CN112978805A - Comprehensive recovery method of titanium, iron and sulfate radicals in titanium white waste acid - Google Patents
Comprehensive recovery method of titanium, iron and sulfate radicals in titanium white waste acid Download PDFInfo
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Abstract
The invention relates to a comprehensive recovery method of titanium, iron and sulfate radicals in titanium white waste acid, which specifically comprises the following steps: 1) the titanium white waste acid is frozen and crystallized to produce ferrous sulfate heptahydrate; 2) titanium white waste acid and phosphoric acid are used as reactants to prepare titanium phosphate; 3) and continuously leaching pyrolusite and rhodochrosite from the filtrate after titanium extraction to prepare a manganese sulfate solution. The method has the advantages that: the comprehensive utilization of titanium white waste acid resources is realized, the cost is saved, the operation is simple, and no new three wastes are generated.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment and environmental protection processes, and particularly relates to a comprehensive recovery method of titanium, iron and sulfate radicals in titanium white waste acid.
Background
At present, the titanium dioxide industry mainly comprises two production processes of a sulfuric acid method and a chlorination method. The sulfuric acid method has mature technology, simple equipment and easy replication of a production line, is a production process mainly used by titanium white enterprises in China, and accounts for 84 percent of the national capacity. But about 8-10 t of waste acid containing 20% of sulfuric acid is generated every 1t of titanium dioxide. With the wide application of the sulfuric acid method production process in China, the recycling of waste acid becomes a difficult point of sustainable development of the titanium dioxide industry. At present, the titanium white waste acid treatment process is mainly divided into two types, firstly, the waste acid is neutralized by lime, the treatment method is easy to generate a large amount of titanium gypsum, the titanium gypsum generated by 1t of titanium white is about 6-10t, calcium sulfate particles in the titanium gypsum are fine, the free water content is high, the treatment is difficult, most enterprises mainly use stockpiling, and the problems of land occupation and environment are increasingly serious. Secondly, the concentration of the waste acid is improved to more than 60 percent by a concentration mode, and the waste acid is returned to the process for use by acid preparation, but the process is complex, the cost is high, and the wide application is difficult. Therefore, a new way for utilizing the titanium white waste acid is explored, the step of comprehensive utilization of the waste acid is accelerated, the harm is turned into the benefit, the waste is changed into the valuable, and the method has important significance for environmental protection.
Titanium phosphate is a novel inorganic chemical product and can be used as an antirust pigment, a filler, a catalyst and the like. When titanium phosphate is used as an antirust pigment, the antirust pigment not only has the advantages of low toxicity or no toxicity, no public nuisance, good antirust performance and the like of common phosphate series antirust pigments, but also has the advantages of long duration of antirust effect and good adhesion to metal substrates and upper coatings; has strong ultraviolet reflection capability. When titanium phosphate is used as pigment added into rubber plastic, the heat resistance and electrical property of the product can be improved. When used as a paper filler, the whitening agent is a very good raw material for producing high-quality copper plate paper and water-resistant photosensitive paper, has a remarkable whitening effect when being particularly used for photosensitive materials, and can improve the reflectivity of the photosensitive materials to ultraviolet rays with the wavelength of below 400 mu m. When it is used as cyclohexanol deoxidizing catalyst, polyester condensation catalyst and ketone condensation catalyst, it has high catalytic efficiency and excellent catalytic effect. Has strong adsorption capacity to alkali metals, and can be used for recovering activators in activation analysis. Recovering and separating cesium and strontium isotopes, and extracting potassium, cesium and the like from seawater, thereby having wide application prospect.
With the rapid development of the industry in China, manganese and manganese series products are widely applied to the fields of the steel industry, the nonferrous metal industry, the chemical industry, the electronic industry, the battery industry and the like. However, the manganese ore in China has complex structural properties, fine granularity and high impurity content, and the development and utilization of the manganese ore are hindered to a certain extent. In the face of increasing market demands, domestic high-grade manganese ore resources are becoming exhausted. The reasonable, high-efficiency and economic development and utilization of domestic low-grade manganese ore resources are important ways for solving the shortage of manganese resources and are inevitable trends. By coordinating the titanium ore industry with the manganese ore industry, the method reduces the stress game relation to the environment, reduces the dependence on the ecological environment, develops circular economy and promotes social development.
The invention discloses a method for preparing barium sulfate from titanium white waste acid (CN111439771A), and relates to a method for preparing barium sulfate from titanium white waste acid, wherein reduced iron powder is firstly added to obtain a small amount of Fe in titanium white waste acid3+Conversion to Fe2+Adding a barium hydroxide solution to neutralize titanium white waste acid, combining barium ions and sulfate ions to separate out barium sulfate precipitate, and regulating pH to prevent other precipitates from being generated; and adding a sodium carbonate solution, separating out ferrous hydroxide precipitate and metatitanic acid precipitate to obtain a relatively pure sodium sulfate solution, reacting the filtrate with a barium chloride solution to generate barium sulfate, and recovering sulfate ions for the second time. Although the method has higher recovery rate for sulfate radicals, the iron and the titanium are filtered out in a coprecipitation mode, the subsequent separation operation is difficult, the cost is higher, and the separation effect needs to be examined.
The patent document 'a process for preparing building gypsum by comprehensively utilizing titanium white waste acid and acidic wastewater' (CN112047370A), the invention relates to a process for preparing building gypsum by comprehensively utilizing titanium white waste acid and acidic wastewater, chelating agent is added into titanium white acidic wastewater, pH is adjusted, sludge filter cake is obtained by filtering, titanium white waste acid is added into the sludge filter cake and is uniformly mixed, filter residue is obtained by filtering after uniform mixing, and building gypsum which meets the building gypsum standard is obtained by drying at high temperature. Although the invention eliminates the problem of secondary pollution caused by titanium gypsum generated by neutralization, the method has low comprehensive utilization rate of titanium white waste acid.
The invention discloses a process for fully recycling titanium white waste liquid (CN111485102A), and relates to a process for fully recycling titanium white waste liquid, which is characterized in that manganese sulfate and iron oxide normal-temperature desulfurizing agents are prepared by reacting manganese oxide ore and titanium white waste acid, and valuable elements are recovered by extracting and removing iron, hydrolyzing and precipitating titanium, ammonium salt and vanadium and oxalic acid and precipitating scandium. According to the invention, theoretically, the recycling of the whole resources is realized, but the titanium, vanadium and scandium elements exist in the titanium white waste acid in trace amounts, and the trace element content is further reduced by recycling the iron and manganese in the early stage, so that the follow-up titanium, vanadium and scandium recycling scheme is difficult to implement. Meanwhile, the extraction conditions of P204 on ferrotitanium are almost the same, ferrotitanium is difficult to realize effective separation, the operation is difficult, the process is complex, and the overall feasibility needs to be examined.
In conclusion, although the titanium white waste acid is utilized in multiple ways, the cost is high, the operation is complex, the comprehensive utilization rate is not high, and a comprehensive recovery process method for multiple titanium white waste acid resources, which has the advantages of reasonable technology, simple process, economy and feasibility and high resource utilization rate, is not found so far.
Disclosure of Invention
The invention aims to provide a method for comprehensively recovering titanium, iron and sulfate radicals in titanium white waste acid, so that the comprehensive utilization of titanium white waste acid resources is realized, the cost is saved, the operation is simple, and no new three wastes are generated.
In order to achieve the purpose, the invention adopts the following technical scheme:
a comprehensive recovery method of titanium, iron and sulfate radicals in titanium white waste acid comprises the following steps:
the method comprises the following steps:
conveying titanium white waste acid into a freezing crystallizer, forcibly cooling to below 0 ℃ at a cooling speed of 10-20 ℃/h through a freezing system, stirring for a period of time at a stirring speed of 50-100 rpm/min, performing solid-liquid separation to obtain filtrate 1 and filter residue 1, and performing centrifugal dehydration on the filter residue 1 to obtain a ferrous sulfate heptahydrate product;
step two:
preheating the filtrate 1 to 20-100 ℃, slowly adding phosphoric acid, uniformly mixing, reacting at a stirring speed of 100-300 rpm/min for 20-60 min, and aging for 6-24 h after the reaction is finished to obtain a precipitate;
step three:
filtering the precipitate obtained in the second step to obtain a filtrate 2 and a filter residue 2, washing the filter residue 2 with dilute sulfuric acid with the mass concentration of 10-30% for 3-5 times, washing with distilled water for 3-5 times, and drying to obtain amorphous titanium phosphate;
step four:
and roasting the amorphous titanium phosphate obtained in the step three at the temperature of 200-1200 ℃ for 2-3 h to obtain titanium phosphate or titanium pyrophosphate.
The method according to the present invention, wherein as an option, the method further comprises:
step five:
adding pyrolusite into the pickling water washing solution of the filtrate 2 and the filter residue 2 obtained by filtering the precipitate in the third step for reaction, and filtering and washing after the reaction to obtain a filtrate 3 and a filter residue 3;
step six:
adding rhodochrosite into the filtrate 3 obtained in the fifth step for reaction, and filtering and washing after the reaction to obtain filtrate 4 and filter residue 4;
step seven:
evaporating and crystallizing the filtrate 4 obtained in the sixth step to obtain manganese sulfate monohydrate, or electrolyzing to obtain electrolytic manganese metal;
the filter residue 3 and the filter residue 4 are used for preparing environmental mineral materials, and the environmental mineral materials are used for ecological restoration.
According to the method, MnO required by reaction of the filtrate (the acid washing solution of the filtrate 2 and the filter residue 2) is added in the fifth step20.8 to 1.2 times of theoretical dosage, and reactingThe temperature is 40-100 ℃, the reaction time is 1.5-3 h, and the stirring speed is 100-300 rpm/min.
According to the method, as an option, rhodochrosite is added in the sixth step in an amount of MnCO required for the reaction of the filtrate 331.1-1.3 times of theoretical dosage, 0.3-0.6 acid-ore ratio, 40-100 ℃ reaction temperature, 3-4 h reaction time and 100-500 rpm/min stirring speed.
According to the method, as an option, in the first step, the initial temperature of the titanium white waste acid is 30-40 ℃, the temperature reduction time is 2-4 h, and Fe in the liquid in the container is subjected to freezing crystallization2+≤17g/L。
According to the method of the invention, wherein, as an option, in the second step, the molar ratio of titanyl sulfate to phosphoric acid in the filtrate 1 is 1: 1.5 to 2.6.
According to the method, as an option, in the third step, the drying temperature is 50-100 ℃, and the drying time is 2-4 hours.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) the invention recovers the iron in the titanium white waste acid to produce the ferrous sulfate heptahydrate product. The method is simple, the product purity is high, and the economic value is high.
(2) Compared with the prior art, the method for preparing titanium phosphate by recovering titanium from titanium white waste acid has the advantages of cost saving, simple operation, higher product recovery rate and no generation of new three wastes.
(3) According to the method, on the premise that sulfuric acid and a reducing agent are not required to be added, pyrolusite and rhodochrosite are continuously leached to prepare a manganese sulfate solution, and the manganese sulfate solution is evaporated and crystallized to obtain manganese sulfate monohydrate or electrolyzed metal manganese is obtained through electrolysis, so that the cost is effectively reduced, the industrial combination is realized, and the resource utilization rate and the economic benefit are improved.
Drawings
FIG. 1 is a schematic flow chart of a comprehensive recovery method of titanium, iron and sulfate radicals in titanium white waste acid.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following description should be taken in conjunction with the accompanying drawings and the embodiments.
A comprehensive recovery method of titanium, iron and sulfate radicals in titanium white waste acid comprises the following steps:
the method comprises the following steps: conveying titanium white waste acid into a freezing crystallizer, forcibly cooling to below 0 ℃ at a cooling speed of 10-20 ℃/h through a freezing system, stirring for a period of time at a stirring speed of 50-100 rpm/min, performing solid-liquid separation to obtain filtrate 1 and filter residue 1, and performing centrifugal dehydration on the filter residue 1 to obtain a ferrous sulfate heptahydrate product;
step two: preheating the filtrate 1 to 20-100 ℃, slowly adding phosphoric acid, uniformly mixing, reacting at a stirring speed of 100-300 rpm/min for 20-60 min, and aging for 6-24 h after the reaction is finished to obtain a precipitate;
step three: filtering the precipitate obtained in the second step to obtain a filtrate 2 and a filter residue 2, washing the filter residue 2 with dilute sulfuric acid with the mass concentration of 10-30% for 3-5 times, washing with distilled water for 3-5 times, and drying to obtain amorphous titanium phosphate;
step four: and roasting the amorphous titanium phosphate obtained in the step three at the temperature of 200-1200 ℃ for 2-3 h to obtain titanium phosphate or titanium pyrophosphate.
Step five: adding pyrolusite into the pickling water washing solution of the filtrate 2 and the filter residue 2 obtained by filtering the precipitate in the third step for reaction, and filtering and washing after the reaction to obtain a filtrate 3 and a filter residue 3;
step six: adding rhodochrosite into the filtrate 3 obtained in the fifth step for reaction, and filtering and washing after the reaction to obtain filtrate 4 and filter residue 4;
step seven: and (5) evaporating and crystallizing the filtrate 4 obtained in the sixth step to obtain manganese sulfate monohydrate, or electrolyzing to obtain electrolytic manganese metal. The filter residue 3 and the filter residue 4 are used for preparing environmental mineral materials, and the environmental mineral materials are used for ecological restoration.
In the fifth step, MnO required by the reaction of the filtrate (the acid washing liquid of the filtrate 2 and the filter residue 2) is added into the pyrolusite20.8 to 1.2 times of theoretical dosage, 40 to 100 ℃ of reaction temperature and 1.5 to EThe stirring speed is 100-300 rpm/min for 3 hours.
In the sixth step, the amount of rhodochrosite added is MnCO required by the reaction of the filtrate 331.1-1.3 times of theoretical dosage, 0.3-0.6 acid-ore ratio, 40-100 ℃ reaction temperature, 3-4 h reaction time and 100-500 rpm/min stirring speed.
In the first step, the initial temperature of the titanium white waste acid is 30-40 ℃, the temperature reduction time is 2-4 h, and Fe in liquid in a container is subjected to freezing crystallization2+≤17g/L。
In the second step, the molar ratio of titanyl sulfate to phosphoric acid in the filtrate 1 is 1: 1.5 to 2.6.
In the third step, the drying temperature is 50-100 ℃, and the drying time is 2-4 h.
Example 1
A certain amount of titanium dioxide waste acid liquor of a certain titanium dioxide factory of the Panzhihua Sichuan is conveyed into a small-sized refrigerating device, the temperature is forcibly reduced to-2 ℃ by a refrigerating system, the temperature reduction time is 2.5 hours, the stirring speed is 50rpm/min, and liquid Fe in the device2+The content is 16g/L, solid-liquid separation is carried out, and a ferrous sulfate heptahydrate product is obtained by centrifugal dehydration of a solid phase product. Weighing a certain amount of filtrate, adding into a conical flask, wherein the sulfuric acid concentration in the filtrate is 20% and the titanium content (TiO) in the filtrate2Metering) 6.6g/L and 16g/L of iron, heating to 90 ℃ by using a magnetic stirrer, slowly adding concentrated phosphoric acid, fully mixing, stirring and reacting at 200rpm/min for 60min, aging for 12 hours after the reaction is finished, filtering, stirring and washing for 4 times by using 20% sulfuric acid at 100-200 rpm/min, washing for 4 times by using 200ml of distilled water, analyzing the titanium and iron contents in the filtrate, and drying the filter residue in an oven at 90 ℃ for 2.5 hours.
MnO was added to the filtrate20.8 times of the theoretical amount of pyrolusite (with 20% of Mn content) in Guizhou area is stirred at 80 ℃ and 100-200 rpm/min for reaction for 3 hours, then the reaction product is filtered, 200ml of distilled water is used for washing for 4 times, and the iron content in the filtrate and the manganese content in the filter residue are analyzed.
Adding MnCO into the filtrate31.1 times of theoretical amount of rhodochrosite (Mn content: 10%) in Guizhou region, controlling acid-ore ratio to be 0.4, stirring and reacting at 85 ℃ for 3h at 350rpm/min, washing with 200ml distilled water for 4 times,obtaining the manganese sulfate solution.
Through analysis, the purity of ferrous sulfate heptahydrate is more than 98 percent and reaches the national standard GB/T664-2011, the recovery rate of titanium is 95.61 percent, the purity is 98.1 percent, the leaching rate of manganese in pyrolusite is 94 percent, the leaching rate of rhodochrosite is 93 percent, and the recovery rate of iron is more than 99.5 percent.
Manganese sulfate solution is used for electrolyzing manganese, and CaCO is added3Adjusting the pH value to 7, carrying out solid-liquid separation to remove residues, adding sodium dimethyldithiocarbamate into the filtrate, removing ions such as nickel, cobalt and iron, and carrying out secondary solid-liquid separation to remove sulfide precipitates to obtain the manganese sulfate electrolyte. The manganese recovery rate is 91.5 percent after 8 hours of electrolysis at 45 ℃.
Example 2
Conveying a certain amount of titanium dioxide waste acid solution of Hebei Chengde certain titanium dioxide factory into a small-sized refrigerating device, forcibly cooling to-1 ℃ through a refrigerating system, wherein the cooling time is 3h, the stirring speed is 70rpm/min, and the liquid Fe in the device2+The content is 16.44g/L, solid-liquid separation is carried out, and a ferrous sulfate heptahydrate product is obtained by centrifugal dehydration of a solid phase product. Weighing a certain amount of filtrate, adding into a conical flask, wherein the sulfuric acid concentration in the titanium white waste acid is 22%, and the titanium content (TiO) is2Metering) 4.5g/L and 15.4g/L of iron, heating to 95 ℃ by using a magnetic stirrer, slowly adding concentrated phosphoric acid, fully mixing, stirring and reacting at 200rpm/min for 50min, aging for 12 hours after the reaction is finished, filtering, stirring and washing for 4 times at 100-200 rpm/min by using 20% sulfuric acid, washing for 4 times by using 200ml of distilled water, analyzing the contents of titanium and iron in the filtrate, and drying the filter residue in an oven at 105 ℃ for 2 hours.
MnO was added to the filtrate2The method comprises the following steps of stirring and reacting certain pyrolusite (Mn content is 17%) in Liaoning with a theoretical dosage of 1 time at 90 ℃ at a speed of 100-200 rpm/min for 2 hours, filtering, washing with 200ml of distilled water for 4 times, and analyzing the iron content in filtrate and the manganese content in filter residue.
Adding MnCO into the filtrate3The theoretical amount of rhodochrosite (Mn content is 8.4%) in Liaoning area is 1.2 times, the acid-ore ratio is controlled to be 0.45, the mixture is stirred and reacted for 3 hours at the reaction temperature of 90 ℃ and at the speed of 400rpm/min, and 200ml of distilled water is used for washing for 4 times to obtain a manganese sulfate solution.
Through analysis, the purity of ferrous sulfate heptahydrate is more than 98 percent and reaches the national standard GB/T664-2011, the recovery rate of titanium is 95.34 percent, the purity is 98.2 percent, the leaching rate of manganese in pyrolusite is 95 percent, the leaching rate of rhodochrosite is 94 percent, and the recovery rate of iron is more than 99.5 percent.
Manganese sulfate solution is used for electrolyzing manganese, and CaCO is added3Adjusting the pH value to 7, carrying out solid-liquid separation to remove residues, adding sodium dimethyldithiocarbamate into the filtrate, removing ions such as nickel, cobalt and iron, and carrying out secondary solid-liquid separation to remove sulfide precipitates to obtain the manganese sulfate electrolyte. The manganese recovery rate is 92 percent after the electrolysis is carried out for 8 hours at the temperature of 45 ℃.
Example 3
Conveying a certain amount of titanium dioxide waste acid solution of a certain titanium dioxide factory in Hunbei Xiangyang into a small-sized refrigerating device, forcibly cooling to-2 ℃ through a refrigerating system, wherein the cooling time is 4h, the stirring speed is 60rpm/min, and the liquid Fe in the device2+The content is 15.78g/L, solid-liquid separation is carried out, and a ferrous sulfate heptahydrate product is obtained by centrifugal dehydration of a solid phase product. Weighing a certain amount of filtrate, adding the filtrate into a conical flask, wherein the sulfuric acid concentration of titanium white waste acid is 18 percent, and the titanium content (TiO) is2Metering) 4.3g/L and 15.6g/L of iron, heating to 80 ℃ by using a magnetic stirrer, slowly adding concentrated phosphoric acid, fully mixing, stirring and reacting at 200rpm/min for 45min, aging for 24h after the reaction is finished, filtering, stirring and washing for 4 times at 100-200 rpm/min by using 20% sulfuric acid, washing for 4 times by using 200ml of distilled water, analyzing the contents of titanium and iron in the filtrate, and drying the filter residue in an oven at 80 ℃ for 3 h.
MnO was added to the filtrate2Stirring and reacting 1 time of pyrolusite (Mn content is 22%) in certain areas of Hunan at 100 ℃ under 100-200 rpm/min for 2h, filtering, washing with 200ml of distilled water for 4 times, and analyzing the iron content in the filtrate and the manganese content in the filter residue.
Adding MnCO into the filtrate3The theoretical amount of 1.1 times of rhodochrosite (Mn content is 11%) in certain areas of Hunan province, the acid-mineral ratio is controlled to be 0.5, the mixture is stirred and reacted for 3 hours at the reaction temperature of 95 ℃ at the speed of 300rpm/min, and 200ml of distilled water is used for washing for 4 times to obtain a manganese sulfate solution.
Through analysis, the purity of ferrous sulfate heptahydrate is more than 98 percent and reaches the national standard GB/T664-2011, the recovery rate of titanium is 95.66 percent, the purity is 98.2 percent, the leaching rate of manganese in pyrolusite is 94 percent, the leaching rate of rhodochrosite is 94 percent, and the removal rate of iron is more than 99.5 percent.
Manganese sulfate solution is used for producing manganese sulfate monohydrate, and CaCO is added3Adjusting pH to 6, carrying out solid-liquid separation to remove residues, gradually adding sodium dimethyldithiocarbamate and sodium fluoride into the filtrate, carrying out second solid-liquid separation to remove sulfide and fluoride precipitate, and carrying out evaporative crystallization to obtain manganese sulfate monohydrate with the purity of 98.5%.
The method can be realized by upper and lower limit values and interval values of intervals of process parameters (such as temperature, time and the like), and embodiments are not listed.
Conventional technical knowledge in the art can be used for the details which are not described in the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. A comprehensive recovery method of titanium, iron and sulfate radicals in titanium white waste acid comprises the following steps:
the method comprises the following steps:
forcibly cooling titanium white waste acid to below 0 ℃ at a cooling rate of 10-20 ℃/h, stirring at a stirring speed of 50-100 rpm/min for a period of time, and carrying out solid-liquid separation to obtain a filtrate 1 and a filter residue 1, and carrying out centrifugal dehydration on the filter residue 1 to obtain a ferrous sulfate heptahydrate product;
step two:
preheating the filtrate 1 to 20-100 ℃, slowly adding phosphoric acid, uniformly mixing, reacting at a stirring speed of 100-300 rpm/min for 20-60 min, and aging for 6-24 h after the reaction is finished to obtain a precipitate;
step three:
filtering the precipitate obtained in the second step to obtain a filtrate 2 and a filter residue 2, washing the filter residue 2 with dilute sulfuric acid with the mass concentration of 10-30% for 3-5 times, washing with distilled water for 3-5 times, and drying to obtain amorphous titanium phosphate;
step four:
and roasting the amorphous titanium phosphate obtained in the step three at the temperature of 200-1200 ℃ for 2-3 h to obtain titanium phosphate or titanium pyrophosphate.
2. The integrated recovery process of claim 1, further comprising:
step five:
adding pyrolusite into the pickling water washing solution of the filtrate 2 and the filter residue 2 obtained in the third step for reaction, and filtering and washing after the reaction to obtain a filtrate 3 and a filter residue 3;
step six:
adding rhodochrosite into the filtrate 3 obtained in the fifth step for reaction, and filtering and washing after the reaction to obtain filtrate 4 and filter residue 4;
step seven:
evaporating and crystallizing the filtrate 4 obtained in the sixth step to obtain manganese sulfate monohydrate, or electrolyzing to obtain electrolytic manganese metal;
the filter residue 3 and the filter residue 4 are used for preparing environmental mineral materials.
3. The comprehensive recovery method of claim 2, wherein the amount of MnO required for the reaction of the acid washing solution of the filtrate 2 and the residue 2 is added in the step five20.8-1.2 times of theoretical dosage, 40-100 ℃ of reaction temperature, 1.5-3 hours of reaction time and 100-300 rpm/min of stirring speed.
4. The integrated recovery method of claim 2, wherein the amount of rhodochrosite added in step six is MnCO required for reaction of filtrate 331.1-1.3 times of theoretical dosage, 0.3-0.6 acid-ore ratio, 40-100 ℃ reaction temperature, 3-4 h reaction time and 100-500 rpm/min stirring speed.
5. The composition according to any one of claims 1 to 4The comprehensive recovery method is characterized in that in the step one, the initial temperature of the titanium white waste acid is 30-40 ℃, the temperature reduction time is 2-4 h, and Fe in the liquid is cooled and crystallized2+≤17g/L。
6. The integrated recovery method according to any one of claims 1 to 4, wherein in the second step, the molar ratio of titanyl sulfate to phosphoric acid in the filtrate 1 is 1: 1.5 to 2.6.
7. The comprehensive recovery method according to any one of claims 1 to 4, wherein in the third step, the drying temperature is 50 to 100 ℃ and the drying time is 2 to 4 hours.
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| CN115231540A (en) * | 2022-08-05 | 2022-10-25 | 山东鲁北国际新材料研究院有限公司 | Method for preparing titanium phosphate from byproduct waste acid generated in titanium dioxide production by chlorination process |
| CN115959642A (en) * | 2022-10-29 | 2023-04-14 | 宜宾天原科创设计有限公司 | Method for utilizing hydrochloric acid byproduct of titanium dioxide chloride |
| CN115924870A (en) * | 2022-12-09 | 2023-04-07 | 山东鲁北企业集团总公司 | Method and device for preparing iron phosphate and co-producing white gypsum by using artificial rutile waste liquid |
| CN116002768A (en) * | 2022-12-14 | 2023-04-25 | 攀枝花市海峰鑫化工有限公司 | Method for recycling ferrous sulfate heptahydrate and sulfuric acid from titanium dioxide waste acid |
| CN116143181A (en) * | 2023-02-01 | 2023-05-23 | 武汉新培新能源科技有限公司 | Method for removing impurities in titanium dioxide byproduct ferrous sulfate heptahydrate and application thereof |
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