CN101254966A - Recovery method of phosphate discharge liquid - Google Patents
Recovery method of phosphate discharge liquid Download PDFInfo
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- CN101254966A CN101254966A CNA2008101039357A CN200810103935A CN101254966A CN 101254966 A CN101254966 A CN 101254966A CN A2008101039357 A CNA2008101039357 A CN A2008101039357A CN 200810103935 A CN200810103935 A CN 200810103935A CN 101254966 A CN101254966 A CN 101254966A
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Abstract
The invention relates to a method for treating and reclaiming phosphatic waste liquor with low concentration. The method comprises the following steps: firstly solid impurity is removed through filtering the waste liquor containing phosphoric acid, then ion exchange is performed through anion exchange resin to ensure phosphate radical ion to be attached to the resin, and therefore the phosphoric acid is separated from the waste liquor. Then elution is performed to the anion exchange resin by using sodium salts, such as sodium chloride or sodium carbonate, and ammonia salt solution, to displace the phosphate radical ion, and to generate phosphatic sodium salt with higher concentration or ammonium saltwater solution. Then ion-exchange treatment is performed to the water solution by using the anion exchange resin, sodium ion or ammonia ion is replaced by hydrogen ion, and phosphatic water solution with higher concentration is generated. At last, moisture in the phosphatic water solution is removed by using vacuum evaporation, and pure phosphoric acid is obtained to be circularly used. The method is applied to other phosphatic waste liquor with little dissoluble impurity.
Description
Technical field
The invention belongs to technical field of chemical separation, particularly a kind of processing of low phosphorus acid waste liquid and recovery method.
Background technology
Phosphoric acid comprises polyphosphoric acid, is comparatively common solvent.In the process of using phosphoric acid, can produce the waste liquid that contains phosphoric acid.Particularly in the production process of pbo fiber, can produce a large amount of low phosphorus acid waste liquids.
Pbo fiber claims phenylene benzo-dioxazole fiber again, penylene benzene and two oxazole fibers.The intensity of pbo fiber product can reach 5.8GPa, modulus 180GPa; Heat resisting temperature reaches 600 ℃, and limiting oxygen index(LOI) 68 does not burn in flame, do not shrink, and thermotolerance and flame retardancy are higher than other any organic fibre.Be mainly used in heat-resisting technical textile and fiber reinforced material.The preparation of pbo fiber is divided into composite salt preparation, synthetic, the spinning three phases of polymkeric substance.Composite salt is made by monomer salt, terephthalic acid, additive.Monomer salt is diamino resorcin hydrochlorate.Composite salt and polyphosphoric acid, Vanadium Pentoxide in FLAKES mix, and carry out polycondensation under the state of stirring heating, and the polymkeric substance after polycondensation is finished enters twin screw extruder and extrudes, and carries out the one-off drawing moulding at shower nozzle.Then, remove the phosphoric acid in the fiber, after drying coiling and molding through washing.
In the production process of pbo fiber, wash-out phosphoric acid can produce the very low waste liquid of a large amount of phosphoric acid concentrations.Handle and reclaim the phosphoric acid in the waste liquid, not only can reduce phosphoric acid consumption effectively, reduce cost, and help environment protection.
Use a large amount of phosphoric acid that use for other in addition, and produce the production process of phosphate discharge liquid, also need phosphate discharge liquid is recycled.
The recovery of phosphate discharge liquid generally adopts chemical precipitation method or biological method to remove.The chemical process final product is phosphoric acid salt such as calcium phosphate, and phosphoric acid can not directly be recycled.And the biological method production cycle is long, and the weak point that equally also exists phosphoric acid directly not recycle.
Except chemical precipitation method and biological process, phosphate discharge liquid can also adopt evaporation to wait gasification method to remove moisture and recycle.But for the very rare phosphate aqueous solution of concentration, evaporation capacity of moisture content is very big, thereby energy consumption is big, and cost is higher.If the employing reduction vaporization because the pressure of operating environment reduces, impels the boiling point lowering of material, can adopt lower service temperature, thereby reduce energy consumption.But for the lower phosphate discharge liquid of concentration, even adopt underpressure distillation, still need the moisture of vaporizing in a large number, energy consumption is still bigger.
Ion-exchange is the lower novel separation method of a kind of energy consumption, is specially adapted to the lower situation of concentration.
Compare with traditional chemical precipitation, biology and method of evaporating, ion exchange method, it is low, simple to operate to have a cost, the advantage that separated phosphoric acid can recycling.And ion exchange resin is regenerated easily, can reuse.
Ion exchange resin is a kind of functional high molecule material that contains ion-exchange group in cross-linked polymer structures.Ion exchange resin is insoluble to acid, alkaline solution, water and various organic solvent, is fused porousness solid not.Each resin particle all is made of the crosslinked network skeleton with three-dimensional space three-dimensional arrangement, is connecting many comparatively active functional groups on skeleton.This functional group ion that can dissociate out can exchange with ion on every side.The modular construction of ion exchange resin is made up of three parts: insoluble three-dimensional space mesh skeleton, be connected functional groups on the skeleton and functional group with the exchangable ion of opposite charges.
Press the difference of cross-linked polymer, ion exchange resin can be divided into polystyrene, acrylic acid series, phenolic aldehyde system, epoxy system, vinylpyridine system, urea aldehyde system, vinyl chloride etc.According to form, can be divided into gel-type and macroporous type.Character according to functional group can be divided into seven classes such as strong acid, weak acid, highly basic, weak base, chelating, soda acid both sexes and oxidation-reduction type again.
Ion exchange reaction is a reversible, so ion exchange resin can be recycled by exchange and regeneration.Ion-exchange can only take place in weak base anion-exchange resin in acidity or neutral solution, can use yellow soda ash and ammoniacal liquor to regenerate; Strongly basic anion exchange resin carries out ion exchange reaction under acidity, alkalescence and neutrallty condition, use highly basic to regenerate.Weakly acidic cation-exchange resin can only carry out ion-exchange in alkalescence, neutrality or weakly acidic solution; Storng-acid cation exchange resin can all can carry out ion-exchange in acid and basic solution.The equipment that ion-exchange is adopted mainly contains three kinds of steel basin, fixed bed and moving-beds.
Japan Nippon Gosei company (ippon company) has proposed a kind of method that reclaims phosphoric acid in Japanese Patent JP07155607: the waste phosphoric acid catalyzer enters extraction tower, under stirring condition, phosphoric acid extraction is separated, filter then, re-use strong-acid ion exchange resin and remove metal ion.The phosphoric acid of purifying is used for hydration reaction with reclaiming also.
Proposed a kind of processing and reclaimed the phosphoric acid wastewater treatment method among the Chinese patent CN200510090241 of day Benshen's steel loop border Shu Lijing company application.The process of this method is: be under the tart state, waste liquid contacts with anionite-exchange resin, make other ions such as nitrate ion in the waste liquid, iodide ion carry out ion-exchange, and then contact with anionite-exchange resin, make phosphate ion and anionite-exchange resin carry out ion-exchange, reclaim phosphate ion.
Summary of the invention
The processing method that the present invention relates to is fit to handle and reclaim the low phosphorus acid waste liquid, and waste liquid does not contain influential other soluble impurity except that phosphoric acid and water that recycles.
The method of existing recovery phosphoric acid is mainly chemical precipitation method and biological method.Two kinds of methods all can't directly obtain purified phosphoric acid.Methods such as employing evaporation can be removed the moisture in the phosphate discharge liquid, thereby obtain comparatively purified phosphoric acid.But for the very low waste liquid of phosphoric acid concentration, this method need expend a large amount of energy in order to vaporization moisture, and cost is higher.The present invention at first adopts the method for two step ion-exchanges, the phosphate discharge liquid very low to concentration concentrates, then carry out reduction vaporization, not only can reduce energy consumption greatly, and in base exchange process, can remove other cation impurity in the waste liquid, thereby obtain comparatively purified phosphoric acid.The present invention is suitable for the processing and the recovery of the phosphate discharge liquid in the pbo fiber production process, and it is lower simultaneously also to be suitable for other phosphoric acid concentration, and the processing that does not contain the phosphate discharge liquid that other influence recycles is reclaimed.
Contain phosphate discharge liquid except containing phosphoric acid and water, can contain a spot of solid nonsoluble usually.Solid particulate deposition in ion exchange resin can cause the duct to be stopped up, and therefore solid particulate must be removed.Solid particulate can remove by filter by strainer in the waste liquid.Strainer can adopt filter cloth, also can adopt metal system filter core.For guaranteeing filter effect, filter core or filter cloth generally should be not less than 50 orders.For guaranteeing the work-ing life of strainer, reduce corrosive wear, strainer and waste liquid contact part should adopt corrosion resistant material.
Waste liquid after the filtration treatment at first enters anion exchange procedures and carries out ion-exchange, and phosphate anion is adsorbed on the anionite-exchange resin; Moisture does not adsorb with it and separates with it, discharges, can circular treatment through further purification.The ion exchange resin of this part adopts anionite-exchange resin, and for guaranteeing mass-transfer efficiency, resin particle is unsuitable excessive; Consider resistance to flow, resin particle is unsuitable too small.Generally be not less than 50 orders.Because phosphoric acid concentration is very low, phosphate discharge liquid is a slightly acidic generally speaking, can adopt weak base anion-exchange resin, also can adopt strongly basic anion exchange resin.For regenerating conveniently, preferably adopt weak base anion-exchange resin.Cause phosphate discharge liquid to be alkalescence as containing stronger positively charged ion in the phosphate discharge liquid, should adopt strongly basic anion exchange resin to handle.
Waste liquid through after the anion exchange process mainly contains water, can recycle through handling.Anionite-exchange resin need carry out manipulation of regeneration after using for some time.Can adopt yellow soda ash or ammonia soln to carry out manipulation of regeneration for weak base anion-exchange resin, the phosphoric acid on the resin is eluted.Contain sodium ion or ammonium ion in the elutriant.For obtaining purified phosphoric acid, this elutriant need be removed sodium ion or ammonium ion wherein.This elutriant enters Zeo-karb and handles for this reason, removes sodium ion or ammonium ion in the solution, and the hydrogen ion on the resin enters in the solution, forms the higher phosphoric acid solution of concentration.
This phosphoric acid solution enters to evaporate in the vacuum-evaporator at last removes moisture, obtains comparatively purified phosphoric acid at last.Further heating as required is with products such as generation polyphosphoric acid.
For anion exchange procedures, can adopt strongly basic anion exchange resin, in this case, need to adopt highly basic to carry out manipulation of regeneration, can adopt sodium hydroxide solution to handle, this regeneration soln is the sodium-salt aqueous solution of phosphoric acid, and the sodium ion in the solution can be removed in base exchange process.When adopting weak base anion-exchange resin, should avoid adopting solution such as yellow soda ash to regenerate, in case the purity that negatively charged ion such as blocking acid group enter solution influenced recovery phosphoric acid.When adopting weak base anion-exchange resin absorption phosphate anion, can adopt ammoniacal liquor to regenerate, the elutriant that generate this moment is an ammonium phosphate solution.
Be converted to the higher phosphoric acid solution of concentration through the waste liquid after the two step ion exchange treatment.Initial waste liquid phosphoric acid concentration is low more, and spissated ratio is high more.Therefore the present invention is suitable for the lower phosphate discharge liquid processing of concentration.
Enter reduction vaporization workshop section through the phosphoric acid solution after the two-stage ion exchange treatment, this section can adopt vacuum-evaporator, also the novel separating device that can adopt employing vacuum-evaporation principles such as thin film evaporation, molecular distillation to handle.For reaching separating effect preferably, the vacuum tightness of vacuum-evaporation operating environment need reach certain numerical value, and the pounds per square inch absolute (psia) of general operation environment should be greater than 10 kPas.
All the sepn process of phosphate discharge liquid is divided into five parts: first part is the solid particulate sepn process, and this process adopts filter method; Second section is an anion exchange procedures, and this process adopts anionite-exchange resin to carry out ion-exchange, and the phosphate anion in the waste liquid is removed; Third part is the regenerative process of anionite-exchange resin, generates the sodium salt or the ammonium salt solution of phosphoric acid; The 4th part is a base exchange process, and sodium phosphate that regeneration generates or ammonium phosphate solution are through the processing of Zeo-karb, and sodium ion or ammonium ion are adsorbed on the resin, and resin discharges hydrogen ion, generates comparatively purified phosphoric acid solution; The 5th part is the concentration process of phosphoric acid, and the method for employing reduction vaporization is removed most or all moisture in the phosphoric acid solution, generates purified phosphoric acid.This phosphoric acid can recycle.
Should not contain in the phosphate discharge liquid of handling and to be adsorbed in other negatively charged ion that anionite-exchange resin and adsorptive power are better than phosphoric acid, otherwise the final phosphoric acid that reclaims will contain other anionic impurity.
The equipment that ion-exchange is adopted mainly contains three kinds of steel basin, fixed bed and moving-beds.Can adopt in three kinds of equipment any one for the present invention.For easy to operate, generally adopt fixed bed.Because the corrodibility of phosphoric acid, equipment claimed adopts corrosion resistant material, perhaps material surface is carried out corrosion-resistance treatment.Corrosion resistant material can adopt stainless steel, pottery etc.
Description of drawings
Fig. 1 is the outline flowchart of the phosphoric acid process for treating waste liquor of invention.Phosphoric acid waste liquid 1 is removed solid impurity through strainer 2, enters anion-exchange column 3, and phosphate anion is adsorbed on the ion exchange resin, and water 4 flows out.The aqueous phosphatic 5 that regenerative elution gets off enters cationic exchange coloum 6, replace the positively charged ion that removes in the water by the hydrogen ion on the resin, the phosphate aqueous solution 7 that forms enters in the vacuum-evaporator 9, and moisture and 10 evaporations of volatile impurity are removed, and residue phosphoric acid 11 continues to recycle.
Embodiment
Embodiment of the present invention is described as follows:
Embodiment 1
The phosphate discharge liquid that contains phosphoric acid 0.5%, 20 ℃ of temperature, flow 1.5m
3/ h.At first filter through 200 order Stainless Steel Filters.Then enter ion exchange tower A and carry out ion-exchange.Filling polystyrene strongly basic anion exchange resin among the exchange column A, loadings is 1.8m
3Effluent enters water treatment device and handles.After exchange is carried out 1 hour, feed sodium hydroxide solution and carry out manipulation of regeneration, regenerated liquid enters ion exchange tower B and carries out ion-exchange.Filling polystyrene storng-acid cation exchange resin among the exchange column B, loadings is 1.8m
3, after exchange is carried out 1 hour, feed hydrochloric acid soln and regenerate.The ion-exchange effluent liquid enters vacuum-evaporator, and service temperature is 30 ℃, and vacuum tightness is 2 kPas of pounds per square inch absolute (psia).Steaming thing is volatile components, is mainly moisture.Residue is comparatively purified phosphoric acid, carries back the production systemic circulation to use.
The phosphate discharge liquid that contains phosphoric acid 0.1%, 20 ℃ of temperature, flow 2.5m
3/ h.At first filter through 200 order Stainless Steel Filters.Then enter ion exchange tower A and carry out ion-exchange.Filling polystyrene strongly basic anion exchange resin among the exchange column A, loadings is 1.0m
3Effluent enters water treatment device and handles.After exchange is carried out 1 hour, feed sodium hydroxide solution and carry out manipulation of regeneration, regenerated liquid enters ion exchange tower B and carries out ion-exchange.Filling polystyrene storng-acid cation exchange resin among the exchange column B, loadings is 1.0m
3, after exchange is carried out 1 hour, feed hydrochloric acid soln and regenerate.The ion-exchange effluent liquid enters vacuum-evaporator, and service temperature is 110 ℃, and vacuum tightness is 10 kPas of pounds per square inch absolute (psia).Steaming thing is volatile components, is mainly moisture.Residue is comparatively purified phosphoric acid, carries back the production systemic circulation to use.
The phosphate discharge liquid that contains phosphoric acid 0.1%, 15 ℃ of temperature, flow 2.5m
3/ h.At first filter through 100 keevil frame strainers.Then enter ion exchange tower A and carry out ion-exchange.Filling polystyrene strongly basic anion exchange resin among the exchange column A, loadings is 1.0m
3Effluent enters water treatment device and handles.After exchange is carried out 1 hour, feed sodium hydroxide solution and carry out manipulation of regeneration, regenerated liquid enters ion exchange tower B and carries out ion-exchange.Filling polystyrene weakly acidic cation-exchange resin among the exchange column B, loadings is 1.5m
3, after exchange is carried out 1 hour, feed hydrochloric acid soln and regenerate.The ion-exchange effluent liquid enters vacuum-evaporator, and service temperature is 40 ℃, and vacuum tightness is 5 kPas of pounds per square inch absolute (psia).Steaming thing is volatile components, is mainly moisture.Residue is comparatively purified phosphoric acid, carries back the production systemic circulation to use.
The phosphate discharge liquid that contains phosphatase 11 %, 20 ℃ of temperature, flow 2m
3/ h.At first filter through 200 order liquid filters.Then enter ion exchange tower A and carry out ion-exchange.Filling polystyrene strongly basic anion exchange resin among the exchange column A, loadings is 1.8m
3Effluent enters water treatment device and handles.After exchange is carried out 2 hours, feed sodium hydroxide solution and carry out manipulation of regeneration, regenerated liquid enters ion exchange tower B and carries out ion-exchange.Filling polystyrene storng-acid cation exchange resin among the exchange column B, loadings is 1.8m
3, after exchange is carried out 2 hours, feed hydrochloric acid soln and regenerate.The ion-exchange effluent liquid enters decompression evaporator, and service temperature is 100 ℃, and vacuum tightness is 4 kPas of pounds per square inch absolute (psia).Steaming thing is volatile components, is mainly moisture.Residue is comparatively purified phosphoric acid, carries back the production systemic circulation to use.
The phosphate discharge liquid that contains phosphatase 11 %, 20 ℃ of temperature, flow 2m
3/ h.At first filter through 50 order liquid filters.Then enter ion exchange tower A and carry out ion-exchange.Filling polystyrene weak base anion-exchange resin among the exchange column A, loadings is 2.2m
3Effluent enters water treatment device and handles.After exchange is carried out 2.5 hours, feed ammonia soln and carry out manipulation of regeneration, regenerated liquid enters ion exchange tower B and carries out ion-exchange.Filling polystyrene storng-acid cation exchange resin among the exchange column B, loadings is 1.8m
3, after exchange is carried out 2 hours, feed hydrochloric acid soln and regenerate.The ion-exchange effluent liquid enters decompression evaporator, and service temperature is 90 ℃, and vacuum tightness is 5 kPas of residue pressure.Steaming thing is volatile components, is mainly moisture.Residue is comparatively purified phosphoric acid, carries back the production systemic circulation to use.
Claims (6)
1, a kind of processing recovery method of low phosphorus acid waste liquid, it is characterized in that: the waste liquid that contains phosphoric acid, at first pass through solids removed by filtration impurity, then carrying out ion-exchange with anionite-exchange resin is attached to phosphate anion on the resin, then with containing sodium salt, perhaps ammonium salt, perhaps sodium hydroxide, perhaps the aqueous solution of ammoniacal liquor is with phosphate anion wash-out from the resin, produce the sodium salt or the ammonium salt aqueous solution of the higher phosphoric acid of concentration, this aqueous solution adopts Zeo-karb to remove sodium ion or ammonium ion, then adopt reduction vaporization to remove moisture in the aqueous solution, obtain purified phosphoric acid and recycle.
2, low phosphorus acid waste liquid according to claim 1, it is characterized in that: the phosphoric acid concentration in the described phosphate discharge liquid is no more than 5%, be not less than 1,000,000/.
3, reduction vaporization according to claim 1 is characterized in that: the pounds per square inch absolute (psia) of reduction vaporization is not more than 10 kPas.
4, anionite-exchange resin according to claim 1 is characterized in that: ion exchange resin is strong basicity or weak base anion-exchange resin.
5, Zeo-karb according to claim 1 is characterized in that: ion exchange resin is strongly-acid or weakly acidic cation-exchange resin.
6, ion-exchange according to claim 1 is characterized in that: ion-exchange unit is at least three groups, and one group is carried out ion-exchange, regenerates for one group, and one group is carried out standby.
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| CN102059022A (en) * | 2010-11-23 | 2011-05-18 | 浦坚 | Filter medium for removing sodium in drinking water |
| CN102774929A (en) * | 2012-07-06 | 2012-11-14 | 华南师范大学 | Method for recovering phosphor from eutrophic water |
| CN104176867A (en) * | 2013-05-22 | 2014-12-03 | 北京思践通科技发展有限公司 | Recovery method for amine |
| CN104555963A (en) * | 2014-12-28 | 2015-04-29 | 江苏绿利来股份有限公司 | Method for recycling waste phosphoric acid during production of butachlor |
| CN104628086A (en) * | 2015-01-06 | 2015-05-20 | 大连东泰资源再生有限公司 | Novel phosphorus removal method for alkaline leaching solution containing molybdenum and vanadium |
| CN104973725A (en) * | 2014-04-09 | 2015-10-14 | 中国石油化工股份有限公司 | Treatment and recycle method of phosphoric acid waste liquid |
| CN104973581A (en) * | 2014-04-09 | 2015-10-14 | 中国石油化工股份有限公司 | Treatment method of phosphoric acid waste liquid |
| WO2016131389A1 (en) * | 2015-02-16 | 2016-08-25 | 秦才东 | Method and device for exchanging and concentrating ion in solution |
| CN106746391A (en) * | 2016-11-16 | 2017-05-31 | 环境保护部南京环境科学研究所 | A kind of phosphatization recycling sludge method of disposal |
| TWI608989B (en) * | 2014-07-18 | 2017-12-21 | Oci有限公司 | Method for removing metal ions in phosphoric acid solution |
| CN110697919A (en) * | 2019-10-14 | 2020-01-17 | 江苏永葆环保科技有限公司 | Method for efficiently recovering electrode foil waste acid by using special short bed acid retardation resin |
| CN112499606A (en) * | 2021-01-20 | 2021-03-16 | 江苏电科环保有限公司 | Purification method of phosphoric acid waste liquid |
| CN112624082A (en) * | 2021-01-20 | 2021-04-09 | 江苏电科环保有限公司 | Method for preparing lithium iron phosphate by using phosphoric acid waste liquid |
| CN113233696A (en) * | 2021-04-12 | 2021-08-10 | 厦门建霖健康家居股份有限公司 | Plastic electroplating chemical nickel wastewater treatment system and method |
| CN113754169A (en) * | 2021-09-27 | 2021-12-07 | 成都清境环境科技有限公司 | Treatment method for regenerating anode phosphoric acid waste liquid |
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- 2008-04-14 CN CN2008101039357A patent/CN101254966B/en not_active Expired - Fee Related
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| CN102059022A (en) * | 2010-11-23 | 2011-05-18 | 浦坚 | Filter medium for removing sodium in drinking water |
| CN102774929A (en) * | 2012-07-06 | 2012-11-14 | 华南师范大学 | Method for recovering phosphor from eutrophic water |
| CN102774929B (en) * | 2012-07-06 | 2014-04-23 | 华南师范大学 | Method for recovering phosphor from eutrophic water |
| CN104176867A (en) * | 2013-05-22 | 2014-12-03 | 北京思践通科技发展有限公司 | Recovery method for amine |
| CN104973581B (en) * | 2014-04-09 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of processing method of phosphate discharge liquid |
| CN104973725A (en) * | 2014-04-09 | 2015-10-14 | 中国石油化工股份有限公司 | Treatment and recycle method of phosphoric acid waste liquid |
| CN104973581A (en) * | 2014-04-09 | 2015-10-14 | 中国石油化工股份有限公司 | Treatment method of phosphoric acid waste liquid |
| CN104973725B (en) * | 2014-04-09 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of processing recovery method of phosphate discharge liquid |
| TWI608989B (en) * | 2014-07-18 | 2017-12-21 | Oci有限公司 | Method for removing metal ions in phosphoric acid solution |
| CN104555963A (en) * | 2014-12-28 | 2015-04-29 | 江苏绿利来股份有限公司 | Method for recycling waste phosphoric acid during production of butachlor |
| CN104628086A (en) * | 2015-01-06 | 2015-05-20 | 大连东泰资源再生有限公司 | Novel phosphorus removal method for alkaline leaching solution containing molybdenum and vanadium |
| WO2016131389A1 (en) * | 2015-02-16 | 2016-08-25 | 秦才东 | Method and device for exchanging and concentrating ion in solution |
| CN106746391A (en) * | 2016-11-16 | 2017-05-31 | 环境保护部南京环境科学研究所 | A kind of phosphatization recycling sludge method of disposal |
| CN110697919A (en) * | 2019-10-14 | 2020-01-17 | 江苏永葆环保科技有限公司 | Method for efficiently recovering electrode foil waste acid by using special short bed acid retardation resin |
| CN112499606A (en) * | 2021-01-20 | 2021-03-16 | 江苏电科环保有限公司 | Purification method of phosphoric acid waste liquid |
| CN112624082A (en) * | 2021-01-20 | 2021-04-09 | 江苏电科环保有限公司 | Method for preparing lithium iron phosphate by using phosphoric acid waste liquid |
| CN112499606B (en) * | 2021-01-20 | 2022-04-08 | 江苏电科环保有限公司 | Purification method of phosphoric acid waste liquid |
| CN113233696A (en) * | 2021-04-12 | 2021-08-10 | 厦门建霖健康家居股份有限公司 | Plastic electroplating chemical nickel wastewater treatment system and method |
| CN113754169A (en) * | 2021-09-27 | 2021-12-07 | 成都清境环境科技有限公司 | Treatment method for regenerating anode phosphoric acid waste liquid |
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