CN114835325A - Iron phosphate mother liquor and rinsing water recycling treatment process thereof - Google Patents
Iron phosphate mother liquor and rinsing water recycling treatment process thereof Download PDFInfo
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- CN114835325A CN114835325A CN202210489063.2A CN202210489063A CN114835325A CN 114835325 A CN114835325 A CN 114835325A CN 202210489063 A CN202210489063 A CN 202210489063A CN 114835325 A CN114835325 A CN 114835325A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- 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
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a recycling treatment process for ferric phosphate mother liquor and rinsing water. The treatment process comprises the following steps: s1, carrying out plate exchange cooling treatment; s2, performing microfiltration; s3, ultrafiltration, clarification and filtration; s4, filtering by using a plate-and-frame filter press (recovering iron phosphate); s5, a reverse osmosis membrane concentration device I (ammonium sulfate recovery); s6, performing a reverse osmosis membrane concentration device II (pre-concentration treatment on the rinsing water); s7, and a reverse osmosis membrane concentration device III (a water quality purification system performs water quality purification). The invention reduces the pH adjusting process, reduces the acid-base consumption and controls the pollution risk of the metal ions separated out to the membrane. Particularly, aiming at the iron phosphate mother liquor and the washing water, the special reverse osmosis membrane is adopted to concentrate the dilute sulfuric acid and the sulfate on the premise of not carrying out acid-base regulation and sedimentation, metal ions are not separated out in the concentration process, the membrane concentration multiple is high, the evaporation water quantity is small, the acid-base consumption is low, the steam consumption is small, the comprehensive treatment cost is low, and the system operation is safe and reliable.
Description
Technical Field
The invention relates to wastewater treatment in the field of battery materials, in particular to a recycling treatment process for iron phosphate mother liquor and rinsing water thereof.
Background
With the rapid development of society, people are constantly updating energy development. The new energy batteries mainly comprise lithium ion batteries and ternary batteries, and the production and application of the lithium ion batteries and the ternary batteries are continuously explored. The key material iron phosphate for lithium ion battery production is the key to whether excellent lithium ion batteries can be manufactured. In the production process of the iron phosphate, the iron phosphate needs to be driven into a filter pressing plate frame for washing for three times, and the iron phosphate mother liquor and iron phosphate rinsing water are generated in the section, contain metal ions with different concentrations, sulfate ions and phosphate ions and contain acid-containing high-salt inorganic wastewater, are difficult to treat, and cause serious damage and influence on the surrounding environment due to the discharge of the wastewater.
At present, the mainstream treatment schemes for the wastewater generated in the iron phosphate production comprise a lime precipitation method, a magnesium salt treatment method and a traditional membrane treatment and evaporation combined method:
(1) the lime precipitation method has the advantages that more added agents are used, a large amount of sludge is generated and is difficult to treat, the treatment cost is increased, and high-salt water is not scientifically treated;
(2) magnesium salt treatment, 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 needs to consume a large amount of magnesium salts and steam, the treatment cost is high, and the wastewater is difficult to discharge after reaching the standard;
(3) by the traditional membrane method and the multi-effect evaporation combined process, the fertilizer containing the ammonium sulfate and the ammonium phosphate is generated, and meanwhile, distilled water can be recycled, so that the resource utilization of the wastewater is realized; but the pretreatment process is complex, the consumption of acid and alkali is large, the operation cost is high, the flow is long, the operation scaling risk of a membrane system is high, the occupied area is large, and the investment cost is high.
The applicant has found that the prior art has at least the following technical problems:
1. in the prior art, the treatment process of the ferric phosphate mother liquor and the rinsing water thereof has very high requirements on the control of pH, and if the adjustment fails, the normal operation of the treatment process is influenced, even the membrane element is damaged;
2. in the prior art, the treatment process of the ferric phosphate mother liquor and the rinsing water thereof has limited pH adjusting range in the mother liquor concentration stage, and has the risk of partial metal ion precipitation after concentration;
3. in the prior art, the treatment process of ferric phosphate mother liquor and rinsing water thereof has high medicament consumption, large evaporation water amount and high evaporation energy consumption, so that the comprehensive treatment cost is high, and the economic benefits of mother liquor and washing water treatment are not obvious.
Disclosure of Invention
The invention aims to provide a recycling treatment process for ferric phosphate mother liquor and rinsing water thereof, which comprehensively solves the problems of high cost, large occupied area of equipment and civil engineering and low economic benefit of resource recovery in the prior art for mother liquor and rinsing water treatment.
Aiming at the ferric phosphate mother liquor and the washing water, the special reverse osmosis membrane is adopted to concentrate the dilute sulfuric acid and the sulfate on the premise of not carrying out acid-base regulation and sedimentation, metal ions are not separated out in the concentration process, the membrane concentration multiple is high, the evaporated water quantity is small, the acid-base consumption is low, the steam consumption is small, the comprehensive treatment cost is low, and the system operation is safe and reliable.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a recycling treatment process for iron phosphate mother liquor and rinsing water thereof, which comprises the following steps:
s1, cooling the ferric phosphate mother liquor and the ferric phosphate rinsing water to 20-40 ℃ through a first plate heat exchanger and a second plate heat exchanger respectively to obtain a cooling mother liquor and a cooling washing water respectively;
s2, filtering the mother liquor obtained in the step S1 through a first microporous filter to obtain a first microporous filtering concentrated phase and a first microporous filtering filtered phase; filtering the rinsing water of S1 by a microporous filter II to obtain a microporous filtering concentrated phase II and a microporous filtering filtered phase II;
s3, carrying out ultrafiltration clarification on the clear phase I obtained in the step S2 through a first ultrafiltration device to obtain an ultrafiltration first filtered phase and an ultrafiltration first concentrated phase; ultrafiltering the clear phase two obtained in the step S2 by an ultrafiltration device II to obtain an ultrafiltration phase II and an ultrafiltration concentrated phase II;
s4, mixing the microfiltration concentrated phase I and the microfiltration concentrated phase II obtained in the step S2 with the ultrafiltration concentrated phase I and the ultrafiltration concentrated phase II obtained in the step S3, and then performing plate-and-frame filtration through a plate-and-frame filter press I to recover the iron phosphate;
s5, concentrating the first ultrafiltration clear phase obtained in the step S3 by a first reverse osmosis membrane concentration device to obtain a first reverse osmosis concentrated phase and a first reverse osmosis clear phase, and sequentially performing neutralization and precipitation on the first reverse osmosis concentrated phase and performing plate-and-frame clarification and filtration on a second plate-and-frame filter press; filtering by a plate-and-frame filter press II to obtain liquid, and evaporating and crystallizing by MVR to obtain an ammonium sulfate product; solid waste obtained by filtering through the plate-and-frame filter press II is used as a building material;
s6, mixing the reverse osmosis clear phase I obtained in the step S5 with the ultrafiltration clear phase II obtained in the step S3, concentrating the mixture by a reverse osmosis membrane concentration device II to obtain a reverse osmosis concentrated phase II and a reverse osmosis clear phase II, and returning the obtained reverse osmosis concentrated phase II to the front reverse osmosis membrane concentration device I for continuous concentration treatment;
s7, adjusting the pH value of the reverse osmosis clear phase II obtained in the step S6 to 5.5-6, and purifying the water through a reverse osmosis membrane concentration device III to obtain a reverse osmosis concentrated phase III and a reverse osmosis clear phase III; and returning the reverse osmosis concentrated phase III to the reverse osmosis membrane concentration device II for continuous concentration, wherein the conductivity of the reverse osmosis clear phase III is less than 20us/cm, and reusing the reverse osmosis clear phase III for production.
Further, in the step S2, the first microporous filter and the second microporous filter are both filtered by polymer filter elements, and the filtering flux is 200- 2 H; the operation flow rate of the first microporous filter and the second microporous filter is as low as 1m/s, and the operation pressure is 0.1-0.3 Mpa; the obtained first microporous filtering phase and the second microporous filtering phase both meet the turbidity of less than 10 NTU.
Furthermore, in the step S3, the cut-off molecular weights of the ultrafiltration membrane filter elements used in the first ultrafiltration device and the second ultrafiltration device are both 10KD to 300 KD.
Further, in the step S3, when the first ultrafiltration device and the second ultrafiltration device perform ultrafiltration, the operating pressure is 0.1 to 0.3Mpa, and the operating temperature is 20 to 40 ℃; the obtained ultrafiltration clear phase I and ultrafiltration clear phase II both meet the turbidity of 0.1-1 NTU.
Further, in the step S5, when the reverse osmosis membrane concentration device i performs concentration treatment, the operation pressure is 0.5Mpa-12Mpa, and the operation temperature is 20 ℃ to 40 ℃; TDS in the obtained reverse osmosis concentrated phase I reaches 150-220g/L, and TDS in the obtained reverse osmosis clear phase I is 2-5 g/L.
Further, in the step S5, the operating PH of the first reverse osmosis membrane concentration device may be in a variable range of 0.3 to 3.
Further, in the step S6, when the reverse osmosis membrane concentration device two is used for concentration treatment, the operation pressure is 0.5Mpa-8Mpa, and the operation temperature is 20 ℃ to 40 ℃; TDS in the obtained reverse osmosis concentrated phase II reaches 60-120g/L, and TDS in the obtained reverse osmosis clear phase II is 0.1-0.5 g/L.
Further, in the step S7, when the reverse osmosis membrane concentration device three is used for concentration and purification, the operation pressure is 0.5Mpa-4Mpa, and the operation temperature is 20-40 ℃; TDS in the obtained reverse osmosis concentrated phase III is 1.1-3.5g/L, and TDS in the obtained reverse osmosis clear phase III is 0.005-0.01 g/L.
Further, in the step S7, when the reverse osmosis clear phase two is concentrated by the reverse osmosis membrane concentration device three, the pH of the reverse osmosis clear phase two is adjusted by adding ammonia water or sodium hydroxide according to the iron phosphate production system and the final sulfate product.
Furthermore, the first reverse osmosis membrane concentration device and the second reverse osmosis membrane concentration device both adopt acid-resistant high-pressure reverse osmosis membrane elements which are connected with fluid, and the third reverse osmosis membrane concentration device adopts a high-interception reverse osmosis membrane which is connected with fluid.
Based on the technical scheme, the embodiment of the invention can at least produce the following technical effects:
(1) according to the iron phosphate mother liquor and the rinsing water recycling treatment process thereof, the PH regulation is not carried out at the working section of iron phosphate recovery and before the reverse osmosis membrane concentration device II, and the consumption of ammonia water or sodium hydroxide is small in the whole process; and (3) only carrying out reverse osmosis concentrated phase-metal sedimentation treatment in the step S5 and adjusting a small amount of ammonia water before water quality purification in the reverse osmosis membrane concentration device III in the step S7 to ensure that the effluent index is stable and the conductivity meets the project requirements.
(2) According to the iron phosphate mother liquor and the rinsing water recycling treatment process thereof, the pH value of an ultrafiltration clear phase obtained from the iron phosphate mother liquor is reduced to 0.6 from 1.2 of a feed liquor after the ultrafiltration clear phase is concentrated by a reverse osmosis membrane concentration device I, acids and salts in the iron phosphate mother liquor are synchronously concentrated in the process, the acidity is improved, no precipitation is ensured after concentration, and the process is safer and more reliable.
(3) According to the iron phosphate mother solution and rinse water recycling treatment process provided by the invention, a continuous overflow membrane process is combined with a special high-pollution-resistance acid-resistant membrane, so that the concentration and recovery of residual acid and salt in the iron phosphate mother solution and the iron phosphate rinse water are realized, the salt concentration of a concentrated solution (reverse osmosis concentrated phase I) can reach 150-220g/l, the membrane dehydration amount is large, and the energy consumption and equipment investment of rear-stage MVR evaporation crystallization dehydration are reduced;
(4) according to the iron phosphate mother liquor and the rinsing water recycling treatment process thereof, iron phosphate is recovered in step S4; in step S5, sulfate, evaporative condensate from evaporative crystallization, and solid waste applicable as a construction material are recovered; obtaining a reverse osmosis clear phase III which can be recycled and produced in step S7; in addition, the corresponding process of the invention only adds medicine twice; from the view of operating cost consumption, the cost of removing 1 ton of water by the traditional evaporation process is 20-30 yuan, and the cost of removing 1 ton of water by the membrane concentration of the invention is 3-5 yuan; compared with the treatment process in the prior art, the invention has lower consumption cost and obvious project economic benefit.
(5) The iron phosphate mother liquor and the rinsing water recycling treatment process thereof provided by the invention have the advantages that the applied treatment equipment is high in integration, small in equipment volume and small in occupied area, and can exert greater energy efficiency in a limited space.
(6) According to the iron phosphate mother liquor and rinsing water recycling treatment process provided by the invention, the iron phosphate mother liquor and rinsing water thereof are subjected to graded treatment through a combined process of microfiltration, plate-and-frame filter press, acid-resistant ultrafiltration and multi-stage high-pollution-resistance reverse osmosis membrane concentration filtration, so that concentration and filtration of all stages of reverse osmosis membranes are protected from being influenced by solid particles, continuous and stable production of multi-stage membrane systems is realized, the overall production running cost is low, the resource recovery rate is high, wastewater is recycled, and zero discharge of projects is realized.
Detailed Description
Firstly, equipment description:
a first microporous filter and a second microporous filter: filtering by adopting a high-molecular polymerization filter element; the filtration flux is 200-1000L/m 2 H; the operation flow rate of the first microporous filter and the second microporous filter is as low as 1m/s, and the operation pressure is 0.1-0.3Mpa
A first ultrafiltration device and a second ultrafiltration device: all the components are connected with an acid-resistant ultrafiltration membrane filter element provided by fluid separation technology Limited, the model of the membrane is LJ6T-UF9050, the cut-off molecular weight is 10KD-300KD, the operating pressure is 0-0.3MPa, the operating temperature is 0-50 ℃, and the pH is 0-11;
the first reverse osmosis membrane concentration device and the second reverse osmosis membrane concentration device adopt an acid-resistant high-pressure reverse osmosis membrane which is connected with fluid separation technology company Limited, and the model is as follows: LJ 6T-RO58040F35, 1800psi; the reverse osmosis membrane concentration device III adopts a reverse osmosis membrane element with high desalination rate which is connected with the fluid separation technology company Limited.
Second, embodiment:
example 1:
a recycling treatment process for iron phosphate mother liquor and rinsing water thereof comprises the following steps:
s1, cooling the ferric phosphate mother liquor and the ferric phosphate washing water to 40 ℃ through a first plate heat exchanger and a second plate heat exchanger respectively to obtain a cooling mother liquor and a cooling washing water respectively;
s2, filtering the S1 ferric phosphate mother liquor through a first microporous filter to obtain a first microporous filtering concentrated phase, a first microporous filtering filtered phase and a first microporous filtering slag liquid; filtering the S1 ferric phosphate rinsing water through a microporous filter II to obtain a microporous filtration concentrated phase II, a microporous filtration filtering phase II and a microporous filtration residue liquid II; the obtained first microporous filtering phase and the second microporous filtering phase both meet the turbidity less than 10 NTU;
the first microporous filter and the second microporous filter are both filtered by polymer filter elements, and the filtering flux is respectively 500L/m 2 H and 800L/m 2 H; the operation flow rate of the first microporous filter and the second microporous filter is as low as 1m/s, and the operation pressure is 0.2 Mpa;
s3, carrying out ultrafiltration clarification on the cooled clear phase I obtained in the step S2 through an ultrafiltration device I, wherein the molecular weight cut-off of an ultrafiltration membrane filter element adopted in the ultrafiltration device I is 200KD, and when the ultrafiltration device I carries out ultrafiltration, the operating pressure is 0.2Mpa, the operating temperature is 40 ℃, so that an ultrafiltration filtration phase I and an ultrafiltration concentrated phase I are obtained; carrying out ultrafiltration clarification on the cooled clear phase two obtained in the step S2 through an ultrafiltration device II, wherein the cut-off molecular weight of an ultrafiltration membrane filter element adopted in the ultrafiltration device II is 200KD, and the operating pressure and the operating temperature of the ultrafiltration device II are 0.2Mpa and 40 ℃ respectively when the ultrafiltration device II carries out ultrafiltration, so as to obtain an ultrafiltration clear phase two and an ultrafiltration concentrated phase two; obtaining an ultrafiltration clear phase I and an ultrafiltration clear phase II, wherein the turbidity is less than 1 NTU;
s4, mixing the microporous filtration concentrated phase I and the microporous filtration concentrated phase II obtained in the step S2 with the ultrafiltration concentrated phase I and the ultrafiltration concentrated phase II obtained in the step S3 to obtain iron phosphate slag liquid, and performing plate-and-frame filtration on the iron phosphate slag liquid through a plate-and-frame filter press, wherein the solid phase is recyclable iron phosphate, the effluent is clear water, and the effluent can continuously return to the step S2 to enter the microporous filter I for filtration;
s5, concentrating the first ultrafiltration clear phase obtained in the step S3 by a first reverse osmosis membrane concentration device, wherein when the first reverse osmosis membrane concentration device is used for concentrating, the change trend of the operating pH is 1.0-0.6, the trend of the operating pressure is 0.5-10.5 MPa, and the operating temperature is 40-42 ℃, so that a first reverse osmosis concentrated phase and a first reverse osmosis clear phase are obtained; the first reverse osmosis concentrated phase is mainly sulfate, partial impurities, redundant sulfuric acid and phosphoric acid, ammonia water neutralization and precipitation are sequentially carried out on the obtained first reverse osmosis concentrated phase, and clarification and filtration are carried out on a plate-and-frame filter press; filtering by the plate and frame filter press II to obtain liquid which is ammonium sulfate solution, evaporating and crystallizing by MVR to obtain an ammonium sulfate product and recyclable evaporation condensate water, and using solid waste obtained by filtering by the plate and frame filter press II as a building material;
s6, mixing the reverse osmosis clear phase I obtained in the step S5 with the ultrafiltration clear phase II obtained in the step S3, and concentrating by using a reverse osmosis membrane concentration device II, wherein when the reverse osmosis membrane concentration device II is used for concentrating, the operating pressure growth trend is 0.5-6.5Mpa, and the operating temperature is 40 ℃, so that a reverse osmosis concentrated phase II and a reverse osmosis clear phase II are obtained; returning the obtained reverse osmosis concentrated phase II to a front reverse osmosis membrane concentration device I for continuous concentration;
s7, firstly adjusting the pH value of the reverse osmosis clear phase II obtained in the step S6 to 5 by ammonia water, and then concentrating and purifying by a reverse osmosis membrane concentration device III, wherein when the reverse osmosis membrane concentration device III is used for concentrating and purifying, the operating pressure growth trend is 0.5-3.5Mpa, and the operating temperature is 40 ℃, so that a reverse osmosis concentrated phase III and a reverse osmosis clear phase III are obtained; and returning the reverse osmosis concentrated phase III to the reverse osmosis membrane concentration device II for continuous concentration, and recycling the reverse osmosis clear phase III for production, wherein the conductivity of the reverse osmosis clear phase III is 12 us/cm.
The treatment process in this example is shown in table 1 below:
TABLE 1 iron phosphate mother liquor and rinsing water recycling process in example 1
As can be seen from Table 1, in this example, there are two water inlets, one concentrate outlet, one purified water outlet, and one iron phosphate recovery port; the total amount of inlet water (ferric phosphate mother liquor and ferric phosphate rinsing water) is 135m 3 H, water outlet: the first reverse osmosis concentrated phase is 15.2m 3 The third reverse osmosis clear phase is 119.8m 3 The water yield was 88.7%.
Example 2:
a recycling treatment process for iron phosphate mother liquor and rinsing water thereof comprises the following steps:
s1, cooling the ferric phosphate mother liquor and the washing water to 38 ℃ through the plate heat exchanger I and the plate heat exchanger II respectively to obtain the cooled ferric phosphate mother liquor and the cooled ferric phosphate washing water respectively;
s2, filtering the S1 mother liquor through a first microporous filter to obtain a first microporous filtering concentrated phase, a first microporous filtering filtered phase and a first microporous filtering slag liquid; filtering the rinsing water of S1 by a microporous filter II to obtain a microporous filtration concentrated phase II, a microporous filtration filtering phase II and a microporous filtration residue liquid II; the obtained first microporous filtering phase and the second microporous filtering phase both meet the turbidity less than 10 NTU;
the first microporous filter and the second microporous filter are both filtered by polymer filter elements, and the filtering flux is respectively 200L/m 2 H and 300L/m 2 H; the operation flow rate of the first microporous filter and the second microporous filter is as low as 1m/s, and the operation pressure is 0.1 Mpa;
s3, performing ultrafiltration clarification on the clear phase I obtained in the step S2 through a first ultrafiltration device, wherein the molecular weight cut-off of an ultrafiltration membrane filter element adopted in the first ultrafiltration device is 300KD, and when the first ultrafiltration device performs ultrafiltration, the operation pressure is 0.3Mpa, the operation temperature is 38 ℃, so that an ultrafiltration filtration phase I and an ultrafiltration concentrated phase I are obtained; carrying out ultrafiltration clarification on the cooled clear phase two obtained in the step S2 through an ultrafiltration device II, wherein the molecular weight cut-off of an ultrafiltration membrane filter element adopted in the ultrafiltration device II is 300KD, and the operating pressure and the operating temperature of the ultrafiltration device II are respectively 0.3Mpa and 38 ℃ when the ultrafiltration device II carries out ultrafiltration, so that an ultrafiltration clear phase two and an ultrafiltration concentrated phase two are obtained; the obtained ultrafiltration clear phase I and ultrafiltration clear phase II both meet the turbidity less than 1 NTU;
s4, mixing the microporous filtration concentrated phase I and the microporous filtration concentrated phase II obtained in the step S2 with the ultrafiltration concentrated phase I and the ultrafiltration concentrated phase II obtained in the step S3 to obtain iron phosphate slag liquid, and performing plate-and-frame filtration on the iron phosphate slag liquid through a plate-and-frame filter press, wherein the solid phase is recyclable iron phosphate, the effluent is clear water, and the effluent can continuously return to the step S2 to enter the microporous filter I for filtration;
s5, concentrating the clear ultrafiltration phase I obtained in the step S3 by a reverse osmosis membrane concentration device I, wherein when the reverse osmosis membrane concentration device I is used for concentrating, the change trend of the operating pH is 1.1-0.7, the operating pressure trend is 0.5-9Mpa, and the operating temperature is 40 ℃, so that a reverse osmosis concentrated phase I and a reverse osmosis clear phase I are obtained; the first reverse osmosis concentrated phase is mainly sulfate, partial impurities, redundant sulfuric acid and phosphoric acid, ammonia water neutralization and precipitation are sequentially carried out on the obtained first reverse osmosis concentrated phase, and clarification and filtration are carried out on the obtained first reverse osmosis concentrated phase by a plate-and-frame filter press; filtering by the plate and frame filter press II to obtain liquid which is ammonium sulfate solution, evaporating and crystallizing by MVR to obtain sulfate products and recyclable evaporation condensed water, and using solid waste obtained by filtering by the plate and frame filter press II as a building material;
s6, mixing the reverse osmosis clear phase I obtained in the step S5 with the ultrafiltration clear phase II obtained in the step S3, and concentrating by using a reverse osmosis membrane concentration device II, wherein when the reverse osmosis membrane concentration device II is used for concentrating, the operation pressure trend is 0.5-5Mpa, the operation temperature is 38 ℃, and a reverse osmosis concentrated phase II and a reverse osmosis clear phase II are obtained; returning the obtained reverse osmosis concentrated phase II to a front reverse osmosis membrane concentration device I for continuous concentration;
s7, firstly, adjusting the pH value of the reverse osmosis clear phase II obtained in the step S6 to 5.8 by ammonia water, and then, concentrating and purifying by a reverse osmosis membrane concentration device III, wherein when the reverse osmosis membrane concentration device III is used for concentrating and purifying, the operation pressure change trend is 0.5-3Mpa, the operation temperature is 38-40 ℃, and a reverse osmosis concentrated phase III and a reverse osmosis clear phase III are obtained; and returning the reverse osmosis concentrated phase III to the reverse osmosis membrane concentration device II for continuous concentration, and recycling the reverse osmosis clear phase III for production, wherein the conductivity of the reverse osmosis clear phase III is 15 us/cm.
The treatment process in this example is shown in table 2 below:
table 2 iron phosphate mother liquor and rinsing water recycling process in example 2
As can be seen from Table 2, in this example, there are two water inlets, one concentrate outlet, one purified water outlet, and one iron phosphate recovery port; the total amount of inlet water (ferric phosphate mother liquor and ferric phosphate rinsing water) is 136m 3 H, water outlet: the first reverse osmosis concentrated phase is 18.7m 3 The third reverse osmosis clear phase is 117.3m 3 The water yield was 86.25%.
Example 3:
a recycling treatment process for iron phosphate mother liquor and rinsing water thereof comprises the following steps:
s1, cooling the ferric phosphate mother liquor and the washing water to 20 ℃ through the first plate heat exchanger and the second plate heat exchanger respectively to obtain the cooled ferric phosphate mother liquor and the cooled ferric phosphate rinsing water respectively;
s2, filtering the S1 mother liquor through a first microporous filter to obtain a first microporous filtering concentrated phase, a first microporous filtering filtered phase and a first microporous filtering slag liquid; filtering the rinsing water of S1 by a microporous filter II to obtain a microporous filtration concentrated phase II, a microporous filtration filtering phase II and a microporous filtration residue liquid II; the obtained first microporous filtering phase and the second microporous filtering phase both meet the turbidity less than 10 NTU;
the first microporous filter and the second microporous filter are both filtered by polymer filter elements, and the filtering flux is 700L/m 2 H and 1000L/m 2 H; the operation flow rate of the first microporous filter and the second microporous filter is as low as 1m/s, and the operation pressure is 0.3 Mpa;
s3, carrying out ultrafiltration clarification on the cooled clear phase I obtained in the step S2 through an ultrafiltration device I, wherein the molecular weight cut-off of an ultrafiltration membrane filter element adopted in the ultrafiltration device I is 50KD, and when the ultrafiltration device I carries out ultrafiltration, the operation pressure is 0.1Mpa, the operation temperature is 20 ℃, so that an ultrafiltration filtration phase I and an ultrafiltration concentrated phase I are obtained; carrying out ultrafiltration clarification on the cooled clear phase two obtained in the step S2 through an ultrafiltration device II, wherein the molecular weight cut-off of an ultrafiltration membrane filter element adopted in the ultrafiltration device II is 50KD, and the operating pressure and the operating temperature of the ultrafiltration device II are 0.1MPa and 20 ℃ respectively when the ultrafiltration device II carries out ultrafiltration, so as to obtain an ultrafiltration clear phase two and an ultrafiltration concentrated phase two; the obtained ultrafiltration clear phase I and ultrafiltration clear phase II both meet the turbidity less than 1 NTU;
s4, mixing the microporous filtration concentrated phase I and the microporous filtration concentrated phase II obtained in the step S2 with the ultrafiltration concentrated phase I and the ultrafiltration concentrated phase II obtained in the step S3 to obtain iron phosphate slag liquid, and performing plate-and-frame filtration on the iron phosphate slag liquid through a plate-and-frame filter press, wherein the solid phase is recyclable iron phosphate, the effluent is clear water, and the effluent can continuously return to the step S2 to enter the microporous filter I for filtration;
s5, concentrating the first ultrafiltration clear phase obtained in the step S3 by a first reverse osmosis membrane concentration device, wherein when the first reverse osmosis membrane concentration device is used for concentrating, the variation trend of the operating pH is 1.2-0.8, the variation trend of the operating pressure is 0.5-12.0Mpa, and the variation trend of the operating temperature is 20-23 ℃, so that a first reverse osmosis concentrated phase and a first reverse osmosis clear phase are obtained; the first reverse osmosis concentrated phase is mainly sulfate, partial impurities, redundant sulfuric acid and phosphoric acid, ammonia water neutralization and precipitation are sequentially carried out on the obtained first reverse osmosis concentrated phase, and clarification and filtration are carried out on a plate-and-frame filter press; filtering by the plate and frame filter press II to obtain liquid which is ammonium sulfate solution, evaporating and crystallizing by MVR to obtain an ammonium sulfate product and recyclable evaporation condensate water, and using solid waste obtained by filtering by the plate and frame filter press II as a building material;
s6, mixing the reverse osmosis clear phase I obtained in the step S5 with the ultrafiltration clear phase II obtained in the step S3, and concentrating by using a reverse osmosis membrane concentration device II, wherein when the reverse osmosis membrane concentration device II is used for concentrating, the operation pressure change trend is 0.5-6.0Mpa, the operation temperature is 20 ℃, so that a reverse osmosis concentrated phase II and a reverse osmosis clear phase II are obtained; returning the obtained reverse osmosis concentrated phase II to a front reverse osmosis membrane concentration device I for continuous concentration;
s7, firstly, adjusting the pH value of the reverse osmosis clear phase II obtained in the step S6 to 6 by ammonia water, and then, concentrating and purifying by a reverse osmosis membrane concentration device III, wherein when the reverse osmosis membrane concentration device III is used for concentrating and purifying, the change trend of the operating pressure is 0.5-4.0Mpa, the operating temperature is 20 ℃, and a reverse osmosis concentrated phase III and a reverse osmosis clear phase III are obtained; and returning the reverse osmosis concentrated phase III to the reverse osmosis membrane concentration device II for continuous concentration, and recycling the reverse osmosis clear phase III for production, wherein the conductivity of the reverse osmosis clear phase III is 20 us/cm.
The treatment process in this example is shown in table 3 below:
TABLE 3 iron phosphate mother liquor and rinsing water recycling process in example 3
As can be seen from Table 3, there are two water inlets, one concentrate outlet, one purified water outlet, and one iron phosphate recovery port in this embodiment; the total amount of inlet water (ferric phosphate mother liquor and ferric phosphate rinsing water) is 136m 3 H, water outlet: the first reverse osmosis concentrated phase is 15.5m 3 Per hour, reverse osmosis phase III is 120.5m 3 The water yield was 88.6%.
Claims (10)
1. The iron phosphate mother liquor and the rinsing water recycling treatment process thereof are characterized by comprising the following steps:
s1, cooling the mother liquor and the washing water to 20-40 ℃ through a first plate heat exchanger and a second plate heat exchanger respectively to obtain the mother liquor and the washing water at target temperatures respectively;
s2, filtering the ferric phosphate mother liquor obtained in the step S1 through a first microporous filter to obtain a first microporous filtering concentrated phase and a first microporous filtering filtered phase; filtering the cooled ferric phosphate rinsing water through a microporous filter II to obtain a microporous filtering concentrated phase II and a microporous filtering filtered phase II;
s3, carrying out ultrafiltration clarification on the clear phase I obtained in the step S2 through a first ultrafiltration device to obtain an ultrafiltration first filtered phase and an ultrafiltration first concentrated phase; ultrafiltering the clear phase two obtained in the step S2 by an ultrafiltration device II to obtain an ultrafiltration phase II and an ultrafiltration concentrated phase II;
s4, mixing the microfiltration concentrated phase I and the microfiltration concentrated phase II obtained in the step S2 with the ultrafiltration concentrated phase I and the ultrafiltration concentrated phase II obtained in the step S3, and then performing plate-and-frame filtration through a plate-and-frame filter press I to recover the iron phosphate;
s5, concentrating the first ultrafiltration clear phase obtained in the step S3 by a first reverse osmosis membrane concentration device to obtain a first reverse osmosis concentrated phase and a first reverse osmosis clear phase, and sequentially performing neutralization and precipitation on the first reverse osmosis concentrated phase and performing plate-and-frame clarification and filtration on a second plate-and-frame filter press; filtering by a plate-and-frame filter press II to obtain liquid, and evaporating and crystallizing by MVR to obtain an ammonium sulfate product; solid waste obtained by filtering with the plate-and-frame filter press II is used as a building material;
s6, mixing the reverse osmosis clear phase I obtained in the step S5 with the ultrafiltration clear phase II obtained in the step S3, concentrating the mixture by a reverse osmosis membrane concentration device II to obtain a reverse osmosis concentrated phase II and a reverse osmosis clear phase II, and returning the obtained reverse osmosis concentrated phase II to the front reverse osmosis membrane concentration device I for continuous concentration treatment;
s7, adjusting the pH value of the reverse osmosis clear phase II obtained in the step S6 to 5.5-6, and purifying the water through a reverse osmosis membrane concentration device III to obtain a reverse osmosis concentrated phase III and a reverse osmosis clear phase III; and returning the reverse osmosis concentrated phase III to the reverse osmosis membrane concentration device II for continuous concentration, wherein the conductivity of the reverse osmosis clear phase III is less than 20us/cm, and reusing the reverse osmosis clear phase III for production.
2. The iron phosphate mother liquor and rinsing water recycling process thereof as claimed in claim 1, wherein in step S2, the first microporous filter and the second microporous filter are both filtered by polymer filter elements, and the filtering flux is 200-1000L/square meter h; the operation flow rate of the first microporous filter and the second microporous filter is as low as 1m/s, and the operation pressure is 0.1-0.3 Mpa; the obtained first microporous filtering phase and the second microporous filtering phase both meet the turbidity of less than 10 NTU.
3. The iron phosphate mother liquor and rinsing water recycling process thereof according to claim 1, wherein in step S3, the cut-off molecular weights of ultrafiltration membrane filter elements adopted in the first ultrafiltration device and the second ultrafiltration device are both 10KD to 300 KD.
4. The iron phosphate mother liquor and rinsing water recycling treatment process thereof according to claim 1, wherein in the step S3, when the first ultrafiltration device and the second ultrafiltration device are used for ultrafiltration, the operation pressure is 0.1-0.3Mpa, and the operation temperature is 20-40 ℃; the obtained ultrafiltration clear phase I and ultrafiltration clear phase II both meet the turbidity of 0.1-1 NTU.
5. The iron phosphate mother liquor and rinsing water recycling process thereof according to claim 1, wherein in the step S5, when a reverse osmosis membrane concentration device performs concentration treatment, the operation pressure is 0.5Mpa-12Mpa, and the operation temperature is 20-40 ℃; TDS in the obtained reverse osmosis concentrated phase I reaches 150-220g/L, and TDS in the obtained reverse osmosis clear phase I is 2-5 g/L.
6. The iron phosphate mother liquor and rinsing water recycling process thereof according to claim 1, wherein in step S5, the operating PH of the first reverse osmosis membrane concentration device varies from 0.3 to 3.
7. The iron phosphate mother liquor and rinsing water recycling treatment process thereof according to claim 1, wherein in the step S6, when a reverse osmosis membrane concentration device two performs concentration treatment, the operation pressure is 0.5Mpa-8Mpa, and the operation temperature is 20-40 ℃; TDS in the obtained reverse osmosis concentrated phase II reaches 60-120g/L, and TDS in the obtained reverse osmosis clear phase II is 0.1-0.5 g/L.
8. The iron phosphate mother liquor and rinsing water recycling treatment process thereof according to claim 1, wherein in the step S7, when a reverse osmosis membrane concentration device three performs concentration and purification, the operation pressure is 0.5Mpa-4Mpa, and the operation temperature is 20-40 ℃; TDS in the obtained reverse osmosis concentrated phase III is 1.1-3.5g/L, and TDS in the obtained reverse osmosis clear phase III is 0.005-0.01 g/L.
9. The iron phosphate mother liquor and rinsing water recycling treatment process thereof according to claim 1, wherein in the step S7, when the reverse osmosis clear phase two is concentrated by the reverse osmosis membrane concentration device three, the pH of the reverse osmosis clear phase two is adjusted by ammonia water.
10. The iron phosphate mother liquor and rinsing water recycling treatment process thereof according to claim 1, wherein the first reverse osmosis membrane concentration device and the second reverse osmosis membrane concentration device both employ acid-resistant high-pressure reverse osmosis membrane elements provided by connecting all of them with a fluid, and the third reverse osmosis membrane concentration device employs a high-interception reverse osmosis membrane provided by connecting all of them with a fluid.
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