CN111908440B - Resource integrated utilization method of fipronil waste salt and titanium dioxide byproduct ferrous sulfate - Google Patents
Resource integrated utilization method of fipronil waste salt and titanium dioxide byproduct ferrous sulfate Download PDFInfo
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Abstract
The invention discloses a resource integrated utilization method of fipronil waste salt and titanium dioxide byproduct ferrous sulfate, which comprises the following steps: preparing waste fipronil salt into an aqueous solution, and converting sodium sulfite in the waste salt into sodium sulfate through gas-liquid catalytic oxidation to obtain a sodium phosphate solution; preparing a titanium dioxide byproduct ferrous sulfate into an aqueous solution, and performing chemical impurity removal, hydrolytic impurity removal and oxidation treatment to obtain a ferric sulfate solution; and dropwise adding the sodium phosphate solution into the ferric sulfate solution to generate ferric phosphate under an acidic condition, filtering to obtain a ferric phosphate filter cake, and performing ball milling desalination in the presence of water to obtain the ferric phosphate for the battery. The invention applies two kinds of waste salt to the preparation of the iron phosphate, changes waste into valuable and opens up a channel for comprehensively utilizing different waste salts in different industries. The invention adopts ball milling for desalination in the presence of water, and the ball milling reduces solid particles of the filter cake, increases the external surface area of the particles, and simultaneously ensures that impurity ions mixed in the solid of the filter cake are easier to remove, thereby greatly reducing the water consumption.
Description
Technical Field
The invention relates to a resource integrated utilization method of fipronil waste salt and titanium dioxide byproduct ferrous sulfate, and relates to the field of chemical industry and pesticide waste salt resource.
Background
Fipronil is a widely used insecticide. The fipronil raw pesticide production workshop produces about 3.3 tons of waste salt every day, the fipronil waste salt is a mixed salt with various types, and the main components of the salt are sodium sulfite and sodium phosphate, and a small amount of sodium bromide, sodium sulfate, sodium trifluoromethyl sulfinate and some benzene series organic matters. Because the organic matter has high toxicity and is difficult to remove, the waste fipronil salt can be only treated as hazardous waste, and great economic pressure is brought to enterprises.
Titanium dioxide is one of important chemical raw materials, is widely applied to the industries of coatings, plastics, papermaking, printing ink, chemical fibers and the like, and the total output of the titanium dioxide is nearly 300 million tons every year in China. The production process of titanium dioxide mainly comprises two processes, namely a sulfuric acid process and a chlorination process, and the two processes are adopted by most manufacturers due to small investment, simple process and high yield. However, a large amount of ferrous sulfate byproducts are generated in the production process, and about 1 to 1.5 tons of the byproduct ferrous sulfate is generated per 1 ton of the titanium dioxide, so that the application of the titanium dioxide is limited due to magnesium, manganese, titanium, aluminum and other impurities.
Patent CN 105692986A proposes a treatment method for comprehensive utilization of waste salt, and provides a separation and purification method aiming at main substances in the waste salt and comprehensive approaches and requirements, and the saline sewage after hardness removal adopts a nanofiltration membrane to separate organic substances and divalent ions, wherein: the nanofiltration membrane concentrated water and the hardness removal concentrated solution are mixed and concentrated, the nanofiltration membrane produced water is further concentrated through a reverse osmosis membrane, then organic matters are removed through advanced oxidation, and finally tail gas treatment is carried out, so that waste salt generated in zero discharge of wastewater is comprehensively utilized. The addition of new substances such as medicaments and the like is reduced to the greatest extent, and secondary pollution is avoided. However, the process is complex to operate, and the nanofiltration membrane and the reverse osmosis membrane have high cost and are difficult to carry out industrial treatment.
Patent application CN 110204123A discloses a resource utilization method for waste salt in fipronil production, which is characterized in that sodium sulfite in the waste salt of fipronil is converted into sodium sulfate, and ferric sulfate is reacted with sodium phosphate in the waste salt to obtain a ferric phosphate product with higher added value, but the ferric sulfate used in the method is from a reagent and still needs to be improved in the aspect of reducing cost.
Patent CN103145197a provides a refining method of ferrous sulfate as a titanium dioxide byproduct: preparing a ferrous sulfate heptahydrate solution by using a titanium dioxide byproduct ferrous sulfate; adjusting the pH value of the solution to 1-2.5, and carrying out titanium hydrolysis treatment on the ferrous sulfate as a titanium dioxide byproduct; fe in ferrous sulfate heptahydrate after titanium hydrolysis treatment 3+ Reducing and adjusting the pH value of the solution to 6.0-6.5, and precipitating ferrous sulfate as a titanium dioxide byproduct by magnesium, manganese and zinc; adding a flocculating agent into the solution, stirring, standing, settling and filtering to obtain a filtrate, namely the refined ferrous sulfate solution. However, the process only carries out refining treatment on the ferrous sulfate as a byproduct of titanium dioxide, so that the added value is not high, and waste is not changed into valuable.
The patent CN 1766005A relates to a method for preparing high-purity iron oxide yellow and iron oxide red from a titanium dioxide byproduct ferrous sulfate, under the condition that the temperature is lower than 60 ℃, refining and impurity removal are carried out on a titanium dioxide byproduct ferrous sulfate solution, under the condition that an oxidant exists, the purpose of removing titanium by water and removing metal ions such as zinc, manganese and the like by coprecipitation is achieved by adjusting the pH value of the solution, then the pH value of the solution is controlled, air is introduced for oxidation under the normal temperature condition, and under different reaction conditions, the iron oxide yellow or the iron oxide red is obtained, wherein the purity reaches 99.5%.
Disclosure of Invention
The invention aims to provide an integrated method for resource utilization of two wastes, namely fipronil waste salt and titanium dioxide by-product ferrous sulfate, aiming at the problems that in the prior art, a ferric sulfate reagent is required to be used when the fipronil waste salt is used for preparing iron phosphate, the cost is high, the by-product ferrous sulfate of titanium dioxide is limited in use due to various impurities such as magnesium, manganese, titanium, aluminum and the like, and the production cost of the iron phosphate can be reduced to the greatest extent. The waste fipronil salt contains sodium sulfite and sodium phosphate, the sodium phosphate can react with ferric sulfate under acidic condition to prepare the precursor ferric phosphate of the lithium battery material, but the sodium sulfite is easily acidified and converted into sulfur dioxide under acidic condition, thereby causing environmental pollution. Therefore, in order to utilize phosphate ions in the waste fipronil salt, sodium sulfite in the waste fipronil salt is firstly converted into sodium sulfate by gas-liquid catalytic oxidation, and then sodium phosphate in the waste salt is utilized. The titanium dioxide byproduct ferrous sulfate contains rich iron elements and a small amount of other metal ions, and can be used for preparing a lithium battery material precursor iron phosphate, but impurities in the byproduct ferrous sulfate can affect the performance of the iron phosphate material, and the byproduct ferrous sulfate must be converted into relatively pure ferric sulfate through impurity ion removal and oxidation treatment. Under the acidic condition, carrying out double decomposition reaction on the pretreated fipronil waste salt and the pretreated titanium dioxide byproduct waste salt ferrous sulfate to generate iron phosphate precipitate, and removing impurity ions in the iron phosphate by a ball milling desalting method to obtain an iron phosphate product meeting the industrial standard.
The purpose of the invention is realized by the following technical scheme:
a method for recycling fipronil waste salt and a titanium dioxide byproduct ferrous sulfate is characterized in that the fipronil waste salt is prepared into an aqueous solution, and sodium sulfite in the waste salt is converted into sodium sulfate through gas-liquid catalytic oxidation to obtain a sodium phosphate solution; preparing a titanium dioxide byproduct ferrous sulfate into an aqueous solution, and performing chemical impurity removal, hydrolytic impurity removal and oxidation treatment to obtain a ferric sulfate solution; dropwise adding a sodium phosphate solution into a ferric sulfate solution, carrying out double decomposition reaction under an acidic condition to generate iron phosphate precipitate, filtering to obtain an iron phosphate filter cake and sodium sulfate filtrate, carrying out ball milling desalination in the presence of water to obtain iron phosphate for batteries meeting the industrial standard, and evaporating the sodium sulfate filtrate to obtain sodium sulfate.
The specific reaction process is represented by the following reaction equation:
2Na 2 SO 3 +O 2 →2Na 2 SO 4
2FeSO 4 +H 2 SO 4 +H 2 O 2 →Fe 2 (SO 4 ) 3 +2H 2 O
2Na 3 PO 4 +Fe 2 (SO 4 ) 3 →2FePO 4 ↓+3Na 2 SO 4
the invention relates to a resource integrated utilization method of fipronil waste salt and titanium dioxide byproduct ferrous sulfate, which comprises the following steps:
preparing a water solution from the waste fipronil salt, introducing air to perform gas-liquid catalytic oxidation in the presence of a catalyst, and converting sodium sulfite in the waste fipronil salt into sodium sulfate to obtain a sodium phosphate solution with the pH value of 11-12;
preparing a titanium dioxide byproduct ferrous sulfate into an aqueous solution with the concentration of 10-20% of anhydrous ferrous sulfate, sequentially carrying out chemical impurity removal and hydrolysis impurity removal to convert impurity metal ions into precipitates, and filtering to remove the precipitates; adding concentrated sulfuric acid, using hydrogen peroxide as an oxidant to perform oxidation treatment, oxidizing ferrous sulfate in the filtrate into ferric sulfate to obtain a ferric sulfate solution, and adjusting the pH value of the ferric sulfate solution to 1-2 by using the concentrated sulfuric acid;
step (3), dropwise adding the sodium phosphate solution obtained in the step (1) into the ferric sulfate solution obtained in the step (2), so that double decomposition reaction is carried out between the sodium phosphate and the ferric sulfate, and a ferric phosphate suspension is obtained;
filtering the iron phosphate suspension obtained in the step (4) and the step (3) to obtain an iron phosphate filter cake and a sodium sulfate filtrate; ball-milling and desalting the iron phosphate filter cake in the presence of water to remove sodium ions and sulfate of other impurity metal ions in the iron phosphate filter cake, and drying to obtain a dihydrate ferric phosphate product for the battery; the sodium sulfate filtrate is evaporated to give a sodium sulfate by-product.
The waste fipronil salt contains sodium sulfite, sodium phosphate, sodium bromide, sodium sulfate, sodium trifluoromethanesulfonate and water; wherein the mass fraction of sodium sulfite is 20-28%, the mass fraction of sodium phosphate is 25-30%, the mass fraction of sodium bromide is 0.1-0.3%, the mass fraction of sodium sulfate is 0.5-1%, the mass fraction of sodium trifluoromethanesulfonate is 0.1-0.5%, and the balance is water.
The mass fraction of ferrous sulfate heptahydrate in the titanium dioxide byproduct ferrous sulfate is 90-99%, and the impurity metal ions and the mass fraction are as follows: 0.3 to 0.6 percent of magnesium ion, 0.1 to 0.3 percent of manganese ion, 0.2 to 0.5 percent of titanium ion, 0.02 to 0.05 percent of aluminum ion and 0.02 to 0.05 percent of zinc ion.
In the step (1), the gas-liquid catalytic oxidation is as follows: the method comprises the steps of preparing an aqueous solution from waste fipronil salt and deionized water or condensed water according to a mass ratio of 1:1-1.5, introducing air according to a ratio of 10-25L/(h.kg aqueous solution) in the presence of a catalyst, oxidizing sodium sulfite into sodium sulfate at a temperature of 30-95 ℃, and stopping reaction when the oxidation rate of the sodium sulfite reaches more than 99.5%. Wherein, the dosage of the catalyst is 0.05 to 5 percent of the mass of the aqueous solution; the catalyst is one of nickel sulfate, chromium sulfate, cobalt sulfate, manganese sulfate, nickel phosphate, chromium phosphate, cobalt phosphate, manganese phosphate, nickel monoxide, manganese dioxide or cobaltosic oxide.
In the step (2), the titanium dioxide byproduct ferrous sulfate is prepared into an aqueous solution by deionized water or condensed water.
The chemical impurity removal treatment comprises the following steps: removing magnesium ions, manganese ions and zinc ions by using a sodium sulfide solution as an impurity removing agent, wherein the concentration of sodium sulfide is 30-80 g/L, and the using amount of sodium sulfide is 1-7% of the mass of ferrous sulfate; controlling the reaction temperature at 20-40 ℃, controlling the reaction time at 1-2 h, standing for 2-4 h after the reaction is finished, filtering to remove precipitates, and obtaining chemical impurity removal filtrate, wherein the contents of magnesium ions, manganese ions and zinc ions in the filtrate are all less than 0.01%.
The hydrolysis impurity removal treatment comprises the following steps: adjusting the pH value of the solution to 2-4, hydrolyzing for 3-5 h at 75-95 ℃, hydrolyzing titanium ions and aluminum ions in the solution into hydroxide precipitates under the condition, and filtering to obtain hydrolysis impurity removal filtrate, wherein the content of the titanium ions and the content of the aluminum ions in the hydrolysis impurity removal filtrate are both less than 0.01%.
The oxidation treatment comprises the following steps: according to H 2 SO 4 Adding concentrated sulfuric acid into the solution according to the molar ratio of the concentrated sulfuric acid to ferrous sulfate of 0.498-0502; controlling the dosage of the hydrogen peroxide to be 110-130% of the theoretical dosage, adding hydrogen peroxide at 25-50 ℃, and feeding for 50-90 min; after the oxidation reaction is finished, the oxidation rate of the ferrous sulfate reaches more than 99.5 percent. Because ferric sulfate can be hydrolyzed in aqueous solution, in order to ensure that the content of iron element in the ferric phosphate meets the quality index of the ferric phosphate for the battery, a method of adding excessive ferric sulfate is usually adopted, but due to the addition of excessive ferric sulfate, unreacted ferric sulfate and sodium sulfate obtained after reaction are difficult to separate, and the difficulty in purifying the sodium sulfate is increased. Therefore, the method inhibits the hydrolysis of the ferric sulfate by adjusting the pH value of the ferric sulfate solution obtained in the step (2) to 1-2 by concentrated sulfuric acid.
The mass fraction of the concentrated sulfuric acid is 98%.
In the step (3), dropwise adding the sodium phosphate solution obtained in the step (1) into the ferric sulfate solution obtained in the step (2) according to a molar ratio of ferric sulfate to sodium phosphate of 0.4-0.8, preferably 0.495-0.505, wherein the dropwise adding time is controlled to be 1-2 h, the double decomposition reaction temperature is 35-55 ℃, the dropwise adding time and the reaction temperature are controlled to obtain ferric phosphate particles with fine and uniform particle size, after the dropwise adding is finished, heating to 70-95 ℃, continuing to react for 1-2 h to obtain a ferric phosphate suspension, and filtering to obtain a ferric phosphate filter cake and sodium sulfate filtrate.
The mass fraction of sodium sulfate in the sodium sulfate filtrate is 9-15%.
The sodium sulfate solution is evaporated in a scraper evaporator under normal pressure, the evaporation temperature is 120-200 ℃, and the water content of the sodium sulfate byproduct obtained after evaporation is less than 1%. And (3) partially evaporating the condensate water to prepare a fipronil waste salt solution and a titanium dioxide byproduct ferrous sulfate solution, and partially evaporating the condensate water to perform ball milling desalination.
Except for firstly adopting deionized water, the water for preparing the waste fipronil salt solution and the ferrous sulfate solution as the titanium dioxide byproduct adopts the evaporation condensate water of the sodium sulfate filtrate obtained by double decomposition reaction.
In the step (4), the ball milling desalination comprises the following steps: in the presence of water, performing ball milling desalting on the iron phosphate filter cake for multiple times by using a planetary ball mill, removing sodium ions and sulfate of other impurity metal ions in the filter cake, and obtaining iron phosphate particles with the particle size of less than 6 mu m; the ball milling desalting times are 3-10 times, and the water consumption of each ball milling desalting time is 5 times of the mass of the iron phosphate filter cake. The content of each element in the iron phosphate obtained after ball milling and desalting meets the quality index of the technical requirements (HG/T4701-2014) in the national industrial standard of the iron phosphate for batteries.
The water adopted for ball milling desalination is deionized water or condensed water.
And mixing the filtrate obtained by ball milling desalination with the sodium sulfate filtrate, and evaporating.
Compared with the prior art, the invention has the beneficial effects that:
the method firstly converts the sodium sulfite in the fipronil waste salt into the sodium sulfate, so that the fipronil waste salt can be used under the strong acid condition, the secondary pollution to the environment caused by toxic gas sulfur dioxide generated by heating or acidolysis of sulfite is avoided, and the application range of the fipronil waste salt is expanded. According to the invention, the titanium dioxide byproduct ferrous sulfate is subjected to impurity removal and oxidation treatment to obtain the sulfate of high-valence iron, so that the sulfate can be applied to the preparation of iron phosphate. The invention applies two waste salts belonging to fine chemical industry and pesticide industry to the preparation of the iron phosphate with high added value, thereby changing waste into valuable and getting through the channel of comprehensive utilization of different waste salts in different industries.
The inventor finds out through experiments that under the condition of no ball milling, water with the mass of 80-100 times of that of an iron phosphate filter cake needs to be used for desalting to enable the content of each element in iron phosphate to meet the quality index of the technical requirement (HG/T4701-2014) in the national industry standard of iron phosphate for batteries. The invention adopts ball milling for desalination in the presence of water, so that solid particles of the filter cake become small by ball milling, the external surface area of the particles is increased, impurity ions mixed in the solid of the filter cake are easier to remove, the water consumption is greatly reduced, the energy consumed by drying and then crushing the filter cake is avoided, the energy is saved, and the preparation cost of the iron phosphate can be reduced.
Drawings
FIG. 1 is a process flow chart of a resource integrated utilization method of fipronil waste salt and ferrous sulfate as a titanium dioxide byproduct.
Detailed description of the invention
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The mass fraction of sodium sulfite in the waste fipronil salt is 24.2%, the mass fraction of sodium phosphate is 25.7%, the mass fraction of sodium bromide is 0.15%, the mass fraction of sodium sulfate is 0.74%, the mass fraction of sodium trifluoromethanesulfonate is 0.3%, and the balance is water.
Adding 50kg of waste salt into a reactor, adding deionized water or condensed water according to the mass ratio of the waste salt to the water of 1.2, stirring at room temperature until the waste salt is completely dissolved, adding 0.5kg of nickel sulfate and 0.3kg of chromium sulfate into the reactor as catalysts, introducing air according to the flow of 12.4L/(h.kg of aqueous solution), reacting for 4 hours at 50 ℃, stopping the reaction, and obtaining a sodium phosphate solution with the pH value of 11.3, wherein the oxidation rate of the sodium sulfite reaches 99.6%.
The method comprises the steps of taking a sodium phosphate solution obtained through gas-liquid catalytic oxidation as a phosphorus source, taking a ferric sulfate solution (with the concentration of 15%) prepared from ferric sulfate (analytically pure) as an iron source to prepare a ferric phosphate product, and adjusting the pH value of the ferric sulfate solution to 1.3 by adopting 98% concentrated sulfuric acid. Dropwise adding a sodium phosphate solution into a ferric sulfate solution at 45 ℃ according to the feeding molar ratio of ferric sulfate to sodium phosphate of 0.5, wherein the dropwise adding time is 1h, heating to 90 ℃ after the dropwise adding is finished, stirring for 1h to obtain a ferric phosphate suspension, and filtering to obtain a filter cake and a filtrate; in the presence of deionized water or condensed water, ball-milling and desalting the filter cake for 10 times by using a planetary ball mill, wherein the using amount of water for ball-milling and desalting each time is 5 times of the mass of the filter cake, obtaining iron phosphate with the particle size of less than 4 mu m after ball-milling and desalting, and drying to obtain an iron phosphate dihydrate product, wherein the content of each element in the iron phosphate product (shown in table 1) meets the quality index of the iron phosphate for the battery.
The content of sodium sulfate in the filtrate was 12.2%, and the filtrate was subjected to atmospheric evaporation in a wiped film evaporator at an evaporation temperature of 150 ℃ to obtain sodium sulfate by-product having a water content of 0.6% and a mass of sodium sulfate by-product of 34.2kg. And the condensate water obtained by evaporation is used for preparing fipronil waste salt solution and ferric sulfate solution.
Example 2
The weight percentage of ferrous sulfate heptahydrate in the ferrous sulfate as the titanium dioxide byproduct is 92.8%, and the metal ions and the weight percentage are as follows: 0.43% of magnesium ions, 0.26% of manganese ions, 0.37% of titanium ions, 0.024% of aluminum ions and 0.022% of zinc ions.
Preparing 40kg of titanium dioxide byproduct ferrous sulfate into an aqueous solution with the concentration of 16% of anhydrous ferrous sulfate by using deionized water or condensed water, adding 27.1L of sodium sulfide solution with the concentration of 45g/L into the aqueous solution according to the condition that the using amount of sodium sulfide is 6% of the mass of the ferrous sulfate, reacting for 2h at the temperature of 25 ℃, standing for 3h, converting magnesium, manganese and zinc ions in the solution into sulfide precipitate, filtering to remove the precipitate, wherein the mass fraction of magnesium in the filtrate is 0.0023%, the mass fraction of manganese is 0.0011% and the mass fraction of zinc is 0%; and then 98% concentrated sulfuric acid is added to adjust the pH value of the filtrate to be 3, the filtrate is hydrolyzed for 3 hours at the temperature of 90 ℃, titanium ions and aluminum ions in the solution are converted into hydroxide precipitates, the precipitates are removed by filtration, the mass fraction of titanium in the filtrate is 0.0062%, and the mass fraction of aluminum is 0.0004%. 6.54kg of 98% concentrated sulfuric acid and sulfuric acid (as H) are added to the solution after impurity removal 2 SO 4 The following is calculated) and ferrous sulfate in a molar ratio of 0.5, slowly adding 9.1kg30% hydrogen peroxide (the hydrogen peroxide amount is 120% of the theoretical amount), reacting at 40 ℃, adding the hydrogen peroxide for 60min, and adjusting the oxidation rate of the ferrous sulfate to 99.7% to obtain a ferric sulfate solution, and adding 98% concentrated sulfuric acid to adjust the pH value of the ferric sulfate solution to 1.3.
A ferric sulfate solution obtained by removing impurities and oxidizing ferrous sulfate serving as a titanium dioxide byproduct is used as an iron source, and a solution prepared from sodium phosphate (analytically pure) is used as a phosphorus source. Dropwise adding a sodium phosphate solution into a ferric sulfate solution at 45 ℃ according to the feeding molar ratio of ferric sulfate to sodium phosphate of 0.5, wherein the dropwise adding time is 1h, heating to 90 ℃ after the dropwise adding is finished, stirring for 1h to obtain a ferric phosphate suspension, and filtering to obtain a filter cake and a filtrate; in the presence of deionized water or condensed water, ball milling desalting is carried out on the filter cake for 10 times by using a planetary ball mill, the water consumption for ball milling desalting is 5 times of the mass of the filter cake each time, iron phosphate with the particle size of less than 4 mu m is obtained after ball milling desalting, a ferric phosphate dihydrate product is obtained after drying, and the content of each element in the ferric phosphate product (shown in table 2) meets the quality index of the ferric phosphate for the battery.
The content of sodium sulfate in the filtrate is 12.2%, normal pressure evaporation treatment is carried out in a scraper evaporator, the evaporation temperature is 145 ℃, the water content of a sodium sulfate byproduct obtained after evaporation is 0.5%, and the mass of the byproduct sodium sulfate is 51.2kg. The condensed water obtained by evaporation is used for preparing ferrous sulfate solution and sodium phosphate solution which are titanium dioxide byproducts.
Example 3
The mass fraction of sodium sulfite in the waste fipronil salt is 24.2%, the mass fraction of sodium phosphate is 25.7%, the mass fraction of sodium bromide is 0.15%, the mass fraction of sodium sulfate is 0.74%, the mass fraction of sodium trifluoromethanesulfonate is 0.3%, and the balance is water.
The weight percentage of ferrous sulfate heptahydrate in the ferrous sulfate as the titanium dioxide byproduct is 92.8%, and the metal ions and the weight percentage are as follows: 0.43 percent of magnesium ions, 0.26 percent of manganese ions, 0.37 percent of titanium ions, 0.024 percent of aluminum ions and 0.022 percent of zinc ions.
Adding 84.4kg of waste salt into a reactor, adding deionized water or condensed water according to the mass ratio of the waste salt to the water of 1.2, stirring at room temperature until the waste salt is completely dissolved, adding 0.5kg of nickel sulfate and 0.3kg of chromium sulfate into the reactor as catalysts, introducing air according to the flow rate of 20.2L/(h.kg of aqueous solution), reacting for 4 hours at 50 ℃ until the oxidation rate of the sodium sulfite reaches 99.6%, and stopping the reaction to obtain a sodium phosphate solution with the pH value of 11.3.
Preparing 40kg of titanium dioxide byproduct ferrous sulfate into an aqueous solution with the concentration of anhydrous ferrous sulfate being 15% by using deionized water or condensed water, adding 27.1L of sodium sulfide solution with the concentration of 45g/L into the aqueous solution according to the condition that the using amount of sodium sulfide is 6% of the mass of the ferrous sulfate, reacting for 2h at the temperature of 25 ℃, standing for 3h, converting magnesium, manganese and zinc ions in the solution into sulfide precipitate, filtering to remove the precipitate, wherein the mass fraction of magnesium in the filtrate is 0.0021%, the mass fraction of manganese is 0.0013% and the mass fraction of zinc is 0%; and adding 98% concentrated sulfuric acid to adjust the pH value of the filtrate to be 3, hydrolyzing for 3 hours at the temperature of 90 ℃, converting titanium ions and aluminum ions in the solution into hydroxide precipitates, filtering to remove the precipitates, wherein the mass fraction of titanium in the filtrate is 0.0055%, and the mass fraction of aluminum is 0%. Adding 6.54kg of 98% concentrated sulfuric acid into the solution subjected to impurity removal, wherein the molar ratio of sulfuric acid to ferrous sulfate is 0.5, slowly adding 9.1kg of 30% hydrogen peroxide (the dosage of hydrogen peroxide is 120% of the theoretical dosage), reacting at 40 ℃, wherein the adding time of the hydrogen peroxide is 60min, the oxidation rate of ferrous sulfate reaches 99.7%, obtaining ferric sulfate solution, and adding 98% concentrated sulfuric acid to adjust the pH value of the ferric sulfate solution to 1.3.
Taking a sodium phosphate solution obtained through gas-liquid catalytic oxidation as a phosphorus source, taking a ferric sulfate solution obtained through impurity removal and oxidation treatment of a titanium dioxide byproduct ferrous sulfate as an iron source, dropwise adding the sodium phosphate solution into the ferric sulfate solution at the temperature of 40 ℃ according to the feeding molar ratio of ferric sulfate to sodium phosphate of 0.5, wherein the dropwise adding time is 1h, heating to 90 ℃ after the dropwise adding is finished, stirring for 1h to obtain a ferric phosphate suspension, and filtering to obtain a filter cake and a filtrate; in the presence of deionized water or condensed water, ball-milling and desalting the filter cake for 10 times by using a planetary ball mill, wherein the amount of water for ball-milling and desalting each time is 5 times of the mass of the filter cake, ball-milling and desalting to obtain iron phosphate with the particle size of less than 4 mu m, and drying to obtain an iron phosphate dihydrate product, wherein the content of each element in the iron phosphate product (shown in tables 1 and 2) meets the quality index of the iron phosphate for the battery.
The content of sodium sulfate in the filtrate was 11.7%, and the filtrate was subjected to atmospheric evaporation in a wiped film evaporator at 145 ℃ to obtain sodium sulfate by-product having a water content of 0.5% and a mass of sodium sulfate by-product of 52.8kg.
TABLE 1 comparison of quality indexes of iron phosphate products obtained under two iron sources
TABLE 2 comparison of quality indexes of iron phosphate products obtained under two phosphorus sources
Example 4
The mass fraction of sodium sulfite in the waste fipronil salt is 21.3%, the mass fraction of sodium phosphate is 25.3%, the mass fraction of sodium bromide is 0.25%, the mass fraction of sodium sulfate is 0.64%, the mass fraction of sodium trifluoromethanesulfonate is 0.2%, and the balance is water.
The mass fraction of ferrous sulfate heptahydrate in the ferrous sulfate as the titanium dioxide byproduct is 96.8%, and the metal ions and the mass fraction are as follows: 0.33% of magnesium ions, 0.16% of manganese ions, 0.35% of titanium ions, 0.022% of aluminum ions and 0.027% of zinc ions.
74.9kg of waste fipronil salt is added into a reactor, deionized water or condensed water is added according to the mass ratio of the waste salt to the water being 1.5, the mixture is stirred at room temperature until the waste salt is completely dissolved, 0.8kg of nickel monoxide and 1.3kg of cobaltosic oxide are added into the reactor as catalysts, air is introduced according to the flow rate of 19.3L/(h.kg of aqueous solution), the reaction is carried out for 4 hours at 80 ℃, the oxidation rate of the sodium sulfite reaches 99.9 percent, the reaction is stopped, and the sodium phosphate solution with the pH value of 11.9 is obtained.
Taking 35.5kg of titanium dioxide byproduct ferrous sulfate, preparing an aqueous solution with the concentration of anhydrous ferrous sulfate being 12% by using deionized water or condensed water, adding 38.7L of 34g/L sodium sulfide solution into the aqueous solution according to the condition that the amount of sodium sulfide is 7% of the mass of the ferrous sulfate, reacting for 1.5h at 43 ℃, standing for 3h, converting magnesium ions, manganese ions and zinc ions in the solution into sulfide precipitate, filtering to remove the precipitate, wherein the mass fraction of the magnesium ions in the filtrate is 0.0014%, the mass fraction of the manganese ions is 0.0008% and the mass fraction of the zinc is 0%. Adding concentrated sulfuric acid to adjust the pH value of the filtrate to 4, hydrolyzing at 90 ℃ for 3.5h, converting titanium ions and aluminum ions in the hydrolysis solution into hydroxide precipitates, filtering to remove the precipitates, wherein the mass fraction of the titanium ions and the mass fraction of the aluminum ions in the hydrolysis impurity removal filtrate are 0.0031% and 0%. Adding 6.04kg of 98% concentrated sulfuric acid into the solution subjected to impurity removal treatment, wherein the molar ratio of sulfuric acid to ferrous sulfate is 0.495, slowly adding 9.1kg30% hydrogen peroxide (the dosage of hydrogen peroxide is 130% of the theoretical dosage), reacting at 48 ℃ for 75min, and obtaining a ferric sulfate solution, wherein the oxidation rate of ferrous sulfate reaches 99.8%. Adding 98% concentrated sulfuric acid to adjust the pH value of the ferric sulfate solution to 1.
The sodium phosphate solution obtained by gas-liquid catalytic oxidation is used as a phosphorus source, and the ferric sulfate solution obtained by impurity removal and oxidation treatment of ferrous sulfate as a titanium dioxide byproduct is used as an iron source. Dropwise adding a sodium phosphate solution into a ferric sulfate solution at 45 ℃ according to the feeding molar ratio of ferric sulfate to sodium phosphate of 0.5, wherein the dropwise adding time is 1h, heating to 88 ℃ after the dropwise adding is finished, stirring for 1h to obtain a ferric phosphate suspension, and filtering to obtain a filter cake and a filtrate; in the presence of deionized water or condensed water, ball-milling and desalting the filter cake for 4 times by using a planetary ball mill, wherein the water consumption for ball-milling and desalting each time is 5 times of the mass of the filter cake, ball-milling and desalting to obtain iron phosphate with the particle size of less than 3 mu m, and drying to obtain an iron phosphate dihydrate product, wherein the content of each element in the iron phosphate product meets the quality index of the iron phosphate for the battery (see table 3).
The content of sodium sulfate in the filtrate is 9.8%, normal pressure evaporation treatment is carried out in a scraper evaporator, the evaporation temperature is 125 ℃, the water content of a sodium sulfate byproduct obtained after evaporation is 0.9%, and the mass of the byproduct sodium sulfate is 45.1kg.
Example 5
The mass fraction of sodium sulfite in the waste fipronil salt is 27.6%, the mass fraction of sodium phosphate is 28.2%, the mass fraction of sodium bromide is 0.18%, the mass fraction of sodium sulfate is 0.77%, the mass fraction of sodium trifluoromethanesulfonate is 0.23%, and the balance is water.
The mass fraction of ferrous sulfate heptahydrate in the ferrous sulfate as the titanium dioxide byproduct is 95.5%, and the impurity metal ions and the mass fraction are as follows: 0.51% of magnesium ions, 0.12% of manganese ions, 0.27% of titanium ions, 0.046% of aluminum ions and 0.033% of zinc ions.
139.2kg of waste fipronil salt is added into a reactor, deionized water or condensed water is added according to the mass ratio of 1:1 of the waste salt to the water, the mixture is stirred at room temperature until the waste salt is completely dissolved, 0.9kg of manganese phosphate and 0.6kg of manganese dioxide are added into the reactor as catalysts, air is introduced according to the flow rate of 24.6L/(h.kg of aqueous solution), the reaction is carried out for 4 hours at 80 ℃, the oxidation rate of the sodium sulfite reaches 99.9 percent, the reaction is stopped, and the sodium phosphate solution with the pH value of 11.7 is obtained.
Taking 62.3kg of titanium dioxide byproduct ferrous sulfate, preparing an aqueous solution with the concentration of 19% of anhydrous ferrous sulfate by using deionized water or condensed water, adding 10.7L of 77g/L sodium sulfide solution into the aqueous solution according to the condition that the amount of sodium sulfide is 2.5% of the mass of the ferrous sulfate, reacting for 2 hours at 25 ℃, standing for 2.5 hours, converting magnesium ions, manganese ions and zinc ions in the solution into sulfide precipitates, filtering to remove the precipitates, wherein the mass fraction of the magnesium ions, the mass fraction of the manganese ions and the mass fraction of the zinc in the impurity-removing filtrate are 0.011%, 0.0015% and 0.0002% respectively. And adding 98% concentrated sulfuric acid to adjust the pH value of the filtrate to 2, hydrolyzing at 76 ℃ for 5h, converting titanium ions and aluminum ions in the hydrolysis solution into hydroxide precipitates, filtering to remove the precipitates, wherein the mass fraction of the titanium ions and the mass fraction of the aluminum ions in the hydrolysis impurity removal filtrate are 0.0031% and 0%. Adding 10.44kg of 98% concentrated sulfuric acid into the solution subjected to impurity removal treatment, wherein the molar ratio of sulfuric acid to ferrous sulfate is 0.497, slowly adding 13.9kg of 30% hydrogen peroxide (the dosage of hydrogen peroxide is 115% of the theoretical dosage), reacting at 25 ℃ for 90min, and obtaining a ferric sulfate solution, wherein the oxidation rate of ferrous sulfate reaches 99.9%. And adding 98% concentrated sulfuric acid to adjust the pH value of the ferric sulfate solution to 2.
The sodium phosphate solution obtained by gas-liquid catalytic oxidation is used as a phosphorus source, and the ferric sulfate solution obtained by impurity removal and oxidation treatment of ferrous sulfate as a titanium dioxide byproduct is used as an iron source. Dropwise adding a sodium phosphate solution into a ferric sulfate solution at 39 ℃ according to the feeding molar ratio of ferric sulfate to sodium phosphate of 0.5, wherein the dropwise adding time is 2 hours, heating to 88 ℃ after the dropwise adding is finished, stirring for 2 hours to obtain a ferric phosphate suspension, and filtering the ferric phosphate suspension to obtain a filter cake and a filtrate; in the presence of deionized water or condensed water, ball-milling and desalting the filter cake for 10 times by using a planetary ball mill, wherein the using amount of water for ball-milling and desalting each time is 5 times of the mass of the filter cake, and after ball-milling and desalting, obtaining the iron phosphate with the particle size of less than 5 mu m, wherein the content of each element in the iron phosphate product meets the quality index of the iron phosphate for the battery (see table 3).
The filtrate contained 14.3% sodium sulfate, and was subjected to atmospheric evaporation in a wiped film evaporator at 200 deg.C to obtain sodium sulfate byproduct with water content of 0% and sodium sulfate mass of 83.5kg.
Example 6
The mass fraction of sodium sulfite in the waste fipronil salt is 26.4%, the mass fraction of sodium phosphate is 27.7%, the mass fraction of sodium bromide is 0.17%, the mass fraction of sodium sulfate is 0.84%, the mass fraction of sodium trifluoromethanesulfonate is 0.29%, and the balance is water.
The mass fraction of ferrous sulfate heptahydrate in the titanium dioxide byproduct ferrous sulfate is 98.2%, and the impurity metal ions and the mass fraction are as follows: 0.34% of magnesium ions, 0.16% of manganese ions, 0.21% of titanium ions, 0.028% of aluminum ions and 0.024% of zinc ions.
Adding 56.6kg of waste fipronil salt into a reactor, adding deionized water or condensed water according to the mass ratio of the waste salt to the water being 1.6, stirring at room temperature until the waste salt is completely dissolved, adding 2.6kg of chromium sulfate serving as a catalyst into the reactor, introducing air according to the flow rate of 14.2L/(h.kg of aqueous solution), reacting for 5 hours at 40 ℃, stopping the reaction, and obtaining a sodium phosphate solution with the pH value of 11.8, wherein the oxidation rate of the sodium sulfite reaches 99.6%.
Taking 28.6kg of titanium dioxide byproduct ferrous sulfate, preparing an aqueous solution with the concentration of 18% of anhydrous ferrous sulfate by using deionized water or condensed water, adding 9.5L of a sodium sulfide solution with the concentration of 65g/L into the aqueous solution according to the condition that the amount of sodium sulfide is 4% of the mass of the ferrous sulfate, reacting for 2h at 36 ℃, standing for 3h, converting magnesium ions, manganese ions and zinc ions in the solution into sulfide precipitates, filtering to remove the precipitates, wherein the mass fraction of the magnesium ions, the mass fraction of the manganese ions and the mass fraction of the zinc in the impurity removal filtrate are 0.0088%, 0.0015% and 0.0002%. Adding concentrated sulfuric acid to adjust the pH value of the filtrate to be 3, hydrolyzing for 3.5h at the temperature of 92 ℃, converting titanium ions and aluminum ions in the hydrolysis solution into hydroxide precipitates, filtering to remove the precipitates, wherein the mass fraction of the titanium ions in the hydrolysis impurity removal filtrate is 0.0016%, and the mass fraction of the aluminum ions is 0%. Adding 5.05kg of 98% concentrated sulfuric acid into the solution subjected to impurity removal treatment, wherein the molar ratio of sulfuric acid to ferrous sulfate is 0.505 to 1, slowly adding 7.2kg of 30% hydrogen peroxide (the dosage of hydrogen peroxide is 125% of the theoretical dosage), reacting at 38 ℃, feeding for 75min, and obtaining a ferric sulfate solution, wherein the oxidation rate of ferrous sulfate reaches 99.8%. Adding 98% concentrated sulfuric acid to adjust the heating pH value of the ferric sulfate solution to 1.3.
The sodium phosphate solution obtained by gas-liquid catalytic oxidation is used as a phosphorus source, and the ferric sulfate solution obtained by removing impurities and oxidizing ferrous sulfate which is a byproduct of titanium dioxide is used as an iron source. Dropwise adding a sodium phosphate solution into a ferric sulfate solution at 50 ℃ according to the feeding molar ratio of ferric sulfate to sodium phosphate of 0.5, wherein the dropwise adding time is 1.5h, heating to 95 ℃ after the dropwise adding is finished, stirring for 1.5h to obtain a ferric phosphate suspension, and filtering the ferric phosphate suspension to obtain a filter cake and a filtrate; in the presence of deionized water or condensed water, carrying out ball milling desalination on the filter cake for 7 times by using a planetary ball mill, wherein the water consumption for ball milling desalination is 5 times of the mass of the filter cake, carrying out ball milling desalination to obtain iron phosphate with the particle size of less than 3 mu m, and drying to obtain an iron phosphate dihydrate product, wherein the content of each element in the iron phosphate product meets the quality index of the iron phosphate for the battery (see table 3).
The filtrate contained 12.8% sodium sulfate, and was subjected to atmospheric evaporation in a wiped film evaporator at 165 ℃ to obtain a sodium sulfate by-product having a water content of 0.25% and a mass of 38.9kg.
TABLE 3 quality index of iron phosphate product
Claims (8)
1. A resource integrated utilization method of fipronil waste salt and titanium dioxide byproduct ferrous sulfate is characterized by comprising the following steps:
preparing a water solution from the waste fipronil salt, introducing air to perform gas-liquid catalytic oxidation in the presence of a catalyst, and converting sodium sulfite in the waste fipronil salt into sodium sulfate to obtain a sodium phosphate solution with the pH value of 11-12;
preparing a titanium dioxide byproduct ferrous sulfate into an aqueous solution with ferrous sulfate concentration of 10-20%, sequentially performing chemical impurity removal and hydrolysis impurity removal to convert impurity metal ions into precipitates, and filtering to remove the precipitates; adding concentrated sulfuric acid, taking hydrogen peroxide as an oxidant to carry out oxidation treatment, oxidizing ferrous sulfate in the filtrate into ferric sulfate to obtain a ferric sulfate solution, and adjusting the pH value of the ferric sulfate solution to be 1-2 by adopting the concentrated sulfuric acid;
the mass fraction of ferrous sulfate heptahydrate in the byproduct ferrous sulfate in the production of titanium dioxide is 90-99%, and the impurity metal ions and the mass fraction are as follows: 0.3 to 0.6 percent of magnesium ion, 0.1 to 0.3 percent of manganese ion, 0.2 to 0.5 percent of titanium ion, 0.02 to 0.05 percent of aluminum ion and 0.02 to 0.05 percent of zinc ion;
the chemical impurity removal treatment comprises the following steps: removing magnesium ions, manganese ions and zinc ions by using a sodium sulfide solution as an impurity removing agent, wherein the contents of the magnesium ions, the manganese ions and the zinc ions in the chemical impurity removing filtrate are all less than 0.01%;
the hydrolysis impurity removal treatment comprises the following steps: adjusting the pH value of the solution to 2-4, hydrolyzing at 75-95 ℃ for 3-5 h, and filtering to obtain hydrolysis impurity removal filtrate, wherein the content of titanium ions and aluminum ions in the hydrolysis impurity removal filtrate is less than 0.01%;
step (3), dropwise adding the sodium phosphate solution obtained in the step (1) into the ferric sulfate solution obtained in the step (2), so that double decomposition reaction is carried out between the sodium phosphate and the ferric sulfate, and a ferric phosphate suspension is obtained;
filtering the iron phosphate suspension obtained in the step (4) and the step (3) to obtain an iron phosphate filter cake and a sodium sulfate filtrate; ball-milling and desalting the iron phosphate filter cake in the presence of water, wherein the ball-milling and desalting times are 3-10 times, the using amount of water for ball-milling and desalting each time is 5 times of the mass of the iron phosphate filter cake, and drying to obtain a dihydrate iron phosphate product for the battery; the sodium sulfate filtrate is evaporated to give a sodium sulfate by-product.
2. The resource integrated utilization method of fipronil waste salt and titanium dioxide byproduct ferrous sulfate according to claim 1, characterized in that the fipronil waste salt contains sodium sulfite, sodium phosphate, sodium bromide, sodium sulfate, sodium trifluoromethanesulfonate and water; wherein the mass fraction of sodium sulfite is 20-28%, the content of sodium phosphate is 25-30%, the content of sodium bromide is 0.1-0.3%, the content of sodium sulfate is 0.5-1%, the content of sodium trifluoromethanesulfonate is 0.1-0.5%, and the balance is water.
3. The resource integrated utilization method of fipronil waste salt and titanium dioxide byproduct ferrous sulfate according to claim 1, characterized in that the gas-liquid catalytic oxidation is: preparing waste fipronil salt and deionized water or condensed water into aqueous solution according to the mass ratio of 1:1-1.5, introducing air according to the mass ratio of 10-25L/(h.kg aqueous solution) in the presence of a catalyst, oxidizing sodium sulfite into sodium sulfate at the temperature of 30-95 ℃, and stopping reaction when the oxidation rate of the sodium sulfite reaches more than 99.5%; wherein, the dosage of the catalyst is 0.05-5% of the mass of the aqueous solution; the catalyst is one of nickel sulfate, chromium sulfate, cobalt sulfate, manganese sulfate, nickel phosphate, chromium phosphate, cobalt phosphate, manganese phosphate, nickel monoxide, manganese dioxide or cobaltosic oxide.
4. The method for resource integrated utilization of fipronil waste salt and ferrous sulfate as a by-product of titanium dioxide according to claim 1, wherein the chemical impurity removal treatment comprises: adopting sodium sulfide solution as an impurity removing agent, wherein the concentration of sodium sulfide is 30-80 g/L, and the using amount of sodium sulfide is 1-7% of the mass of ferrous sulfate; controlling the reaction temperature at 20-40 ℃, the reaction time at 1-2 h, standing for 2-4 h after the reaction is finished, filtering to remove precipitates, and obtaining chemical impurity removal filtrate, wherein the contents of magnesium ions, manganese ions and zinc ions in the filtrate are all less than 0.01%.
5. The resource integrated utilization method of fipronil waste salt and titanium dioxide byproduct ferrous sulfate according to claim 1, characterized in that the oxidation treatment is: firstly, concentrated sulfuric acid is used for adjusting the pH value of the hydrolysis impurity-removal filtrate to 1-2, and then the pH value is adjusted according to H 2 SO 4 Adding concentrated sulfuric acid into the solution according to the molar ratio of the concentrated sulfuric acid to ferrous sulfate of 0.498-0502; controlling the dosage of the hydrogen peroxide to be 110-130% of the theoretical dosage, and adding the hydrogen peroxide at 25-50 ℃ for 50-90 min.
6. The resource integrated utilization method of fipronil waste salt and titanium dioxide by-product ferrous sulfate according to claim 1, characterized in that the sodium phosphate solution is dripped into the ferric sulfate solution according to the molar ratio of ferric sulfate to sodium phosphate of 0.4-0.8, the dripping time is controlled to be 1-2 h, and the double decomposition reaction temperature is 35-55 ℃; after the dropwise addition is finished, heating to 70-95 ℃, continuously reacting for 1-2 h to obtain an iron phosphate suspension, and filtering to obtain an iron phosphate filter cake and a sodium sulfate filtrate.
7. The resource integrated utilization method of fipronil waste salt and titanium dioxide byproduct ferrous sulfate according to claim 6, characterized in that the molar ratio of ferric sulfate to sodium phosphate is 0.495-0.505.
8. The resource integrated utilization method of fipronil waste salt and titanium dioxide byproduct ferrous sulfate according to claim 1, characterized in that the ball milling desalination is as follows: and (3) carrying out ball milling on the iron phosphate filter cake for multiple times by adopting a planetary ball mill in the presence of water to obtain iron phosphate particles with the particle size of less than 6 microns.
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