CN216687797U - Ferric phosphate effluent disposal system - Google Patents
Ferric phosphate effluent disposal system Download PDFInfo
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- CN216687797U CN216687797U CN202123316584.8U CN202123316584U CN216687797U CN 216687797 U CN216687797 U CN 216687797U CN 202123316584 U CN202123316584 U CN 202123316584U CN 216687797 U CN216687797 U CN 216687797U
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Abstract
The utility model relates to the technical field of industrial wastewater treatment, and provides a ferric phosphate wastewater treatment system, which comprises: the first pretreatment device and the second pretreatment device are respectively used for pretreating the iron phosphate mother liquor and the iron phosphate washing water; the evaporation concentration device is respectively communicated with the first pretreatment device and the second pretreatment device and is used for carrying out evaporation concentration on the mother liquor clarified filtrate and the concentrated water A to obtain concentrated water B; the centrifugal device is communicated with the evaporation concentration device and is used for centrifuging the concentrated water B; the cooling crystallization device is communicated with the centrifugal device and is used for cooling and crystallizing the centrifuged product; and the drying device is respectively communicated with the centrifugal device and the cooling crystallization device and is used for drying the products after centrifugation and cooling crystallization, so that ammonium sulfate, ammonium hydrogen phosphate, magnesium sulfate and pure water are recycled, and the purposes of resource recovery and zero emission are achieved.
Description
Technical Field
The utility model relates to the technical field of industrial wastewater treatment, in particular to a ferric phosphate wastewater treatment system.
Background
The ferric phosphate is a precursor of the lithium iron phosphate which is an ideal battery anode material at present. At present, the demand of new energy markets for power batteries, energy storage materials or equipment is increasing, and the demand of iron phosphate is also increasing rapidly. The iron phosphate is subjected to synthesis, washing and other processes in the production process, and the generated synthesis mother liquor and washing water contain metal ions and sulfate ions (SO) with different concentrations4 2-) Phosphate radical ion (PO)4 3-) The high-salt inorganic wastewater has high treatment difficulty, and the discharge of the wastewater can cause serious damage and influence on the surrounding environment.
At present, the mainstream methods for the wastewater generated in the iron phosphate production are divided into a lime precipitation method, a magnesium salt treatment method and a membrane treatment method: (1) the lime precipitation method comprises the steps of adding a large amount of lime into the wastewater, directly discharging the supernatant without considering the standard exceeding of total salt, generating a large amount of sludge which is difficult to treat, and not considering the discharge and treatment of the salt; (2) blowing off high-concentration ammonia nitrogen and precipitating magnesium ammonium phosphate, namely adding magnesium oxide and magnesium hydroxide into the wastewater to generate magnesium ammonium phosphate (struvite); the residual ammonia gas is stripped and absorbed by sulfuric acid to generate ammonium sulfate, but the method has long process flow, needs to consume a large amount of magnesium salts and steam, has high treatment cost and is difficult to discharge the wastewater after reaching the standard; (3) the ammonia sulfate and the phosphorus ammonia fertilizer are generated by a membrane method and a multi-effect evaporation combined process, and the distilled water can be recycled, but the process is complex and the investment cost is high.
In the method adopted in the actual production, the first added medicament is more, the generated sludge amount is large, and the treatment cost is increased under the current environmental management; the second method requires consumption of large amount of magnesium salts and steam, increasing the operating cost; thirdly, the resource utilization of the wastewater is realized, but the process is complex and the investment cost is high.
SUMMERY OF THE UTILITY MODEL
The utility model provides a ferric phosphate wastewater treatment system, which is used for solving the defects of low resource recovery rate, emission pollution and high investment cost in ferric phosphate wastewater treatment in the prior art, respectively treating the wastewater according to the characteristics of ferric phosphate production wastewater, and recovering and utilizing substances such as ammonium sulfate, ammonium hydrogen phosphate, magnesium sulfate and the like, thereby achieving the purposes of resource recovery and zero emission.
The utility model provides a ferric phosphate wastewater treatment system, which comprises:
the first pretreatment device is used for pretreating the ferric phosphate mother liquor to obtain mother liquor clarified filtrate;
the second pretreatment device is used for pretreating the iron phosphate washing water to obtain concentrated water A;
the evaporation concentration device is respectively communicated with the first pretreatment device and the second pretreatment device and is used for carrying out evaporation concentration on the mother liquor clarified filtrate and the concentrated water A to obtain concentrated water B;
the centrifugal device is communicated with the evaporation concentration device and is used for centrifuging the concentrated water B;
the cooling crystallization device is communicated with the centrifugal device and is used for cooling and crystallizing the centrifuged product;
and the drying device is respectively communicated with the centrifugal device and the cooling crystallization device and is used for drying the products after centrifugation and cooling crystallization.
According to the iron phosphate wastewater treatment system provided by the utility model, the first pretreatment device comprises a first pH adjusting device and a first filtering device which are sequentially connected, the first pH adjusting device is provided with an ammonia water inlet, and the first filtering device is provided with a filter residue outlet.
According to the iron phosphate wastewater treatment system provided by the utility model, the second pretreatment device comprises a second pH adjusting device, a second filtering device, a cooling device and a reverse osmosis membrane concentration system which are sequentially connected, wherein the second pH adjusting device is provided with an ammonia water inlet, the second filtering device is provided with a filter residue outlet, and the reverse osmosis membrane concentration system is provided with a water outlet recovery port.
According to the iron phosphate wastewater treatment system provided by the utility model, a manganese sand filtering device is arranged between the reverse osmosis membrane concentration system and the cooling device.
According to the iron phosphate wastewater treatment system provided by the utility model, the evaporation concentration device is an MVR evaporation concentration device.
According to the iron phosphate wastewater treatment system provided by the utility model, the falling film concentration section of the evaporation concentration device is in a two-stage falling film series evaporation mode or a falling film and forced circulation mode.
The iron phosphate wastewater treatment system provided by the utility model further comprises a DTB flash evaporation cooling crystallization device, wherein the DTB flash evaporation cooling crystallization device is communicated with the MVR evaporation concentration device and is used for transferring part of concentrated solution in the MVR evaporation concentration device.
The ferric phosphate wastewater treatment system provided by the utility model further comprises a first return pipe, wherein the first return pipe is connected between the centrifugal device and the evaporation concentration device.
The iron phosphate wastewater treatment system provided by the utility model further comprises a second return pipe, and the second return pipe is connected between the cooling and crystallizing device and the evaporation and concentration device.
The iron phosphate wastewater treatment system provided by the utility model further comprises a third return pipe, and the third return pipe is connected between the evaporation concentration device and the reverse osmosis membrane concentration system.
According to the iron phosphate wastewater treatment system, two pretreatment devices are respectively utilized to respectively treat iron phosphate production wastewater according to characteristics of the iron phosphate production wastewater, then concentrated water subjected to evaporation concentration by an evaporation concentration device is centrifuged in a centrifugal device, cooled and crystallized in a cooling and crystallizing device, dried in a drying device and the like, so that ammonium sulfate, ammonium hydrogen phosphate, magnesium sulfate and pure water in the wastewater are recycled, and the purposes of resource recovery and zero emission are achieved.
Drawings
In order to more clearly illustrate the technical solutions of the present invention or the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic flow diagram of a method for treating iron phosphate wastewater provided by the utility model;
FIG. 2 is a schematic structural diagram of an iron phosphate wastewater treatment system provided by the utility model;
reference numerals:
1: a first pH adjusting device; 2: a first filtering device;
3: a second pH adjusting device; 4: a second filtering device;
5: a cooling device; 6: a reverse osmosis membrane concentration system;
7: an MVR evaporation and concentration device; 8: a centrifugal device;
9: cooling the crystallization device; 10: and (7) a drying device.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The method for treating iron phosphate wastewater according to the present invention will be described with reference to fig. 1. The processing method comprises the following steps:
s1, pretreating the iron phosphate mother liquor to obtain a mother liquor clear filtrate, and pretreating the iron phosphate washing water to obtain concentrated water A. The method mainly comprises the steps of respectively pretreating mother liquor and washing water in the iron phosphate production process, wherein the mother liquor is pretreated to obtain clear filtrate, the washing water is pretreated to be separated into concentrated water and fresh water, and the concentration of the concentrated water A is more than or equal to 12%.
And S2, mixing the mother liquor clear filtrate with the concentrated water A, and then evaporating and concentrating to obtain concentrated water B, wherein the concentration of the concentrated water B is 40-50%. The mixed evaporation concentration can be performed by other devices such as an MVR evaporation concentration device 7, reverse osmosis, a multi-effect evaporation system, electrodialysis and the like, but the reverse osmosis and the electrodialysis need to replace a cleaning membrane, and the steam cost of the multi-effect evaporation system is too high, so that the MVR evaporation concentration (hereinafter, abbreviated as MVR or MVR system) is the most economical and feasible scheme at present.
S3, cooling and crystallizing the concentrated water B by centrifugation to obtain a solid product and drying the solid product. Ammonium sulfate, ammonium hydrogen phosphate and magnesium sulfate products can be obtained through step S3.
Specifically, the step of pretreating the iron phosphate mother liquor in S1 to obtain a mother liquor clarified filtrate includes adjusting the pH value and filtering for multiple times, specifically:
s111, adding ammonia water to adjust the pH of the mother solution in the iron phosphate production process to 7-8 to obtain a mother solution;
and S112, filtering the mother solution for multiple times to obtain a mother solution clear filtrate.
The step of pretreating the ferric phosphate washing water in the S1 to obtain concentrated water A comprises the steps of adjusting the pH value, filtering for multiple times, cooling and concentrating, and specifically comprises the following steps:
s121, adding ammonia water to adjust the pH value of washing water in the iron phosphate production process to 7-8 to obtain a washing water solution;
s122, filtering the washing water solution for multiple times to obtain washing water clear filtrate;
and S123, cooling the clear washing water filtrate, and concentrating by using a reverse osmosis membrane concentration system 6 to obtain concentrated water A and fresh water A.
In one embodiment of the present invention, the step S112 and the step S122 include a plurality of filtering processes, specifically:
pumping the mother solution/washing water solution into a plate-and-frame filter press for filtering, and removing suspended matters in the solution to obtain first-stage solid residues and first-stage filtrate; adding phosphate into the primary filtrate, pumping into a plate-and-frame filter press again for filtering, and removing precipitates generated in the solution to obtain secondary solid residues and secondary filtrate; and pumping the secondary filtrate into a manganese sand filter, and further removing suspended matters in the solution to obtain mother liquor clear filtrate/washing water clear filtrate without suspended matters.
The step of S2 specifically includes:
s21, mixing the mother liquor clear filtrate and the concentrated water A, and introducing the mixture into an MVR evaporation and concentration device 7 to obtain concentrated water B and fresh water B;
and S22, mixing the obtained fresh water B with the cooled clear filtrate of the washing water, introducing the mixture into a reverse osmosis membrane concentration system 6 for concentration treatment, and recovering the obtained fresh water.
It can be understood that the concentrations of the concentrated water B and the fresh water B can be set according to actual reaction conditions, the concentration is only described by qualitative analysis, and the conductivity after concentration treatment by the reverse osmosis membrane concentration system 6 is less than or equal to 10 mus/cm and meets the standard of pure water.
The step of S3 specifically includes:
s31, centrifuging the concentrated water B to obtain a centrifugal mother liquor, and drying and separating part of the centrifugal mother liquor to obtain ammonium sulfate;
and S32, cooling and crystallizing partial centrifugal mother liquor to obtain a mixture of ammonium hydrogen phosphate and magnesium sulfate, and drying the mixture to obtain ammonium hydrogen phosphate and magnesium sulfate products.
Wherein, the concentrated water B is evaporated, concentrated, crystallized and separated to obtain magnesium sulfate at the temperature of 55-45 ℃; and cooling and crystallizing the centrifugal mother liquor at 40-42 ℃ to separate ammonium sulfate, and cooling and crystallizing at 25-28 ℃ to separate ammonium hydrogen phosphate.
Further comprising after the step of S3:
and S4, refluxing the residual centrifugal mother liquor and the cooled and crystallized mixture of ammonium hydrogen phosphate and magnesium sulfate to the MVR evaporation and concentration device 7 for continuous evaporation and concentration, thereby achieving the purposes of resource recovery and zero emission.
The method for treating the iron phosphate wastewater provided by the utility model has the following advantages:
1. according to different production sections of the ferric phosphate wastewater, the wastewater is respectively subjected to pretreatment such as alkalization pH adjustment, filtration and the like, so that the cost of wastewater treatment is reduced.
2. The pretreatment is simple and effective: the pH value is adjusted by adding ammonia water, so that new impurity ions cannot be introduced; meanwhile, the amount of slag is small, the filtering is convenient, and the labor intensity is low.
3. Concentrating the washing water by adopting high-pressure reverse osmosis: the concentrated water amount is less, and the concentration is more than or equal to 12 percent; and before the membrane concentration system, a precise filtration system, such as a manganese sand filtration system, an activated carbon filtration system and an ultrafiltration membrane filtration system, is arranged, so that the filtration precision is high, and the service life of the reverse osmosis system is ensured.
4. The pretreated washing water and the evaporated condensed water enter a reverse osmosis membrane system, so that the energy utilization efficiency can be improved, and the obtained produced water can reach the standard (less than or equal to 10 mu s/cm) of pure water recycling.
5. The problem of fluorine ion to equipment material corruption is solved: according to the content of the fluorine ions in the raw water, a fluorine ion capturing agent adding device is respectively arranged at the front end pretreatment section or the MVR system section, so that the system is ensured not to be corroded by the fluorine ions.
6. The problem of chloride ion to equipment material corruption is solved: according to the content of chloride ions in raw water, different materials such as 316L, 2205 and TA2 are selected by the MVR system in sections, so that the investment of customers is reduced while the system is not corroded by the chloride ions.
7. The MVR system falling film concentration section adopts two-stage falling film serial evaporation: steam generated by the first-effect falling film is used as heating steam of the second-effect falling film, the process combines the advantages of the traditional multiple-effect and MVR processes, theoretically, 2 tons of distilled water can be generated by 1 ton of heating steam, and the operation cost of the system is reduced.
8. The DTB flash evaporation cooling crystallization system is arranged: partial concentrated solution in the MVR system is transferred to a DTB flash evaporation cooling crystallization system, so that the problem of enrichment of ammonium hydrogen phosphate and magnesium sulfate in the MVR system is solved, the boiling point of the system is maintained within a certain range, and continuous and stable operation of the MVR system is guaranteed.
9. After the mother liquor passing through the MVR evaporation system is centrifuged, part of the centrifuged mother liquor and the cooled mother liquor can flow back to the MVR to be concentrated to obtain salt, substances such as magnesium sulfate, ammonium hydrogen phosphate and the like can be separated, the energy utilization efficiency is improved, and the resource utilization of the iron phosphate wastewater is realized.
As shown in fig. 2, the present invention also provides a treatment system using the iron phosphate wastewater treatment method of the above embodiment. The processing system comprises: a first pretreatment device, a second pretreatment device, an evaporation concentration device, a centrifugal device 8, a cooling crystallization device 9 and a drying device 10.
The first pretreatment device is used for pretreating the iron phosphate mother liquor to obtain mother liquor clarified filtrate; the second pretreatment device is used for pretreating the iron phosphate washing water to obtain concentrated water A; the evaporation concentration device is respectively communicated with the first pretreatment device and the second pretreatment device and is used for carrying out evaporation concentration on the mother liquor clarified filtrate and the concentrated water A to obtain concentrated water B; the centrifugal device 8 is communicated with the evaporation concentration device and is used for centrifuging the concentrated water B; the cooling crystallization device 9 is communicated with the centrifugal device 8 and is used for cooling and crystallizing the centrifuged product; the drying device 10 is respectively communicated with the centrifugal device 8 and the cooling crystallization device 9 and is used for drying the products after centrifugation and cooling crystallization.
In one embodiment of the utility model, the first pretreatment device comprises a first pH adjusting device 1 and a first filtering device 2 which are connected in sequence, the first pH adjusting device 1 is provided with an ammonia water inlet, and the first filtering device 2 is provided with a filter residue outlet; the second preprocessing device comprises a second pH adjusting device 3, a second filtering device 4, a cooling device 5 and a reverse osmosis membrane concentration system 6 which are sequentially connected, the second pH adjusting device 3 is provided with an ammonia water inlet, the second filtering device 4 is provided with a filter residue outlet, and the reverse osmosis membrane concentration system 6 is provided with a water outlet recovery port. Specifically, the first pH adjusting device 1 and the second pH adjusting device 3 both supplement ammonia water with corresponding ammonia water inlet like a solution, thereby adjusting the pH; and the pH value is adjusted by adding ammonia water, so that new impurity ions cannot be introduced; meanwhile, the amount of slag is small, the filtering is convenient, and the labor intensity is low. The filtering device is provided with a filter residue outlet for discharging the filtered filter residues such as ferric hydroxide and the like.
In one embodiment of the present invention, the evaporative concentration device is an MVR evaporative concentration device 7. It is understood that the concentration process can be realized by not only MVR equipment, but also other devices such as reverse osmosis, multi-effect evaporation systems, electrodialysis and the like, but the equipment has a plurality of problems in use, such as the reverse osmosis and the electrodialysis need to replace cleaning membranes, and the steam cost of the multi-effect evaporation systems, so that the MVR evaporation concentration is the most economic and feasible scheme at present.
In one embodiment of the utility model, a manganese sand filtering device is arranged between the reverse osmosis membrane concentration system 6 and the cooling device 5 and is used for removing specific ions in water. It is also possible to add precision filtration devices, such as: active carbon filter equipment or milipore filter equipment is through being equipped with the secondary filter system before the concentrated system of membrane, and the filter fineness is high, has improved reverse osmosis system's life. In this example, a precipitation device and a filtration device were provided to remove specific ions and to perform microfiltration on the solution to remove substances having a minute particle size.
In one embodiment of the utility model, the falling film concentration section of the evaporation concentration device is in a two-stage falling film serial evaporation mode or a falling film and forced circulation mode, and the corresponding evaporation mode is matched according to the quality of inlet water. For example: the two-stage falling film serial evaporation mode is adopted, steam generated by the first effect falling film is used as heating steam of the second effect falling film, the process combines the advantages of the traditional multiple effects and the MVR process, theoretically, 2 tons of distilled water can be generated by 1 ton of heating steam, and the operation cost of the system is reduced. It should be understood that a falling film + forced circulation form may be used instead of the above-described two-stage falling film series evaporation form, and the evaporation and concentration apparatus of the present invention is not limited to the above-described evaporation form.
In one embodiment of the utility model, the iron phosphate wastewater treatment system further comprises a DTB flash evaporation cooling crystallization device 9, and the DTB flash evaporation cooling crystallization device 9 is communicated with the MVR evaporation concentration device 7 and used for transferring part of the concentrated solution in the MVR evaporation concentration device 7. In this embodiment, transfer partial concentrate in the MVR system to DTB flash evaporation cooling crystallization system in to having solved the problem of ammonium hydrogen phosphate and the enrichment of magnesium sulfate in the MVR system, having maintained the boiling point of system in certain extent, having guaranteed the continuous steady operation of MVR system
In one embodiment of the present invention, the iron phosphate wastewater treatment system further comprises a first return pipe, wherein the first return pipe is connected between the centrifugal device 8 and the evaporation concentration device, and is used for returning the residual centrifugal mother liquor (underflow) generated by the centrifugal device 8 to the evaporation concentration device for further evaporation concentration, so as to achieve the purpose of zero emission.
In one embodiment of the present invention, the iron phosphate wastewater treatment system further includes a second return pipe, and the second return pipe is connected between the cooling crystallization device 9 and the evaporation concentration device, and is configured to return the residual mother liquor after cooling crystallization to the evaporation concentration device, so as to further perform evaporation concentration, and achieve the purpose of zero emission.
In one embodiment of the utility model, the iron phosphate wastewater treatment system further comprises a third return pipe, and the third return pipe is connected between the evaporative concentration device and the reverse osmosis membrane concentration system 6 and is used for recycling the fresh water B generated by the evaporative concentration device.
According to the iron phosphate wastewater treatment system provided by the utility model, two pretreatment devices are respectively utilized to respectively treat iron phosphate production wastewater according to the characteristics of the iron phosphate production wastewater, then concentrated water evaporated and concentrated by an evaporation concentration device is subjected to operations such as centrifugation in a centrifugal device 8, cooling crystallization in a cooling crystallization device 9, drying in a drying device 10 and the like, so that ammonium sulfate, ammonium hydrogen phosphate, magnesium sulfate and pure water in the wastewater are recycled, and the purposes of resource recovery and zero emission are achieved.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. An iron phosphate wastewater treatment system, comprising:
the first pretreatment device is used for pretreating the ferric phosphate mother liquor to obtain mother liquor clarified filtrate;
the second pretreatment device is used for pretreating the iron phosphate washing water to obtain concentrated water A;
the evaporation concentration device is respectively communicated with the first pretreatment device and the second pretreatment device and is used for carrying out evaporation concentration on the mother liquor clarified filtrate and the concentrated water A to obtain concentrated water B;
the centrifugal device is communicated with the evaporation concentration device and is used for centrifuging the concentrated water B;
the cooling crystallization device is communicated with the centrifugal device and is used for cooling and crystallizing the centrifuged product;
and the drying device is respectively communicated with the centrifugal device and the cooling crystallization device and is used for drying the products after centrifugation and cooling crystallization.
2. The iron phosphate wastewater treatment system according to claim 1, wherein the first pretreatment device comprises a first pH adjusting device and a first filtering device which are connected in sequence, the first pH adjusting device is provided with an ammonia water inlet, and the first filtering device is provided with a filter residue outlet.
3. The iron phosphate wastewater treatment system according to claim 1, wherein the second pretreatment device comprises a second pH adjusting device, a second filtering device, a cooling device and a reverse osmosis membrane concentration system which are connected in sequence, the second pH adjusting device is provided with an ammonia water inlet, the second filtering device is provided with a filter residue outlet, and the reverse osmosis membrane concentration system is provided with an effluent water recycling port.
4. The iron phosphate wastewater treatment system according to claim 3, wherein a manganese sand filtering device is arranged between the reverse osmosis membrane concentration system and the cooling device.
5. The iron phosphate wastewater treatment system of claim 1, wherein the evaporative concentration device is an MVR evaporative concentration device.
6. The iron phosphate wastewater treatment system according to claim 5, wherein the falling film concentration section of the evaporation concentration device is in a two-stage falling film serial evaporation mode or a falling film and forced circulation mode.
7. The iron phosphate wastewater treatment system according to claim 5, further comprising a DTB flash evaporation cooling crystallization device, wherein the DTB flash evaporation cooling crystallization device is communicated with the MVR evaporation concentration device and is used for transferring part of the concentrated solution in the MVR evaporation concentration device.
8. The iron phosphate wastewater treatment system according to claim 1, further comprising a first return pipe connected between the centrifugal device and the evaporative concentration device.
9. The iron phosphate wastewater treatment system according to claim 1, further comprising a second return pipe connected between the cooling crystallization device and the evaporative concentration device.
10. The iron phosphate wastewater treatment system according to claim 3, further comprising a third return pipe connected between the evaporative concentration device and the reverse osmosis membrane concentration system.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010309A (en) * | 2022-06-23 | 2022-09-06 | 武汉天元工程有限责任公司 | Iron phosphate wastewater zero-discharge treatment system and treatment process |
| CN115259516A (en) * | 2022-07-27 | 2022-11-01 | 武汉天元工程有限责任公司 | Iron phosphate wastewater zero-discharge treatment system and process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010309A (en) * | 2022-06-23 | 2022-09-06 | 武汉天元工程有限责任公司 | Iron phosphate wastewater zero-discharge treatment system and treatment process |
| CN115259516A (en) * | 2022-07-27 | 2022-11-01 | 武汉天元工程有限责任公司 | Iron phosphate wastewater zero-discharge treatment system and process |
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