CN111252978A - Method for recovering high-purity sodium sulfate in regenerated lead waste liquid - Google Patents
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Abstract
The invention discloses a method for recovering high-purity sodium sulfate in regenerated lead waste liquid, which comprises the following steps of 1) adding alkali into the regenerated lead waste liquid subjected to primary impurity removal, precipitation and filtration treatment to adjust the pH value; 2) introducing the waste liquid into an aeration tank, and adding an iron-containing catalyst for catalytic oxidation aeration; 3) adding soda into the waste liquid to adjust the pH value, fully stirring, and standing for precipitation; 4) treating with ultrafiltration membrane; 5) softening and impurity removing treatment is carried out through cation resin; 6) concentrating the cation resin treatment liquid through a nanofiltration membrane; 7) carrying out low-temperature freezing crystallization on the nanofiltration concentrated solution to obtain sodium sulfate decahydrate crystals, and dissolving the sodium sulfate decahydrate crystals by adopting pure water to prepare saturated solution; 8) carrying out reduced pressure evaporation crystallization to obtain anhydrous sodium sulfate crystals; 9) and washing the sodium sulfate crystal with clear water. The method can simultaneously meet the requirements of wastewater recycling and salt product recycling, and has low operation cost and high purity of the recycled solid product.
Description
Technical Field
The invention belongs to the technical field of environmental engineering, and particularly relates to a method for recovering high-purity sodium sulfate in secondary lead waste liquid.
Background
The waste water produced in the production process of the regenerated lead smelting enterprise taking waste lead storage batteries and the like as raw materials mainly comprises the waste water of disassembly, the waste water of sodium-alkali desulphurization and the waste flushingThe water and the pure water are used for preparing salt-containing wastewater, initial rainwater and the like. Usually, the multiple waste water streams are collected by the secondary lead recovery enterprises for centralized treatment. The main environmental pollutants in the wastewater comprise heavy metal ions of lead, antimony, arsenic and cadmium, suspended matters (SS), COD and the like, and also contain a large amount of Na2SO4、Na2SO3And a small amount of a salt such as NaCl. If the waste is directly discharged without treatment, the water environment around the plant area can be seriously polluted, the health of surrounding residents can be threatened, and huge waste of chemical raw material resources can be caused. In the technical specification of treating and recycling secondary lead production wastewater of YST 1169-2017 newly issued by the Ministry of industry and informatization, it is more clearly indicated that the terminal treatment process of the secondary lead enterprise production wastewater is preferably mature and reliable, and different depth treatment designs are carried out according to the requirement of recycled water quality, so as to ensure that the recycling rate of the secondary lead production wastewater reaches 100 percent. Therefore, the treatment of the waste water of the secondary lead into the industrial production water which can be recycled, and the realization of the zero discharge of the waste water is the necessary requirement for the related production enterprises of the secondary lead. According to the feasible technical guideline for preventing and treating secondary lead smelting pollution issued by the national environmental protection department, the traditional treatment technology for secondary lead wastewater comprises a lime neutralization method, a sulfide-lime neutralization method, an ion exchange method, a chelation precipitation method, an adsorption method, a membrane separation method, a flocculation precipitation method and the like. The methods have certain removal effect on pollutants in the secondary lead wastewater, but cannot simultaneously reach the standards of final wastewater reuse and salt product purity when in use, and are usually used as a pretreatment or advanced treatment process in a combined process for treating the secondary lead wastewater.
At present, after most of secondary lead enterprises adopt processes such as a medicament precipitation method, an adsorption method or a membrane separation method to treat wastewater, indexes such as SS, COD and heavy metal ion content in the wastewater can meet the recycling requirement of industrial wastewater. And for a large amount of salt products contained in the wastewater, direct evaporation crystallization treatment is adopted, so that the obtained mixed salt has high heavy metal impurity content, cannot be used as a product, and only can be treated as dangerous waste, so that the solid waste production is large, and the unit treatment cost of the wastewater is additionally increased. The waste water contains sodium sulfate, sodium sulfite, sodium bisulfite, sodium chloride, a small amount of impurities such as calcium, magnesium and the like, organic matters, trace heavy metal ions and the like, and the salt content is generally 25 wt%. If the high-salinity wastewater is directly discharged into a water body, the water quality can be mineralized, so that the water quality of soil, surface water and underground water is influenced, and the ecological environment is damaged. Therefore, the salt content of the desulfurization wastewater must be reduced by a proper means, impurity ions in the wastewater are removed by a zero-discharge process, main salt in the wastewater is recovered, and the salt and the wastewater after advanced treatment are recycled.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for recovering high-purity sodium sulfate in secondary lead waste liquid, which can simultaneously meet the requirements of wastewater reuse and salt product recovery, and has low operation cost and high purity of the recovered solid product.
The method for recovering the high-purity sodium sulfate in the regenerated lead waste liquid comprises the following steps:
1) adding alkali into the regenerated lead waste liquid subjected to primary impurity removal, precipitation and filtration treatment to adjust the pH value to 6-8, and standing for precipitation;
2) introducing the waste liquid into an aeration tank, and adding an iron-containing catalyst for catalytic oxidation aeration;
3) adding soda into the waste liquid after aeration to adjust the pH value to 7-9, fully stirring, standing and precipitating, wherein the amount of the soda is 2-8 g/L;
4) treating the waste liquid by using an ultrafiltration membrane, wherein the aperture of the ultrafiltration membrane is 10-100 nm;
5) softening and removing impurities from the obtained ultrafiltrate by using cationic resin;
6) concentrating the cation resin treatment liquid through a nanofiltration membrane;
7) carrying out low-temperature freezing crystallization on the nanofiltration concentrated solution to obtain sodium sulfate decahydrate crystals, and dissolving the sodium sulfate decahydrate crystals by adopting pure water to prepare saturated solution;
8) carrying out reduced pressure evaporation crystallization on the obtained saturated solution to obtain anhydrous sodium sulfate crystals;
9) and washing the sodium sulfate crystal with clear water.
Any one of the following schemes can be used as a preferable scheme of the recovery method of the high-purity sodium sulfate in the regenerated lead waste liquid:
the iron-containing catalyst in the step 1) is scrap iron.
The iron-containing catalyst in the step 2) is obtained by processing the following steps:
firstly, heating and boiling waste scrap iron by adopting a sodium carbonate solution with the weight percentage concentration of 5-10%, and then carrying out surface corrosion treatment on the treated scrap iron by adopting dilute sulfuric acid with the weight percentage concentration of 5-15%.
The dosage of the iron-containing catalyst in the step 2) is 0.1-1 g/L.
In the step 2), the aeration rate of the aeration disc is 0.01-1 m in the catalytic oxidation aeration3and/h.L, wherein the aeration time is 4-12 h.
When the ultrafiltration membrane in the step 4) is used for filtering, the aperture of the ultrafiltration membrane is 30-50 nm.
And 6), recycling the nanofiltration produced water as industrial water.
In the step 7), the control mode of the low-temperature freezing crystallization temperature is as follows: uniformly cooling the raw material liquid in a crystallization container, when the temperature is slowly reduced to 5-10 ℃, precipitating crystals, adding 0.5-2 g/L anhydrous sodium sulfate as seed crystals, rapidly cooling to 0-1 ℃, and obtaining a crystallization product, namely sodium sulfate decahydrate.
In the step 8), the initial heating temperature of the reduced pressure evaporation crystallization is 40-50 ℃, the temperature is raised to 60-80 ℃ in the crystallization process, the vacuum degree of the reduced pressure evaporation crystallization is 0.08-0.1 MPa, and the crystallization product is anhydrous sodium sulfate.
The design principle of the recovery method of high-purity sodium sulfate in the regenerated lead waste liquid is as follows:
the regenerated lead wastewater is treated by adopting a series of combined processes of adjusting the pH value to be neutral by alkali, carrying out catalytic oxidation aeration, adjusting the pH value by soda, precipitating, treating by acidic cation resin, carrying out nanofiltration membrane concentration treatment, carrying out low-temperature freezing crystallization and carrying out reduced pressure evaporation crystallization. Wherein, when the pH value is adjusted to be neutral by alkali, a part of heavy metal ions can be removed by precipitation; catalytic oxidation aeration in neutral environment and Fe2+Under the catalytic action, most of sodium sulfite, sodium bisulfite and partial organic matters in the desulfurization wastewater can be quickly oxidized, and the wastewater is effectively reducedThe COD of (1); the pH of the wastewater is adjusted to be alkalescent by the soda ash, and the residual Ca in the water can be removed by precipitation2+、Mg2+Most of the excess Fe2+，Fe3+And part of heavy metal ions; the ultrafiltration membrane can remove iron-containing suspended matters and partial organic matters in the wastewater, reduce the iron content and COD of resin inlet water and prevent the resin from being polluted; deeply removing various heavy metal ions in the wastewater by using acidic cation resin; because monovalent ions can permeate the nanofiltration membrane, the industrial reuse water contains a small amount of sodium chloride, and the concentration treatment of the nanofiltration membrane can improve the content of sodium sulfate in the wastewater to obtain the recyclable industrial production water. The anhydrous sodium sulfate of class I superior product with the purity of more than 99 percent is prepared by low-temperature freezing and reduced-pressure evaporation crystallization processes, and is cleaned and dried by pure water. The process simultaneously realizes zero discharge of wastewater, and has better industrial application prospect in the field of sodium-alkali desulfurization wastewater treatment.
Compared with the existing desulfurization wastewater zero-discharge treatment process, the process scheme provided by the invention has the advantages that the iron filings are creatively used for treating the sodium-alkali desulfurization wastewater, the iron filings have excellent catalytic oxidation aeration effect and the coprecipitation effect after the aeration reaction, so that the sulfite radicals and heavy metal ions in the wastewater are removed more quickly and thoroughly, the obtained anhydrous sodium sulfate product has higher purity which reaches over 99%, the I-class high-grade standard anhydrous sodium sulfate in GB/T6009-2014 industry is met, and the added value of the product is higher. Especially for the regenerated lead desulfurization wastewater of the storage battery factory, the anhydrous sodium sulfate obtained by crystallization reaches the internal standard of the storage battery factory. The zero-discharge treatment process provided by the invention can be used for recycling industrial water, and simultaneously, the anhydrous sodium sulfate raw material for producing the storage batteries in the factory is obtained, so that the cyclic recycling of the anhydrous sodium sulfate is realized, the medicament cost of enterprise production is saved, and certain economic benefits are brought to enterprises.
The combined process has wide application range of process parameter conditions, mature and reliable process technology adopted in each step, can meet the treatment requirements of desulfurization waste water with different water volumes and different pollutant concentrations, and stably realizes zero discharge of waste water. The method can obtain the industrial reuse water and simultaneously crystallize to obtain the high-purity anhydrous sodium sulfate, and is very suitable for being popularized to all industrial enterprises which adopt a sodium-alkali method to carry out flue gas desulfurization and produce desulfurization wastewater.
Detailed Description
The method for recovering high-purity sodium sulfate from the regenerated lead waste liquid of this patent will be described in further detail below with reference to specific examples.
Example 1
The method is adopted to treat the regenerated lead desulfurization wastewater generated by carrying out flue gas desulfurization on a certain storage battery company in Wuhan City by a sodium-alkali method, and the specific treatment steps are as follows:
1) after 100L of wastewater (pH is about 5) samples are subjected to primary impurity removal, precipitation and filtration treatment, 20g/L of calcium hydroxide is added into the secondary lead desulfurization wastewater of raw water to adjust the pH to about 7, the mixture is stirred for 1 hour and then is subjected to filter pressing treatment by a small plate-and-frame filter press, the obtained filter cakes are stored and concentrated and are sent to a unit with hazardous waste treatment quality for treatment, and the step can precipitate and remove part of heavy metal ions in the wastewater.
2) Introducing the filtrate obtained in the step 1 into an aeration tank with the volume of 200L, adding iron-containing catalyst scrap iron into the aeration tank according to the proportion of 0.6g/L, and using the air flow of 63m3The/h small-sized blower is connected with a D260 silica gel aeration disc, and the aeration rate is 0.7m3h.L, blowing air into the wastewater, fully aerating for 6h, stopping aeration, standing for 30min, depositing unreacted scrap iron at the bottom, and pumping the supernatant to another reaction tank. The step is mainly in Fe2+Under the catalytic action of the catalyst, oxygen is introduced to quickly oxidize and remove part of organic matters in the desulfurization wastewater, and most of sodium sulfite and sodium bisulfite are oxidized into sodium sulfate. The catalyst rust of the step is obtained after being treated in the following way: firstly, heating and boiling waste iron filings by using 8% by weight of sodium carbonate solution, and then carrying out surface corrosion treatment on the treated iron filings by using 12% by weight of dilute sulfuric acid.
3) And (3) adding sodium carbonate into the wastewater obtained by the treatment in the step (2), adjusting the pH value of the wastewater to 8, stirring for 1h, and performing filter pressing treatment by using a small plate-and-frame filter press, wherein the filter cake treatment method is the same as that in the step (1). The amount of sodium carbonate used in this step was 6.4g/L, this timeThe step can fully precipitate and remove Ca in the wastewater2+、Mg2+、Fe2+、Fe3+And a portion of the heavy metal ions.
4) And (4) treating the filtrate obtained in the step (3) by using an ultrafiltration membrane device, wherein the aperture range of the ultrafiltration membrane is 40-50 nm. The step can remove iron-containing suspended matters and partial organic matters in the wastewater, reduce the iron content and COD of the resin inlet water, and prevent the resin from being polluted as a pretreatment process of the resin inlet water.
5) The ultrafiltration membrane obtained in the step 4 produces water with the passing specification of
The running flow rate of the poly PP cation exchange resin column is controlled to be 20-30 m/h, and the concentration of various heavy metal ions in the wastewater can be reduced to be below 1 mg/L.
6) And (4) concentrating and purifying the resin produced water obtained in the step (5) by using a nanofiltration membrane until the weight percentage concentration is more than 10%, wherein a small amount of sodium chloride exists in the nanofiltration produced water because monovalent ions cannot be intercepted by the nanofiltration membrane, and the nanofiltration produced water can be reused as industrial water.
7) Putting the concentrated filtrate into a temperature-adjustable refrigerator for low-temperature freezing crystallization to obtain sodium sulfate decahydrate crystals, and dissolving the sodium sulfate decahydrate crystals by pure water to prepare saturated solution; the low-temperature freezing crystallization temperature control mode is as follows: intermittent crystallization is adopted to ensure that a raw material solution is uniformly cooled in a crystallization container, when the temperature is controlled to slowly decrease to 5-10 ℃, a small amount of crystals are separated out, 0.5-1 g/L of anhydrous sodium sulfate is added to be used as seed crystals, the temperature is rapidly decreased to 0-1 ℃, the crystallization product is sodium sulfate decahydrate, the solid-liquid mixture obtained after crystallization is subjected to suction filtration separation, and the obtained sodium sulfate decahydrate crystals are cleaned by pure water and stored. In the step, the cold crystallization process can be repeated for a plurality of times until 100L of resin produced water is completely crystallized to obtain the sodium sulfate decahydrate. Concentrating the obtained cold crystallization mother liquor by using a nanofiltration membrane device until the weight percentage concentration of sodium sulfate is more than 10%, and continuously freezing and crystallizing the concentrated solution. The obtained sodium sulfate decahydrate crystal was made into a saturated solution with hot water of 40 ℃.
8) Putting 10L of saturated solution into a reduced-pressure evaporation crystallization tank, using a water-ring vacuum pump and an electronic temperature-adjusting heating kettle, wherein the initial heating temperature is 40-50 ℃ in the crystallization process, the temperature rises to 75-80 ℃ after crystals appear, the vacuum degree of the reduced-pressure evaporation crystallization is 0.08-0.09 MPa, keeping vigorous stirring on the solution in the heating process, separating out anhydrous sodium sulfate crystals, continuing to evaporate to a certain evaporation amount, and stopping crystallization. And (3) carrying out suction filtration and separation on the solid-liquid mixture obtained after the pressure reduction evaporation for a period of time, refluxing the thermal crystallization mother liquor to a pressure reduction evaporation crystallization tank for continuous crystallization, washing the obtained anhydrous sodium sulfate crystal by pure water, and drying the anhydrous sodium sulfate crystal and a drying oven at 105 ℃ to constant weight to obtain an anhydrous sodium sulfate product. The obtained water vapor can be used for preparing saturated solution of sodium sulfate after being condensed by a condensing tube.
9) And washing the sodium sulfate crystal with clear water.
A proper amount of the sample in the embodiment is taken and sent to a related professional institution for detection, and the purity of the anhydrous sodium sulfate reaches 99.8%. A proper amount of sample is taken and sent to a storage battery company in North lake for detection, the content of heavy metal ion impurities in the anhydrous sodium sulfate meets the internal requirements of a storage battery factory, and the anhydrous sodium sulfate can be used as a raw material for storage battery production.
Example 2
The method is adopted to treat the regenerated lead desulfurization wastewater generated by carrying out flue gas desulfurization on a certain storage battery company in Xiangyang City of Hubei province by a sodium-alkali method, and the specific treatment steps are as follows:
1) taking 100L of wastewater sample, carrying out primary impurity removal, precipitation and filtration treatment, adding 10g/L of sodium hydroxide into the wastewater, adjusting the pH to about 7, stirring for 1h, carrying out filter pressing treatment by using a small plate-and-frame filter press, storing and concentrating the obtained filter cake, and sending the filter cake to a unit with dangerous waste treatment quality for treatment; the step can precipitate and remove part of heavy metal ions in the wastewater.
2) Introducing the filtrate obtained in the step 1 into an aeration tank with the volume of 200L, adding a scrap iron catalyst into the aeration tank according to the proportion of 0.8g/L, and using the air quantity of 60m3The/h small-sized blower is connected with a D260 silica gel aeration disc, and the aeration rate is 0.35m3h.L, blowing air into the wastewater, aerating for 10h, stopping aeration, standing for 30min, and depositing unreacted scrap ironAt the bottom, the supernatant is pumped to another reaction cell. The catalyst rust is obtained after being treated according to the following modes: firstly, heating and boiling the waste scrap iron by adopting a sodium carbonate solution with the weight percentage of 10%, and then carrying out surface corrosion treatment on the treated scrap iron by adopting dilute sulfuric acid with the weight percentage concentration of 10%.
3) And (3) adding a proper amount of sodium carbonate into the wastewater obtained in the step (2), adjusting the pH value of the wastewater to 8, stirring for 2 hours, and then performing filter pressing treatment by using a small plate-and-frame filter press, wherein the filter cake treatment method is the same as that in the step (1). The amount of sodium carbonate used in this step is 5.3g/L, and this step can sufficiently precipitate and remove Ca in wastewater2+、Mg2+、Fe2+、Fe3+And a portion of the heavy metal ions.
4) And (4) treating the filtrate obtained in the step (3) by using an ultrafiltration membrane device, wherein the aperture range of the ultrafiltration membrane is 30-40 nm. The step can remove iron-containing suspended matters and partial organic matters in the wastewater, reduce the iron content and COD of the resin inlet water, and prevent the resin from being polluted as a pretreatment process of the resin inlet water.
5) The ultrafiltration membrane obtained in the step 4 produces water with the passing specification of
The operation flow rate of the D113 type poly PP cation exchange resin column is controlled to be 20-30 m/h, and the concentration of various heavy metal ions in the wastewater can be reduced to be below 1 mg/L.
6) And (4) concentrating and purifying the resin produced water obtained in the step (5) by using a nanofiltration membrane until the weight percentage concentration is more than 12%, wherein a small amount of sodium chloride exists in the nanofiltration produced water because the nanofiltration membrane can not intercept monovalent ions, and the nanofiltration produced water can be reused as industrial water.
7) Putting the concentrated filtrate into a temperature-adjustable refrigerator for low-temperature freezing crystallization to obtain sodium sulfate decahydrate crystals, and dissolving the sodium sulfate decahydrate crystals by pure water to prepare saturated solution; the low-temperature freezing crystallization temperature control mode is as follows: intermittent crystallization is adopted to ensure that a raw material solution is uniformly cooled in a crystallization container, when the temperature is controlled to slowly decrease to 5-10 ℃, a small amount of crystals are separated out, 1-1.5 g/L of anhydrous sodium sulfate is added to be used as seed crystals, the temperature is rapidly decreased to 0-1 ℃, the crystallization product is sodium sulfate decahydrate, the solid-liquid mixture obtained after crystallization is subjected to suction filtration separation, and the obtained sodium sulfate decahydrate crystals are cleaned by pure water and stored. In the step, the cold crystallization process can be repeated for a plurality of times until 100L of resin produced water is completely crystallized to obtain the sodium sulfate decahydrate. And concentrating the obtained cold crystallization mother liquor by using a nanofiltration membrane device until the mass concentration of sodium sulfate is more than 10%, and continuously freezing and crystallizing the concentrated solution. The obtained sodium sulfate decahydrate crystal was made into a saturated solution with hot water of 40 ℃.
8) Putting 10L of saturated solution into a reduced-pressure evaporation crystallization tank, using a water-ring vacuum pump and an electronic temperature-adjusting heating kettle, wherein the initial heating temperature is 40-50 ℃ in the crystallization process, the temperature rises to 75-80 ℃ after crystals appear, the vacuum degree of the reduced-pressure evaporation crystallization is 0.08-0.09 MPa, keeping vigorous stirring on the solution in the heating process, separating out anhydrous sodium sulfate crystals, continuing to evaporate to a certain evaporation amount, and stopping crystallization. And (3) carrying out suction filtration and separation on the solid-liquid mixture obtained after the pressure reduction evaporation for a period of time, refluxing the thermal crystallization mother liquor to a pressure reduction evaporation crystallization tank for continuous crystallization, washing the obtained anhydrous sodium sulfate crystal by pure water, and drying the anhydrous sodium sulfate crystal and a drying oven at 105 ℃ to constant weight to obtain an anhydrous sodium sulfate product. The obtained water vapor can be used for preparing saturated solution of sodium sulfate after being condensed by a condensing tube.
9) And washing the sodium sulfate crystal with clear water.
And (3) taking a proper amount of sample, and sending the sample to a related professional organization for detection, wherein the purity of the anhydrous sodium sulfate reaches 99.8%. A proper amount of sample is taken and sent to a storage battery company in North lake for detection, the content of heavy metal ion impurities in the anhydrous sodium sulfate meets the requirement of preparing the electrolyte of the lead storage battery, and the anhydrous sodium sulfate can be used as a raw material for producing the storage battery.
Claims (9)
1. A method for recovering high-purity sodium sulfate in secondary lead waste liquid comprises the following steps:
1) adding alkali into the regenerated lead waste liquid subjected to primary impurity removal, precipitation and filtration treatment to adjust the pH value to 6-8, and standing for precipitation;
2) introducing the waste liquid into an aeration tank, and adding an iron-containing catalyst for catalytic oxidation aeration;
3) adding soda into the waste liquid after aeration to adjust the pH value to 7-9, fully stirring, standing and precipitating, wherein the amount of the soda is 2-8 g/L;
4) treating the waste liquid by using an ultrafiltration membrane, wherein the aperture of the ultrafiltration membrane is 10-100 nm;
5) softening and removing impurities from the obtained ultrafiltrate by using cationic resin;
6) concentrating the cation resin treatment liquid through a nanofiltration membrane;
7) carrying out low-temperature freezing crystallization on the nanofiltration concentrated solution to obtain sodium sulfate decahydrate crystals, and dissolving the sodium sulfate decahydrate crystals by adopting pure water to prepare saturated solution;
8) carrying out reduced pressure evaporation crystallization on the obtained saturated solution to obtain anhydrous sodium sulfate crystals;
9) and washing the sodium sulfate crystal with clear water.
2. The method for recovering high-purity sodium sulfate from regenerated lead waste liquid according to claim 1, which is characterized in that: the iron-containing catalyst in the step 1) is scrap iron.
3. The method for recovering high-purity sodium sulfate from regenerated lead waste liquid according to claim 1, which is characterized in that: the iron-containing catalyst in the step 2) is obtained by processing the following steps:
firstly, heating and boiling waste scrap iron by adopting a sodium carbonate solution with the weight percentage of 5-10%, and then carrying out surface corrosion treatment on the treated scrap iron by adopting dilute sulfuric acid with the weight percentage concentration of 5-15%.
4. The method for recovering high-purity sodium sulfate from regenerated lead waste liquid according to claim 1, which is characterized in that: the dosage of the iron-containing catalyst in the step 2) is 0.1-1 g/L.
5. The method for recovering high-purity sodium sulfate from regenerated lead waste liquid according to claim 1, which is characterized in that: in the step 2), the aeration rate of the aeration disc is 0.01-1 m in the catalytic oxidation aeration3and/h.L, wherein the aeration time is 4-12 h.
6. The method for recovering high-purity sodium sulfate from regenerated lead waste liquid according to claim 1, which is characterized in that: during ultrafiltration membrane treatment in the step 4), the aperture of the ultrafiltration membrane is 30-50 nm.
7. The method for recovering high-purity sodium sulfate from regenerated lead waste liquid according to claim 1, which is characterized in that: in the step 7), the control mode of the low-temperature freezing crystallization temperature is as follows: uniformly cooling the raw material liquid in a crystallization container, adding 0.5-2 g/L anhydrous sodium sulfate as seed crystal after the temperature is reduced to 5-10 ℃ and crystal is separated out, and rapidly cooling to 0-1 ℃.
8. The method for recovering high-purity sodium sulfate from regenerated lead waste liquid according to claim 1, which is characterized in that: in the step 8), the initial heating temperature of the reduced pressure evaporation crystallization is 40-50 ℃, the temperature is raised to 60-80 ℃ in the crystallization process, and the vacuum degree of the reduced pressure evaporation crystallization is 0.08-0.1 MPa.
9. The method for recovering high-purity sodium sulfate from regenerated lead waste liquid according to claim 1, which is characterized in that: and 6), recycling the nanofiltration produced water as industrial water.
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| CN114230081A (en) * | 2021-12-24 | 2022-03-25 | 华能辛店发电有限公司 | Method for preparing snow-melting agent and deicing fan blades by using desulfurization wastewater |
| CN114669175A (en) * | 2022-03-18 | 2022-06-28 | 山东省科学院能源研究所 | Integrated process method for wet desulfurization and denitrification |
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