing chlorine salt based on an integrated technique of solvent extraction and salting-out effect according to the present invention;
FIG. 3 is a schematic diagram of XRD of crystals obtained by salting out sodium carbonate in a method for recovering chlorine and preparing chlorine salt based on an integrated technology of solvent extraction and salting out effect.
Detailed Description
The invention is further illustrated in the following figures and examples in order to provide the person skilled in the art with a detailed understanding of the invention, without restricting it in any way. Any variations or modifications made in accordance with the teachings of the present invention are intended to be within the scope of the present invention.
The invention is further elucidated with reference to the drawing.
As shown in FIGS. 1 to 3, the invention provides a method for recovering chlorine and preparing chlorine salt based on solvent extraction and salting-out effect integrated technology, which specifically comprises the following steps:
(1) and wastewater pretreatment: adding salt substances into industrial wastewater containing 1-90 g/L chloride ions, removing calcium and barium ion impurities in the industrial wastewater, and filtering to remove precipitates and suspended particles;
(2) and acidification: preparing an extracting agent, a diluent and a phase modifier into an organic phase according to a volume ratio, mixing the organic phase with an acid, wherein the ratio is 1: 1-3: 1 at normal temperature, and the acidification time is as follows: 30-60 min; standing, phase separating, and using oil phase as extractant;
(3) and (3) extracting: contacting the acidified organic phase with the pretreated industrial chlorine-containing wastewater according to the volume ratio of 1: 1-4: 1 for 5-60 min, carrying out 1-5-stage countercurrent extraction at normal temperature, standing and splitting phases; if the raffinate is discharged after reaching the standard, continuing the extraction operation if the raffinate is not discharged after reaching the standard, and collecting an organic phase to perform a back extraction unit operation;
(4) and back extraction: selecting alkali liquor as a back extraction reagent, mixing a loaded organic phase with the back extraction reagent, carrying out 1-5-stage counter-current or cross-current back extraction at normal temperature, concentrating chloride ions in the solution to 100-200 g/L, wherein the volume ratio of the organic phase to the back extraction reagent is 1-7: 7-1, the concentration of the back extraction reagent is 1-10 mol/L, and the back extraction time is 1-30 min;
(5) salting out: salting out the chloride ion concentrated solution after back extraction, and precipitating crystals from the concentrated solution by adding a salting-out agent, wherein the amount of the salting-out agent added is determined according to Ksp.
In the extraction in the step (3), the raffinate is discharged in a standard-reaching way, in particular to standard-reaching raffinate with the chloride ion concentration lower than 400 mg/L;
in the salting-out of the step (5), the Ksp of the salting-out agent is added to be more than 37.94 mol/L.
In the salting-out, the added salt substances comprise: sodium sulfate, potassium sulfate, sodium carbonate and potassium carbonate.
In the acidification step (2), the extractant, the diluent and the phase modifier are prepared into an organic phase mixed with the acid according to the volume ratio, specifically, the extractant (v.%), the phase modifier (v.%) and the diluent (v.%), and the organic phase mixing range is as follows: 1-3: 2-3: 4-7.
The organic phase is composed of an extracting agent, a phase modifier and a diluent;
the extractant comprises: tertiary amines (R3N) trioctylamine and N235; the diluent comprises: kerosene, 200# mineral spirits, liquid paraffin, hexane, octane, and dodecane; the phase modifier comprises: alcohol organic substances, n-octanol, isooctanol, sec-octanol and 1-octanol.
In the acidification step (2), 1-3 mol/L sulfuric acid is used as an acidification reagent in an acidification organic phase, and compared with (O: A), the acidification reagent is set as follows: 1: 1-3: 1, wherein the acidification time is as follows: 30-60 min.
The extraction temperature range is 20-60 ℃.
In the back extraction in the step (4), the back extraction reagent is specifically alkali, and the alkali comprises: sodium hydroxide, sodium carbonate and sodium bicarbonate.
In the salting out in the step (5), the method comprises the following steps:
the liquid filtered in the salting-out crystallization process is returned to the back extraction step to be used as a back extraction reagent.
Specifically, in the embodiment of the invention, a method for efficiently recovering chlorine and preparing chlorine salt by utilizing a solvent extraction and salting-out effect integrated technology is provided, and the following steps are sequentially carried out:
(1) and wastewater pretreatment: adding salt substances into industrial wastewater containing 1-90 g/L chloride ions to remove impurities such as calcium ions and barium ions, and filtering to remove precipitates and suspended particles;
(2) and acidification: preparing an extracting agent, a diluent and a phase modifier into an organic phase according to a certain volume ratio, mixing the organic phase with an acid at normal temperature for 30-60 min, wherein the ratio is 1: 1-3: 1; standing, phase separating, and using oil phase as extractant;
(3) extracting; contacting the acidified organic phase with the pretreated industrial chlorine-containing wastewater according to the volume ratio of 1: 1-4: 1 for 5-60 min, carrying out 1-5-stage countercurrent extraction at normal temperature, standing, and carrying out phase splitting; the single-stage extraction rate is 75-90%, the raffinate is discharged after reaching the standard (< 400 mg/L), and if the raffinate does not reach the standard, the extraction operation is continued, and the organic phase is collected for carrying out the back extraction unit operation;
(4) and back extraction: selecting alkali liquor as a back extraction reagent, mixing a loaded organic phase with the back extraction reagent, carrying out 1-5-stage counter-current/cross-current back extraction at normal temperature, concentrating chloride ions in the solution to 100-200 g/L, wherein the volume ratio of the organic phase to the back extraction reagent is 1-7: 7-1, the concentration of the back extraction reagent is 1-10 mol/L, and the back extraction time is 1-30 min;
(5) salting out: salting out the chloride ion concentrated solution after back extraction, and adding a salting-out agent to separate out crystals, wherein the amount of the salting-out agent added is determined according to Ksp (> 37.94 mol/L).
Preferably, the added salt substances are sodium sulfate, potassium sulfate, sodium carbonate, potassium carbonate and the like.
The configuration of the organic phase is determined according to the volume ratio of the components, namely the extraction agent (v.%) phase modifier (v.%) diluent (v.%), and the organic phase configuration range is as follows: 1-3: 2-3: 4-7; the organic phase consists of an extracting agent, a phase modifier, a diluent and the like, wherein the extracting agent is tertiary amine (R3N) trioctylamine, N235 and the like; diluents are kerosene (sulfonated kerosene, jet kerosene, hydrogenated kerosene, 260 kerosene), 200# solvent oil, liquid paraffin, hexane, octane and dodecane; the phase modifier is alcohol organic matter, n-octanol, isooctanol, sec-octanol, 1-octanol, etc.
The acidification organic phase uses 1-3 mol/L sulfuric acid as an acidification reagent, compared with (O: A), the acidification reagent is set to be 1: 1-3: 1, and the acidification time is 30-60 min.
Mixing the acidified organic phase with the pretreated industrial wastewater containing chlorine according to a certain ratio (1: 1-4: 1), wherein the extraction time is 5-60 min, and the extraction temperature is 20-60 ℃. Standing, phase splitting, discharging raffinate which meets the standard, and continuing extraction if the raffinate does not meet the standard; the organic phase was collected for stripping unit operation.
Before the high-concentration industrial chlorine-containing wastewater reaches the standard and is discharged, multi-stage countercurrent extraction or multi-stage cross-flow extraction can be carried out as required. The stripping reagent is alkali, and is usually sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water and distilled water.
The back extraction of the loaded organic phase adopts multi-stage counter-current back extraction or multi-stage cross-flow back extraction.
Specifically, the addition amount of the salting-out agent is determined according to Ksp, crystals and filtrate obtained after filtration in the crystallization process are salted out, and the filtrate is returned to the back extraction process to be used as a back extraction reagent.
Example 1
The method for efficiently recovering chlorine and preparing chlorine salt by utilizing the solvent extraction and salting-out effect integrated technology is shown in figure 1 in specific implementation and comprises the following steps of:
(1) firstly, detecting whether the industrial wastewater contains other metal ions, and if the metal ions exist, removing the metal ions; filtering the waste water to remove suspended particles. The concentration of the chloride ions in the wastewater is detected to be 30.96 g/L.
(2) Acidifying an organic phase, wherein the organic phase is prepared according to the volume ratio, trioctylamine (v.%) isooctanol (v.%) sulfonated kerosene (v.%) =3:3:4, 1mol/L sulfuric acid is mixed with the organic phase, and compared with (O: A) =1:1, the acidification time is 60min, standing and phase separation are carried out.
(3) And (3) extracting, mixing the acidified organic phase with the wastewater, setting the phase ratio (O: A) =3:2, extracting for 30min, setting the initial pH of the wastewater to be 0.58, standing, carrying out phase separation, and measuring the concentration of chloride ions in the raffinate to be 6.71g/L, wherein the extraction rate is 78.32%. Extraction operation is required when the standard is not met, three-stage countercurrent extraction is carried out, the concentration of chloride ions in raffinate is lower than 400mg/L, the raffinate is discharged after reaching the standard, the loaded organic phase is collected for back extraction, and the total removal rate of the chloride ions is 98.70%.
(4) And back extraction, wherein NaOH is selected as a back extractant, the concentration of the back extractant is 7.5mol/L, the back extraction time is 10min, the back extraction ratio is 4:1, and the chloride ion content in the raffinate is 53.03 g/L. After three-stage countercurrent extraction, standing and phase separation, the concentration of the water-phase chloride ions reaches 163 g/L. The organic phase returns to the acidification process to realize the recycling of the extractant.
(5) Salting out, back extracting to obtain concentrated chloride ion solution as sodium chloride solution, adding sodium hydroxide, separating out sodium chloride crystal according to the same ion effect when the solution reaches the solubility product Ksp of sodium chloride, filtering to obtain precipitate, XRD pattern of which is shown in figure 2, and returning the filtrate to the extraction process as back extraction reagent.
The whole process does not produce secondary pollution, realizes the cyclic utilization of resources and generates benefits at the same time. In the embodiment, the removal rate of chloride ions reaches 98.70 percent, and the final discharged chlorine-containing wastewater is less than 400mg-1。
Example 2
The method for efficiently recovering chlorine and preparing chlorine salt by utilizing the solvent extraction and salting-out effect integrated technology is shown in figure 1 in specific implementation and comprises the following steps of:
(1) firstly, detecting whether the industrial wastewater contains other metal ions, and if the metal ions exist, removing the metal ions; in addition, the wastewater is filtered to remove suspended particles. The concentration of chloride ions in the wastewater is detected to be 45.96 g/L.
(2) Acidifying an organic phase, wherein the organic phase is prepared according to the volume ratio, N235(v.%) isooctanol (v.%) kerosene (v.%) =3:2:5, 1mol/L sulfuric acid is mixed with the organic phase, and compared with (O: A) =1:1, the acidification time is 60min, standing and phase separation are carried out.
(3) And (3) extracting, mixing the acidified organic phase with the wastewater, setting the phase ratio (O: A) =3:2, extracting for 30min, wherein the initial pH of the wastewater is 0.58, standing for phase separation, and measuring the chloride ion concentration in the raffinate to be 9.47g/L, wherein the extraction rate is 79.39%. Extraction operation is required when the standard is not met, four-stage countercurrent extraction is carried out, the concentration of chloride ions in raffinate is lower than 300mg/L, the raffinate is discharged after reaching the standard, the loaded organic phase is collected for back extraction, and the total removal rate of the chloride ions is 99.34%.
(4) And performing back extraction, namely selecting NaOH as a back extractant, wherein the concentration of the back extractant is 10mol/L, the back extraction time is 5min, and the chloride ion content in the raffinate is 78.52g/L compared with that of the back extraction solution at a ratio of 4: 1. After three-stage countercurrent extraction, standing and phase separation, the concentration of the water-phase chloride ions is up to 172.07 g/L. The organic phase returns to the acidification process to realize the recycling of the extractant.
(5) Salting out, back extracting to obtain concentrated solution of chloride ion as sodium chloride solution, adding sodium carbonate, separating out sodium chloride crystal according to same ion effect when the solution reaches the solubility product Ksp of sodium chloride, filtering to obtain precipitate, XRD pattern of which is shown in figure 3, and returning the filtrate to the extraction process as back extraction reagent.
The whole process does not produce secondary pollution, realizes the cyclic utilization of resources and generates benefits at the same time. In the embodiment, the removal rate of chloride ions reaches 99.34 percent, and the final discharged chlorine-containing wastewater is less than 300 mg.L-1。
Example 3
The method for efficiently recovering chlorine and preparing chlorine salt by utilizing the solvent extraction and salting-out effect integrated technology is shown in figure 1 in specific implementation and comprises the following steps of:
(1) firstly, detecting that no metal ions which can generate precipitates and prevent the extraction operation are contained in the industrial wastewater, filtering and removing suspended particles of the metal ions, and determining that the concentration of the chloride ions in the wastewater is 12.39 g/L.
(2) Acidifying an organic phase, wherein the organic phase is prepared according to the volume ratio, N235(v.%) isooctanol (v.%) kerosene (v.%) =3:2:5, 1mol/L sulfuric acid is mixed with the organic phase, and compared with (O: A) =1:1, the acidification time is 30min, standing and phase separation are carried out.
(3) And (3) extracting, mixing the acidified organic phase with the wastewater, setting the phase ratio (O: A) =2:1, extracting for 20min, setting the initial pH of the wastewater to be 1.5, standing, carrying out phase separation, and measuring the concentration of chloride ions in the raffinate to be 1.57g/L, wherein the extraction rate is 87.23%. Extraction operation is required when the standard is not met, 2-stage countercurrent extraction is carried out, the concentration of chloride ions in raffinate is lower than 100mg/L, the raffinate is discharged after reaching the standard, a loaded organic phase is collected for back extraction, and the total removal rate of the chloride ions is 99.19%.
(4) And back extraction, wherein NaOH is selected as a back extractant, the concentration of the back extractant is 7.5mol/L, the back extraction time is 3min, the back extraction ratio is 5:1, and the chloride ion in the raffinate is 34.87 g/L. After three-stage countercurrent extraction, standing and phase separation, the concentration of the water-phase chloride ions reaches up to 90.57 g/L. The organic phase returns to the acidification process to realize the recycling of the extractant.
(5) Salting out, back extracting to obtain concentrated solution of chloride ion as sodium chloride solution, adding sodium carbonate, separating out sodium chloride crystal according to same ion effect when the solution reaches the solubility product Ksp of sodium chloride, filtering to obtain precipitate, XRD pattern of which is shown in figure 3, and returning the filtrate to the extraction process as back extraction reagent.
The whole process does not produce secondary pollution, realizes the cyclic utilization of resources and generates benefits at the same time. In the embodiment, the removal rate of chloride ions reaches 99.19 percent, and the final discharged chlorine-containing wastewater is less than 100 mg.L-1。
Example 4
The method for efficiently recovering chlorine and preparing chlorine salt by utilizing the solvent extraction and salting-out effect integrated technology is shown in figure 1 in specific implementation and comprises the following steps of:
(1) firstly, detecting whether the industrial wastewater contains other metal ions, and if the metal ions exist, removing the metal ions; in addition, the wastewater is filtered to remove suspended particles. The concentration of the chloride ions in the wastewater is 57 g/L.
(2) Acidifying an organic phase, wherein the organic phase is prepared according to the volume ratio, trioctylamine (v.%) isooctanol (v.%) sulfonated kerosene (v.%) =3:2:5, 1mol/L sulfuric acid is mixed with the organic phase, and compared with (O: A) =2:1, the acidification time is 50min, standing and phase separation are carried out.
(3) And (3) extracting, mixing the acidified organic phase with the wastewater, setting the phase ratio (O: A) =2:1, extracting for 25min, setting the initial pH of the wastewater to be 6, standing, performing phase separation, and measuring the concentration of chloride ions in the raffinate to be 12.64g/L, wherein the extraction rate is 77.82%. Extraction operation is required when the standard is not met, 5-stage countercurrent extraction is carried out, the concentration of chloride ions in raffinate is lower than 200mg/L, the raffinate is discharged after reaching the standard, a loaded organic phase is collected for back extraction, and the total removal rate of the chloride ions is 99.65%.
(4) And back extraction, wherein NaOH is selected as a back extractant, the concentration of the back extractant is 10mol/L, the back extraction time is 5min, the back extraction ratio is 5:1, and the chloride ion content in the raffinate is 93 g/L. After three-stage countercurrent extraction, standing and phase separation, the concentration of the water-phase chloride ions reaches 217 g/L. The organic phase returns to the acidification process to realize the recycling of the extractant.
(5) Salting out, back extracting to obtain concentrated chloride ion solution as sodium chloride solution, adding sodium hydroxide, separating out sodium chloride crystal according to the same ion effect when the solution reaches the solubility product Ksp of sodium chloride, filtering to obtain precipitate, XRD pattern of which is shown in figure 2, and returning the filtrate to the extraction process as back extraction reagent.
The whole process does not produce secondary pollution, realizes the cyclic utilization of resources and generates benefits at the same time. In the embodiment, the removal rate of chloride ions reaches 99.65 percent, and the final discharged chlorine-containing wastewater is less than 200mg-1。
The invention provides a method for recovering chlorine and preparing chlorine salt based on solvent extraction and salting-out effect integrated technology, which has obvious extraction effect on ultra-high concentration chlorine-containing wastewater by adopting a solvent extraction method and combining wastewater pretreatment, acidification, extraction, back extraction and salting-out in the method, and provides a feasible scheme for the treatment of the ultra-high concentration industrial chlorine-containing wastewater. In the whole process flow, the cost is reduced to the lowest, the extraction agent is recycled, the purity of the product obtained by salting out is high, and the filtered solution returns to the back extraction process without secondary pollution. By adding the phase modifier, the problems of low extraction rate, extraction agent layering and the like caused by high viscosity of the extraction agent are solved. The invention has the advantages of easy obtaining of the extracting agent, fast phase separation, less investment, low cost, convenient use, safety, reliability and convenient industrialization.
That is, the scheme method of the invention comprises the following steps: pretreating, namely pretreating chlorine-containing wastewater produced industrially to a certain extent to remove impurities which are easy to generate precipitates and interfere the operation of an extraction unit; acidifying, namely preparing an extracting agent, a diluent and a phase modifier into an organic phase according to a certain proportion, and acidifying the organic phase; extracting, mixing the acidified organic phase with high-concentration industrial chlorine-containing wastewater according to a certain ratio, standing, and splitting phases to obtain raffinate and a loaded organic phase; performing back extraction, namely performing multi-stage counter-current back extraction on the organic phase loaded with the target ions by using alkali liquor as a back extraction reagent to obtain a water phase containing ultrahigh chloride ion concentration to obtain a salt solution, and recovering an extractant; salting out and back extracting to obtain salt solution containing ultra-high concentration chloride ions, and separating out the salt solution as chloride crystals through a salting-out effect, so that the chloride ions are efficiently removed and effectively utilized, the method is suitable for chlorine-containing wastewater in various concentration ranges, and particularly has an obvious effect on the ultra-high concentration chlorine-containing wastewater.
Claims (9)
1. A method for recovering chlorine and preparing chlorine salt based on solvent extraction and salting-out effect integrated technology is characterized by comprising the following steps:
(1) and wastewater pretreatment: adding salt substances into industrial wastewater containing 1-90 g/L chloride ions, removing calcium and barium ion impurities in the industrial wastewater, and filtering to remove precipitates and suspended particles;
(2) and acidification: preparing an extracting agent, a diluent and a phase modifier into an organic phase according to a volume ratio, mixing the organic phase with an acid, wherein the ratio is 1: 1-3: 1 at normal temperature, and the acidification time is as follows: 30-60 min; standing, phase separating, and using oil phase as extractant;
(3) and (3) extracting: contacting the acidified organic phase with the pretreated industrial chlorine-containing wastewater according to the volume ratio of 1: 1-4: 1 for 5-60 min, carrying out 1-5-stage countercurrent extraction at normal temperature, standing and splitting phases; if the raffinate is discharged after reaching the standard, continuing the extraction operation if the raffinate is not discharged after reaching the standard, and collecting an organic phase to perform a back extraction unit operation;
(4) and back extraction: selecting alkali liquor as a back extraction reagent, mixing a loaded organic phase with the back extraction reagent, carrying out 1-5-stage counter-current or cross-current back extraction at normal temperature, concentrating chloride ions in the solution to 100-200 g/L, wherein the volume ratio of the organic phase to the back extraction reagent is 1-7: 7-1, the concentration of the back extraction reagent is 1-10 mol/L, and the back extraction time is 1-30 min;
(5) salting out: salting out the chloride ion concentrated solution after back extraction, and precipitating crystals from the concentrated solution by adding a salting-out agent, wherein the amount of the salting-out agent added is determined according to Ksp.
2. The method for recovering chlorine and preparing chlorine salt based on the integrated technology of solvent extraction and salting-out effect according to claim 1, wherein:
in the extraction in the step (3), the raffinate is discharged in a standard-reaching way, in particular to standard-reaching raffinate with the chloride ion concentration lower than 400 mg/L;
in the salting-out of the step (5), the Ksp of the salting-out agent is added to be more than 37.94 mol/L.
3. The method for recovering chlorine and preparing chlorine salt based on the integrated technology of solvent extraction and salting-out effect according to claim 1 or 2, characterized in that: in the salting-out, the added salt substances comprise: sodium sulfate, potassium sulfate, sodium carbonate and potassium carbonate.
4. The method for recovering chlorine and preparing chlorine salt based on the integrated technology of solvent extraction and salting-out effect as claimed in claim 1, wherein in the step (2) acidification, the extractant, the diluent and the phase modifier are configured into organic phase mixed with acid according to volume ratio, specifically the extractant (v.%) the phase modifier (v.%) the diluent (v.%), and the organic phase is set in the range of: 1-3: 2-3: 4-7.
5. The method for recovering chlorine and preparing chlorine salt based on the integrated technology of solvent extraction and salting-out effect according to claim 1 or 4, wherein: the organic phase is composed of an extracting agent, a phase modifier and a diluent;
the extractant comprises: tertiary amines (R3N) trioctylamine and N235; the diluent comprises: kerosene, 200# mineral spirits, liquid paraffin, hexane, octane, and dodecane; the phase modifier comprises: alcohol organic substances, n-octanol, isooctanol, sec-octanol and 1-octanol.
6. The method for recovering chlorine and preparing chlorine salt based on the integrated technology of solvent extraction and salting-out effect according to claim 1 or 4, wherein: in the acidification step (2), 1-3 mol/L sulfuric acid is used as an acidification reagent in an acidification organic phase, and compared with (O: A), the acidification reagent is set as follows: 1: 1-3: 1, wherein the acidification time is as follows: 30-60 min.
7. The method for recovering chlorine and preparing chlorine salt based on the integrated technology of solvent extraction and salting-out effect according to claim 1 or 2, characterized in that: in the extraction in the step (3), the extraction temperature range is 20-60 ℃.
8. The method for recovering chlorine and preparing chlorine salt based on the integrated technology of solvent extraction and salting-out effect according to claim 1, wherein: in the back extraction in the step (4), the back extraction reagent is specifically alkali, and the alkali comprises: sodium hydroxide, sodium carbonate and sodium bicarbonate.
9. The method for recovering chlorine and preparing chlorine salt based on the integrated technology of solvent extraction and salting-out effect according to claim 1, wherein: in the salting out in the step (5), the method comprises the following steps:
the liquid filtered in the salting-out crystallization process is returned to the back extraction step to be used as a back extraction reagent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011012507.0A CN112299591A (en) | 2020-09-24 | 2020-09-24 | Method for recovering chlorine and preparing chlorine salt based on solvent extraction and salting-out effect integrated technology |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011012507.0A CN112299591A (en) | 2020-09-24 | 2020-09-24 | Method for recovering chlorine and preparing chlorine salt based on solvent extraction and salting-out effect integrated technology |
Publications (1)
Publication Number | Publication Date |
---|---|
CN112299591A true CN112299591A (en) | 2021-02-02 |
Family
ID=74488887
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011012507.0A Pending CN112299591A (en) | 2020-09-24 | 2020-09-24 | Method for recovering chlorine and preparing chlorine salt based on solvent extraction and salting-out effect integrated technology |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112299591A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113754001A (en) * | 2021-09-07 | 2021-12-07 | 福建省长汀金龙稀土有限公司 | Resource recycling method for ammonium chloride wastewater generated by rare earth smelting |
CN114804410A (en) * | 2022-04-13 | 2022-07-29 | 南京工业大学 | Method for extracting chloride ions from wet flue gas desulfurization wastewater |
CN114804275A (en) * | 2022-04-02 | 2022-07-29 | 南京工业大学 | Chloride ion removal extracting agent and preparation method thereof |
CN115010159A (en) * | 2022-02-11 | 2022-09-06 | 昆明理工大学 | Method for dechlorinating high-chlorine rare earth wastewater and synchronously recycling calcium and sodium |
CN115140868A (en) * | 2022-07-26 | 2022-10-04 | 山东奥友生物科技股份有限公司 | Continuous treatment process for waste alkaline water in preparation process of 2,4 '-trichloro-2' -nitrodiphenyl ether |
CN115401060A (en) * | 2022-08-24 | 2022-11-29 | 浙江红狮环保股份有限公司 | Method for removing chlorine content in organic hazardous waste |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN86104840A (en) * | 1986-07-12 | 1987-07-22 | 湖北省化学研究所 | Decomposing phosphate rock by chlorhydric acid liquid-liquid extraction preparation phosphoric acid does not have the discharging of waste liquid circulation technology |
JP2004141786A (en) * | 2002-10-25 | 2004-05-20 | Yamaguchi Technology Licensing Organization Ltd | Method and apparatus for metal separation/collection, and separated/collected metal |
CN102021336A (en) * | 2010-12-12 | 2011-04-20 | 昆明理工大学 | Method for separating zinc, fluorine and chlorine from fluorine- and chlorine-containing zinc sulfate solution |
CN103215449A (en) * | 2013-04-23 | 2013-07-24 | 中国科学院青海盐湖研究所 | Method for separating chlorine from zinc sulfate solution with high chlorine concentration |
CN106882884A (en) * | 2017-02-16 | 2017-06-23 | 华电电力科学研究院 | A kind of method of chlorion in recycling waste water |
CN107399780A (en) * | 2017-08-09 | 2017-11-28 | 大唐(北京)水务工程技术有限公司 | The removal methods of chlorion in a kind of chlorine-contained wastewater |
CN111003834A (en) * | 2018-10-08 | 2020-04-14 | 昆明理工大学 | Method for removing arsenic and chlorine from waste acid |
CN111170499A (en) * | 2019-12-28 | 2020-05-19 | 湖南中冶艾迪环保资源开发有限公司 | Method for recovering nickel sulfate from nickel electroplating waste liquid |
-
2020
- 2020-09-24 CN CN202011012507.0A patent/CN112299591A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN86104840A (en) * | 1986-07-12 | 1987-07-22 | 湖北省化学研究所 | Decomposing phosphate rock by chlorhydric acid liquid-liquid extraction preparation phosphoric acid does not have the discharging of waste liquid circulation technology |
JP2004141786A (en) * | 2002-10-25 | 2004-05-20 | Yamaguchi Technology Licensing Organization Ltd | Method and apparatus for metal separation/collection, and separated/collected metal |
CN102021336A (en) * | 2010-12-12 | 2011-04-20 | 昆明理工大学 | Method for separating zinc, fluorine and chlorine from fluorine- and chlorine-containing zinc sulfate solution |
CN103215449A (en) * | 2013-04-23 | 2013-07-24 | 中国科学院青海盐湖研究所 | Method for separating chlorine from zinc sulfate solution with high chlorine concentration |
CN106882884A (en) * | 2017-02-16 | 2017-06-23 | 华电电力科学研究院 | A kind of method of chlorion in recycling waste water |
CN107399780A (en) * | 2017-08-09 | 2017-11-28 | 大唐(北京)水务工程技术有限公司 | The removal methods of chlorion in a kind of chlorine-contained wastewater |
CN111003834A (en) * | 2018-10-08 | 2020-04-14 | 昆明理工大学 | Method for removing arsenic and chlorine from waste acid |
CN111170499A (en) * | 2019-12-28 | 2020-05-19 | 湖南中冶艾迪环保资源开发有限公司 | Method for recovering nickel sulfate from nickel electroplating waste liquid |
Non-Patent Citations (2)
Title |
---|
张寿华等: "《高等学校实用教材 放射化学》", 原子能出版社, pages: 71 - 72 * |
王树楷: "《铟冶金》", 30 April 2006, 冶金工业出版社, pages: 194 - 195 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113754001A (en) * | 2021-09-07 | 2021-12-07 | 福建省长汀金龙稀土有限公司 | Resource recycling method for ammonium chloride wastewater generated by rare earth smelting |
CN115010159A (en) * | 2022-02-11 | 2022-09-06 | 昆明理工大学 | Method for dechlorinating high-chlorine rare earth wastewater and synchronously recycling calcium and sodium |
CN114804275A (en) * | 2022-04-02 | 2022-07-29 | 南京工业大学 | Chloride ion removal extracting agent and preparation method thereof |
CN114804275B (en) * | 2022-04-02 | 2023-11-17 | 南京工业大学 | Chloride ion removal extractant and preparation method thereof |
CN114804410A (en) * | 2022-04-13 | 2022-07-29 | 南京工业大学 | Method for extracting chloride ions from wet flue gas desulfurization wastewater |
CN115140868A (en) * | 2022-07-26 | 2022-10-04 | 山东奥友生物科技股份有限公司 | Continuous treatment process for waste alkaline water in preparation process of 2,4 '-trichloro-2' -nitrodiphenyl ether |
CN115401060A (en) * | 2022-08-24 | 2022-11-29 | 浙江红狮环保股份有限公司 | Method for removing chlorine content in organic hazardous waste |
CN115401060B (en) * | 2022-08-24 | 2023-11-14 | 浙江红狮环保股份有限公司 | Method for removing chlorine content from organic hazardous waste |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112299591A (en) | Method for recovering chlorine and preparing chlorine salt based on solvent extraction and salting-out effect integrated technology | |
CN101161596B (en) | A method for resource processing non-ferro metals processing wastewater containing ammonia and sulfate radical | |
CN102358645B (en) | Fully-closed circulation treatment method for water used by electrolytic manganese metal production | |
CN105087964A (en) | Technology of removing lead and recycling rare earth from saponified wastewater generated during process of rare earth extraction | |
CN105460972B (en) | A kind of its recovery method as resource of circuit board tin-stripping waste liquid | |
CN109987742A (en) | Nickel hydrometallurgy process without drainage of waste water containing heavy metal, oil and high concentration salt-mixture | |
CN106587105A (en) | Method for recovering copper chloride acid etching liquid in printed circuit board | |
CN101041520A (en) | Treatment method for recycling zinc electrolysis washing wastewater | |
CN100385025C (en) | Method of coproducing modified polyiron from copper extracted PCB acid etching waste liquid | |
CN115369248A (en) | Wet recovery method for waste ternary lithium battery | |
CN106396163A (en) | Method for comprehensive treatment and recycling of ammonium sulfate wastewater of rare-earth smelting | |
CN106477775A (en) | A kind of inorganic high salt advanced treatment of industrial waste water the method realizing zero liquid discharge | |
CN101445268B (en) | Technique for recovering zinc chloride from waste water in reduction process of isooctyl thioglycolate | |
CN110342465B (en) | Method for recovering indium tin oxide and waste acid from ITO etching waste liquid | |
CN109576494B (en) | Method for preparing sodium sulfate by utilizing metal surface treatment waste | |
CN110229964B (en) | Method for extracting rubidium from fly ash | |
CN106145443A (en) | A kind of processing method of Rare Earth Production waste water | |
CN110015796B (en) | Zero-discharge treatment system and process for nickel hydrometallurgy wastewater of mixed high-salt system | |
CN106892479B (en) | Method for recovering oxalic acid and hydrochloric acid from rare earth oxalic acid precipitation wastewater | |
CN110668956A (en) | Method for desalting and purifying water phase through water washing extraction in RT base production process | |
CN109368859B (en) | Zero-discharge treatment process for fluoride-applying wastewater in steroid drug production | |
CN113174484A (en) | Dissolving and leaching device for rare earth raw ore and mineral slag | |
LU501486B1 (en) | Method for recovering chlorine and preparing chlorine salt based on solvent extraction and salting-out effect integration technology | |
CN114031104A (en) | Composite process for producing calcium sulfate and regenerating HCl through solvent replacement | |
CN210481113U (en) | Recycling treatment device for rare earth carbon sedimentation wastewater and raffinate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210202 |
|
RJ01 | Rejection of invention patent application after publication |