CN116730532A - Method for recycling high-salt wastewater from south ionic rare earth separation - Google Patents
Method for recycling high-salt wastewater from south ionic rare earth separation Download PDFInfo
- Publication number
- CN116730532A CN116730532A CN202310692251.XA CN202310692251A CN116730532A CN 116730532 A CN116730532 A CN 116730532A CN 202310692251 A CN202310692251 A CN 202310692251A CN 116730532 A CN116730532 A CN 116730532A
- Authority
- CN
- China
- Prior art keywords
- wastewater
- ammonium chloride
- rare earth
- recycling
- earth separation
- 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.)
- Granted
Links
- 239000002351 wastewater Substances 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000000926 separation method Methods 0.000 title claims abstract description 32
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 27
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 27
- 238000004064 recycling Methods 0.000 title claims abstract description 23
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 160
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 80
- 238000001704 evaporation Methods 0.000 claims abstract description 32
- 239000012452 mother liquor Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000005238 degreasing Methods 0.000 claims abstract description 6
- 239000010413 mother solution Substances 0.000 claims abstract description 4
- 230000008020 evaporation Effects 0.000 claims description 25
- 238000002425 crystallisation Methods 0.000 claims description 23
- 230000008025 crystallization Effects 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 9
- 238000005086 pumping Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229910001385 heavy metal Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007667 floating Methods 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 239000010802 sludge Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 238000007689 inspection Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 230000003203 everyday effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000002354 daily effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012797 qualification Methods 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
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/22—Sulfites of ammonium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/24—Treatment of water, waste water, or sewage by flotation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for recycling high-salt wastewater from south ionic rare earth separation; belonging to the technical field of rare earth wastewater treatment; the method comprises the following steps: pretreatment to obtain ammonium chloride wastewater A; (2) deep degreasing to obtain ammonium chloride wastewater B; (3) Evaporating and crystallizing the ammonium chloride wastewater B to obtain an ammonium chloride product and a centrifugal mother solution A; (4) Carrying out weight removal reaction treatment on the centrifugal mother liquor A to obtain ammonium chloride wastewater C; (5) And (3) evaporating and crystallizing the ammonium chloride wastewater C to obtain an ammonium chloride product. The invention aims to provide a method for recycling the south ionic rare earth separation high-salt wastewater, which has ingenious process, lower operation cost and good effect; the method is used for treating high-salt wastewater in the ionic rare earth separation process.
Description
Technical Field
The invention relates to a rare earth wastewater treatment process, in particular to a method for recycling high-salt wastewater separated by south ionic rare earth.
Background
Along with the continuous implementation of industrial wastewater resource utilization concept in China, the requirements of the industrial park with unified management on the discharge of enterprise wastewater are more and more strict, and the wastewater resource utilization is promoted in response to the call of national wastewater reuse. One serious problem faced by the ion type rare earth separation industry is two problems of ammonia nitrogen pollution and complex impurity components, so that the wastewater reclamation is the attribution of high ammonia nitrogen and high salt wastewater separated by ion type rare earth. The conventional rare earth separation wastewater recycling technology is not to remove impurities firstly and then evaporate and crystallize or condensate water generated by membrane concentration is recycled, and salt products are produced through evaporation and crystallization. The impurity removal process comprises the processes of oil removal, heavy removal and the like, and according to the conventional wastewater recycling process, impurities are removed firstly and then evaporated and crystallized generally so as to ensure the qualification rate of byproducts. The pH value of the raffinate waste water and the carbon precipitation waste water are both in a medium-acid condition and enter a weight removing system, the pH value is required to be adjusted to a higher alkaline condition by alkali in order to ensure the weight removing effect, the pH value is required to be adjusted back to the meta-acid value by acid after the weight removing is finished and then the waste water enters an evaporation crystallization system, a large amount of acid and alkali are required to be consumed for adjusting the pH value at the stage, and the problem of how to reduce the cost of recycling the ionic rare earth separation industrial waste water is a great challenge facing enterprises. Therefore, it is highly desirable to develop a process that reduces the cost of wastewater reclamation operations.
Disclosure of Invention
The invention aims to provide a method for recycling the south ionic rare earth separation high-salt wastewater, which has ingenious process, low operation cost and good effect, aiming at the defects of the prior art.
The technical scheme of the invention is realized as follows: a method for recycling high-salt wastewater from south ionic rare earth separation comprises the following steps: pretreatment to obtain ammonium chloride wastewater A; (2) deep degreasing to obtain ammonium chloride wastewater B; (3) Evaporating and crystallizing the ammonium chloride wastewater B to obtain an ammonium chloride product and a centrifugal mother solution A; (4) Carrying out weight removal reaction treatment on the centrifugal mother liquor A to obtain ammonium chloride wastewater C; (5) And (3) evaporating and crystallizing the ammonium chloride wastewater C to obtain an ammonium chloride product.
In the method for recycling the south ionic rare earth separation high-salt wastewater, the step (1) specifically comprises the following steps: and (3) discharging the raffinate wastewater containing ammonium chloride to an oil separation tank, standing for 1-12h, and separating an oil layer containing the extractant after layering to obtain ammonium chloride wastewater A.
In the method for recycling the south ionic rare earth separation high-salt wastewater, the step (2) specifically comprises the following steps: the ammonium chloride wastewater A obtained in the step (1) is subjected to pretreatment air floatation, the air inlet pressure is not more than 3kg, the water inlet amount is not more than 30t/h, continuous air floatation is carried out, the air floatation is completed, differential oscillation demulsification is carried out, the demulsification time is not more than 20min, a deep oil removal device is adopted to remove floating oil, and the oil enters an organic storage tank after passing through a filter residue device for oil recovery; and filtering the wastewater after degreasing by adopting an active carbon adsorption tank before discharging, wherein the retention time is not more than 10min, and obtaining the ammonium chloride wastewater B after the filtering is completed.
In the method for recycling the south ionic rare earth separation high-salt wastewater, the step (3) specifically comprises the following steps: filtering the ammonium chloride wastewater B and the carbon precipitation wastewater containing high-concentration ammonium chloride in the step (2), uniformly pumping the filtered wastewater to an evaporation crystallization system for treatment, wherein the pH value of the wastewater before the weight removal is not required to be adjusted and is at a target value of the evaporation pH value;
processing by an evaporation crystallization system to obtain ammonium chloride crystals and centrifugal mother liquor A; and drying, packaging and checking the ammonium chloride crystal in sequence to obtain an ammonium chloride product.
In the method for recycling the south ionic rare earth separation high-salt wastewater, the evaporation crystallization system is specifically used for treating: and filtering the ammonium chloride wastewater B and carbon precipitation wastewater containing high-concentration ammonium chloride, uniformly pumping the wastewater to an evaporator for concentration, enabling the evaporation temperature to be 70-90 ℃, enabling the concentrated wastewater to enter a forced circulation evaporator for evaporation crystallization after 1-5 times, enabling the wastewater to enter a cooling crystallization tank for cooling crystallization after evaporation, discharging the wastewater to a centrifugal machine for solid-liquid separation after the concentration reaches more than 40%, enabling the solid phase water content after separation to be 3-10%, enabling the solid phase after the centrifugation to enter a drying system for drying, enabling the drying temperature to be not more than 160 ℃, and carrying out packaging inspection after drying, thus obtaining an ammonium chloride product.
In the method for recycling the south ionic rare earth separation high-salt wastewater, the step (4) specifically comprises the following steps: pumping the centrifugal mother liquor A in the step (3) to a weight removal reaction tank for removing heavy metals, adding an ammonia water solution to adjust the pH to be slightly high alkaline, adding 0.5-10% weight removal agent solution and 1-3% PAC solution after the pH is adjusted to a target value, reacting for 10-30min, automatically flowing to a sludge buffer tank, and filtering by a plate-and-frame filter press to obtain ammonium chloride wastewater C.
After the process is adopted, the invention skillfully carries out evaporation crystallization on the deoiled ammonium chloride wastewater and the carbon precipitation wastewater containing high-concentration ammonium chloride, and then removes the duplicate, compared with the prior art, has the following beneficial effects:
(1) The consumption of a large amount of acid and alkali is reduced, and the addition of the weight removing agent is reduced. The mother solution is evaporated and crystallized first without regulating pH value. Meanwhile, through experimental detection, the ammonium chloride wastewater B is concentrated and evaporated to obtain a centrifugal mother liquor A, and during the period, the concentration multiple of the wastewater can reach 20 times at maximum, and the water quantity of the centrifugal mother liquor A is only 1/20 of that of the ammonium chloride wastewater B according to a theoretical value. Compared with the prior art, the waste water amount is reduced by about 20 times, the consumption of acid, alkali and a weight removing agent is greatly reduced, and the operation cost is greatly saved.
(2) The wastewater resource technology produces qualified agricultural grade ammonium chloride products, which can be sold in the market, under the condition of full load, the daily production of 66.3t of ammonium chloride is 800-1000 yuan per ton, the current selling price is calculated according to 300 days in one year, and the annual income of the ammonium chloride products reaches 1591.2-1989 ten thousand yuan.
(3) The condensate water produced by the evaporation of the wastewater is used for preparing pure water and then is recycled to a production line, the recycling operation cost of the wastewater is reduced, and the estimated 609.9t of reuse water is saved every day, wherein the price of the reuse water is 10.55 yuan/m according to the similar item of the reference of the production cost 3 The annual income of the recycled water reaches 192.1 ten thousand yuan according to 300 days.
Drawings
The invention is described in further detail below in connection with the embodiments in the drawings, but is not to be construed as limiting the invention in any way.
Fig. 1 is a schematic view of the process principle of the present invention.
Detailed Description
Referring to fig. 1, the method for recycling the south ionic rare earth separation high-salt wastewater comprises the following steps:
(1) Pretreating, namely discharging the raffinate wastewater containing ammonium chloride to an oil separation tank, standing for 1-12h, layering, and separating an oil layer containing an extractant to obtain ammonium chloride wastewater A.
(2) Deep oil removal, namely floating the ammonium chloride wastewater A obtained in the step (1) through pretreatment gas, wherein the gas inlet pressure is not more than 3kg, the water inlet amount is not more than 30t/h, continuous gas floating is carried out, the gas floating is completed, differential oscillation demulsification is carried out, the demulsification time is not more than 20min, a deep oil removal device is adopted to remove floating oil, and oil enters an organic storage tank after passing through a filter residue device for oil recovery; and filtering the wastewater after degreasing by adopting an active carbon adsorption tank before discharging, wherein the retention time is not more than 10min, and obtaining the ammonium chloride wastewater B after the filtering is completed. The specific parameters mentioned above depend on the actual amount of wastewater, which is common knowledge of a person skilled in the art and will not be described in detail herein.
(3) Filtering the ammonium chloride wastewater B and the carbon precipitation wastewater containing high-concentration ammonium chloride in the step (2), uniformly pumping the filtered wastewater to an evaporation crystallization system for treatment, wherein the pH value of the wastewater before the weight removal is not required to be adjusted and is at a target value of the evaporation pH value;
the evaporative crystallization is specifically as follows: and filtering the ammonium chloride wastewater B and carbon precipitation wastewater containing high-concentration ammonium chloride, uniformly pumping the wastewater to an evaporator for concentration, enabling the evaporation temperature to be 70-90 ℃, enabling the concentrated wastewater to enter a forced circulation evaporator for evaporation crystallization after concentration is 1-5 times, enabling the wastewater to enter a cooling crystallization tank for cooling crystallization after evaporation is finished, discharging the wastewater to a centrifugal machine for solid-liquid separation after crystallization, obtaining a centrifugal mother liquor A of a liquid phase and a solid phase with a certain water content, namely ammonium chloride crystals after separation, enabling the solid phase to enter a drying system for drying after centrifugation is finished, enabling the drying temperature to be not more than 160 ℃, and packaging and checking after drying to obtain an ammonium chloride product. The crystallization point of the ammonium chloride is lower than that of the heavy metal chloride, and the ammonium chloride is crystallized at a reasonable evaporation temperature, so that heavy metal ions are remained in the centrifugal mother liquor A.
(4) Pumping the centrifugal mother liquor A in the step (3) to a weight removal reaction tank for removing heavy metals, adding an ammonia water solution to adjust the pH to be slightly high alkaline, adding 0.5-10% weight removal agent solution and 1-3% PAC solution after the pH is adjusted to a target value, reacting for 10-30min, automatically flowing to a sludge buffer tank, and filtering by a plate-and-frame filter press to obtain ammonium chloride wastewater C.
(5) And (3) evaporating and crystallizing the ammonium chloride wastewater C to obtain an ammonium chloride product. The evaporative crystallization operation and parameters of the step are the same as those of the step (3).
Experimental example
The same batch of high-salt wastewater generated in the same batch of ionic rare earth separation process is divided into two equal parts, each part is 10 tons. And dividing each part of high-salt wastewater into three equal parts, and respectively adopting the process and the prior process (weight removal and evaporation) to treat, namely respectively carrying out the process and the prior process three times, wherein the results are shown in the following table:
note that: the agricultural grade ammonium chloride national standard heavy metal detection has As, pb, cd, cr and Hg, and according to the actual wastewater multiple detection, as, cd, cr and Hg are all at the detection lower limit, so the heavy metal detection does not contain As, cd, cr and Hg.
According to the national agricultural grade ammonium chloride standard, the ammonia content of the agricultural grade ammonium chloride superior product is more than or equal to 25.4 percent, namely the ammonium chloride content is more than or equal to 97.03 percent; the ammonia content of the agricultural grade ammonium chloride first-class product is more than or equal to 24.5%, namely the ammonium chloride content is more than or equal to 93.59%, and the ammonium chloride and ammonia content of the process of the invention are more than the standard of the agricultural grade ammonium chloride first-class product. Therefore, the process and the existing process can produce stable agricultural grade ammonium chloride first grade products, and the process is proved to be feasible on the premise of saving acid and alkali and removing the weight agent.
In the experiment, when the existing technology is adopted, the pH value of the ammonium chloride wastewater B is required to be regulated to be slightly alkaline, an 8N ammonia water is used for regulating the pH value, 9.89N hydrochloric acid is required to be used for regulating the pH value after the weight is removed, through the experiment, per 200mL of the ammonium chloride wastewater B, the maximum consumption of the 8N ammonia water is approximately 33mL, the maximum consumption of the 9.89N hydrochloric acid is approximately 27mL, if the full-load condition is adopted, the wastewater amount reaches 720t/d, approximately 118.8t of ammonia water and 97.2t of hydrochloric acid are saved every day, the supply price of the ammonia water and the hydrochloric acid is 1050 yuan/t and 350 yuan/t respectively, the calculation is carried out according to 300 days in one year, and the acid-base saving is approximately 4762.8 yuan/a.
The weight removing agent consumption of the prior art is approximately 0.05t calculated according to the 10t of the experimental wastewater consumption, the weight removing wastewater amount of the process is only 1/20 of that of the prior art, compared with the weight removing agent consumption of the prior art, the weight removing agent consumption can be reduced by 0.0475t, the market price of the weight removing agent purchased by the existing company is 13000 yuan/t, if the weight removing agent is produced under the full load condition, the wastewater amount reaches 720t/d, the weight removing agent consumption is calculated according to 300 days in one year, and the weight removing agent consumption is approximately 1333.80 ten thousand yuan/a.
The process disclosed by the invention saves acid and alkali and the consumption of a weight removing agent by 6096.6 ten thousand yuan/a and has very good economic benefit; the addition of acid and alkali in the process of adjusting the pH value of the wastewater can increase the wastewater quantity, the pH value of the process does not need to be adjusted, the wastewater quantity is reduced to a certain extent, and the method has good environmental benefit.
The above examples are provided for convenience of description of the present invention and are not to be construed as limiting the invention in any way, and any person skilled in the art will make partial changes or modifications to the invention by using the disclosed technical content without departing from the technical features of the invention.
Claims (6)
1. The method for recycling the south ionic rare earth separation high-salt wastewater is characterized by comprising the following steps of: pretreatment to obtain ammonium chloride wastewater A; (2) deep degreasing to obtain ammonium chloride wastewater B; (3) Evaporating and crystallizing the ammonium chloride wastewater B to obtain an ammonium chloride product and a centrifugal mother solution A; (4) Carrying out weight removal reaction treatment on the centrifugal mother liquor A to obtain ammonium chloride wastewater C; (5) And (3) evaporating and crystallizing the ammonium chloride wastewater C to obtain an ammonium chloride product.
2. The method for recycling the south ionic rare earth separation high-salt wastewater according to claim 1, wherein the step (1) is specifically as follows: and (3) discharging the raffinate wastewater containing ammonium chloride to an oil separation tank, standing for 1-12h, and separating an oil layer containing the extractant after layering to obtain ammonium chloride wastewater A.
3. The method for recycling the south ionic rare earth separation high-salt wastewater according to claim 1, wherein the step (2) is specifically as follows: the ammonium chloride wastewater A obtained in the step (1) is subjected to pretreatment air floatation, the air inlet pressure is not more than 3kg, the water inlet amount is not more than 30t/h, continuous air floatation is carried out, the air floatation is completed, differential oscillation demulsification is carried out, the demulsification time is not more than 20min, a deep oil removal device is adopted to remove floating oil, and the oil enters an organic storage tank after passing through a filter residue device for oil recovery; and filtering the wastewater after degreasing by adopting an active carbon adsorption tank before discharging, wherein the retention time is not more than 10min, and obtaining the ammonium chloride wastewater B after the filtering is completed.
4. The method for recycling the south ionic rare earth separation high-salt wastewater according to claim 1, wherein the step (3) is specifically as follows: filtering the ammonium chloride wastewater B and the carbon precipitation wastewater containing high-concentration ammonium chloride in the step (2), uniformly pumping the filtered wastewater to an evaporation crystallization system for treatment, wherein the pH value of the wastewater before the weight removal is not required to be adjusted and is at a target value of the evaporation pH value;
processing by an evaporation crystallization system to obtain ammonium chloride crystals and centrifugal mother liquor A; and drying, packaging and checking the ammonium chloride crystal in sequence to obtain an ammonium chloride product.
5. The method for recycling the south ionic rare earth separation high-salt wastewater according to claim 4, wherein the evaporation crystallization system is used for treating specifically: and filtering the ammonium chloride wastewater B and carbon precipitation wastewater containing high-concentration ammonium chloride, uniformly pumping the wastewater to an evaporator for concentration, enabling the evaporation temperature to be 70-90 ℃, enabling the concentrated wastewater to enter a forced circulation evaporator for evaporation crystallization after 1-5 times, enabling the wastewater to enter a cooling crystallization tank for cooling crystallization after evaporation, discharging the wastewater to a centrifugal machine for solid-liquid separation after the concentration reaches more than 40%, enabling the solid phase water content after separation to be 3-10%, enabling the solid phase after the centrifugation to enter a drying system for drying, enabling the drying temperature to be not more than 160 ℃, and carrying out packaging inspection after drying, thus obtaining an ammonium chloride product.
6. The method for recycling the south ionic rare earth separation high-salt wastewater according to claim 1, wherein the step (4) is specifically as follows: pumping the centrifugal mother liquor A in the step (3) to a weight removal reaction tank for removing heavy metals, adding an ammonia water solution to adjust the pH to be slightly high alkaline, adding 0.5-10% weight removal agent solution and 1-3% PAC solution after the pH is adjusted to a target value, reacting for 10-30min, automatically flowing to a sludge buffer tank, and filtering by a plate-and-frame filter press to obtain ammonium chloride wastewater C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310692251.XA CN116730532B (en) | 2023-06-12 | 2023-06-12 | Method for recycling high-salt wastewater from south ionic rare earth separation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310692251.XA CN116730532B (en) | 2023-06-12 | 2023-06-12 | Method for recycling high-salt wastewater from south ionic rare earth separation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116730532A true CN116730532A (en) | 2023-09-12 |
| CN116730532B CN116730532B (en) | 2024-04-30 |
Family
ID=87900703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310692251.XA Active CN116730532B (en) | 2023-06-12 | 2023-06-12 | Method for recycling high-salt wastewater from south ionic rare earth separation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116730532B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008272669A (en) * | 2007-04-27 | 2008-11-13 | Tokyo Gas Co Ltd | Wastewater treatment method |
| CN102531025A (en) * | 2012-01-04 | 2012-07-04 | 南昌大学 | Method for treating rare earth ammonium chloride wastewater |
| CN104140174A (en) * | 2014-07-18 | 2014-11-12 | 燕山大学 | Combined treatment method for ammonia chloride waste water through rare earth extraction separation |
| CN109867381A (en) * | 2017-12-04 | 2019-06-11 | 阿奎泰克国际公司 | Pure salt is produced from waste water |
| US20200346961A1 (en) * | 2019-07-17 | 2020-11-05 | Qingdao University Of Science And Technology | Saline glycerine wastewater treatment system and technology |
| CN113072229A (en) * | 2020-12-30 | 2021-07-06 | 湖南天为环保科技有限公司 | Full-quantitative treatment method for landfill leachate |
| CN115626624A (en) * | 2022-10-26 | 2023-01-20 | 衢州华友钴新材料有限公司 | Method for preparing battery-grade lithium iron phosphate from waste lithium iron phosphate powder |
-
2023
- 2023-06-12 CN CN202310692251.XA patent/CN116730532B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008272669A (en) * | 2007-04-27 | 2008-11-13 | Tokyo Gas Co Ltd | Wastewater treatment method |
| CN102531025A (en) * | 2012-01-04 | 2012-07-04 | 南昌大学 | Method for treating rare earth ammonium chloride wastewater |
| CN104140174A (en) * | 2014-07-18 | 2014-11-12 | 燕山大学 | Combined treatment method for ammonia chloride waste water through rare earth extraction separation |
| CN109867381A (en) * | 2017-12-04 | 2019-06-11 | 阿奎泰克国际公司 | Pure salt is produced from waste water |
| US20200346961A1 (en) * | 2019-07-17 | 2020-11-05 | Qingdao University Of Science And Technology | Saline glycerine wastewater treatment system and technology |
| CN113072229A (en) * | 2020-12-30 | 2021-07-06 | 湖南天为环保科技有限公司 | Full-quantitative treatment method for landfill leachate |
| CN115626624A (en) * | 2022-10-26 | 2023-01-20 | 衢州华友钴新材料有限公司 | Method for preparing battery-grade lithium iron phosphate from waste lithium iron phosphate powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116730532B (en) | 2024-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114105392A (en) | Iron phosphate wastewater treatment method and system | |
| CN109678196B (en) | Method for fully recycling anions and cations in microetching waste liquid | |
| CN105502551A (en) | Technology for recycling lithium from industrial wastewater | |
| CN109867400A (en) | A kind of method that the depth of nickel (cobalt) raffinate removes nickel, cobalt | |
| CN114933288B (en) | High-purity potassium dihydrogen phosphate and preparation method thereof | |
| CN216687797U (en) | Ferric phosphate effluent disposal system | |
| CN116730532B (en) | Method for recycling high-salt wastewater from south ionic rare earth separation | |
| CN107416863B (en) | Method for preparing industrial-grade ammonium salt from wastewater generated in iron phosphate production | |
| CN103288135A (en) | Method for recycling all chemical components in filament melting molybdenum-containing waste acid | |
| CN108128958B (en) | Production process for treating ammonia nitrogen wastewater | |
| CN112340716A (en) | Method for recycling electrode foil formation phosphoric acid waste liquid | |
| CN114212935A (en) | Zero-emission device and method for recycling high-quality sodium sulfate from lead-containing wastewater | |
| CN114956126A (en) | Method for recycling mother solution in sodium method iron phosphate production process | |
| CN213103752U (en) | Cyaniding tailings comprehensive treatment and resource recovery device | |
| CN211111482U (en) | Lithium carbonate washing water resource comprehensive utilization's device | |
| CN1158320A (en) | Method for reclaiming waste keto-acid liquid in prodn. of soluble gluside | |
| CN106396195A (en) | Cycle treatment method for waste liquid produced during refining of cobalt and nickel by virtue of acid leaching process | |
| CN214244092U (en) | Equipment for recycling waste water generated by ammonium lead plaster desulfurization | |
| CN110921949A (en) | Electroplating wastewater recycling treatment method | |
| CN215879199U (en) | Solid waste treatment system | |
| CN115353241B (en) | Method and system for rapidly recovering urea in high-concentration urea production wastewater | |
| CN214457267U (en) | Pretreatment system for sodium sulfate wastewater evaporative crystallization | |
| CN108217614A (en) | Nitric acid recovery method in electrode foil for aluminum electrolytic capacitors production technology | |
| CN219971894U (en) | Treatment system for recycling chemical nickel aging liquid | |
| CN116287787A (en) | MVR evaporation crystallization mother liquor recovery process |
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 | ||
| GR01 | Patent grant |