CN1396119A - Process for comprehensive utilization of waste acid containing titanium oxide - Google Patents
Process for comprehensive utilization of waste acid containing titanium oxide Download PDFInfo
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Abstract
A process for reclaiming the water acid generated during preparing titanium oxide includes such steps as heating waste acid for hydrolysis to obtain metatitanic acid, returning it to the production line to prepare titanium yellow powder; and wet metallurgy of the filtrate generated by the said hydrolysis and the zinc contained oxide to obtain active zinc oxide, alkaline zinc carbonate, Fe2O3 and Zn-contained ammonium sulfate.
Description
One, the technical field
The invention relates to a method for treating waste acid generated in titanium dioxide production by a sulfuric acid method.
Second, background Art
The production methods of titanium dioxide (titanium dioxide) mainly include two methods: the chlorination process and the sulfuric acid process are mainly adopted in China due to the limitation of raw materials. The biggest problem of the sulfuric acid method is that 5-7 tons of waste sulfuric acid with the concentration of about 20 percent and a large amount of dilute acid are generated when one ton of titanium dioxide is produced, so that the treatment of the waste acid is a key problem which needs to be solved when the sulfuric acid method is used for preparing the titanium dioxide.
Regarding the treatment of titanium white waste acid, titanium white manufacturers in China have various modes: the method comprises the steps of neutralization discharge, production of salts such as potassium sulfate, ammonium sulfate, magnesium sulfate and the like, concentration and reuse and the like, but the method is not a satisfactory method, and is not large in investment and small in output, namely, one pollution is converted into the other pollution. Japan Shiyuan company has proposed a "stone method", namely produce the artificial rutile with the waste acid produced by sulfate process titanium dioxide production; the Beijing color metals research institute is also working on the research of preparing synthetic rutile from titanium white waste acid (see "Sichuan non-ferrous metals", No. 3 of 2001, P65), but there is a problem of treating waste acid containing high concentration of iron in view of the present disclosure.
Third, the invention
The invention provides a comprehensive utilization method for treating waste acid generated in titanium dioxide production by a sulfuric acid method aiming at the problems in the prior art, the process flow of the method is basically closed cycle by a full wet method, the technology is mature, the equipment is conventional, and no pollution is caused; can comprehensively recover acid, titanium and iron in the titanium white waste acid and prepare various products with high quality and added value and large market demand.
The technical scheme of the invention is as follows: and (3) treating titanium white waste acid by using a zinc hydrometallurgy process. Firstly, titanium white waste acid is heated and hydrolyzed, metatitanic acid obtained by hydrolysis returns to the main process of titanium white production or is used for preparing titanium yellow powder, and zinc-containing oxide raw materials are leached from filtrate obtained by hydrolysis and are used for preparing active zinc oxide, ferric oxide and zinc-containing ammonium sulfate.
1. The chemical reaction formula of the titanium white waste acid by heating hydrolysis is as follows: the process conditions are as follows: adding the variety, completing the reaction under stirring, boiling the temperature, controlling the time to limit the completion of the hydrolysis reaction,generally 1.5 to 2.5 hours. Filtering the metatitanic acid precipitate obtained by hydrolysis, washing with acidified water until no iron is detected, and washing with pure water. If the physical and chemical properties of the titanium dioxide are the same as those of the main process of titanium dioxide production, the titanium dioxide can return to the main process; if the physical and chemical properties are different from the main flow of titanium white production or titanium yellow powder needs to be prepared, the titanium yellow powder is used as a raw material for preparing the titanium yellow powder.
2. Preparation of titanium yellow powder from metatitanic acid
The process steps of preparing the titanium yellow powder by the metatitanic acid sequentially comprise drying, calcining and crushing; the drying and calcining is to obtain titanium yellow by drying and calcining a metatitanic acid filter cake obtained by filtering and washing, wherein the thermal decomposition chemical reaction formula of the metatitanic acid during calcining is as follows: the calcination temperature is 650-850 ℃, and the calcination time is 2-3 hours; the grinding is to prepare the titanium yellow into a powdery finished product.
3. Preparation of active zinc oxide from filtrate
The process steps of preparing the active zinc oxide from the filtrate sequentially comprise leaching, neutralizing, filtering and washing, precipitating alum, filtering and washing, secondary oxidation, filtering and washing, replacement, filtering and washing, precipitating ammonium, filtering and washing, drying, calcining and crushing. The leaching is to add zinc-containing oxide into the filtrate so as to make full use of a large amount of sulfuric acid contained in the filtrate. The main chemical reactions of the leaching process are as follows:
the accompanying side reactions are:
the leaching process conditions are as follows: and (3) completing the reaction under stirring, controlling the temperature to be 80-90 ℃, controlling the end point pH to be 1.5-1.8, and controlling the time to be 1-2 hours. And the neutralization is to add a neutralizing agent into the mixed liquid formed in the leaching process, and the end point pH is controlled to be 5-5.4, so that the impurity removal of the mixed liquid formed in the leaching process is facilitated. The alum deposition is that ammonium persulfate is added into the filtrate after primary impurity removal (Pb, In, Ge, etc.) by filtration and washing to ensure that Fe2+Oxidation to Fe3+And producing ammonioiarosite, thus purifying the raw material for preparing the active zinc oxide and obtaining the raw material for preparing the ferric oxide. Oxidation of Fe by ammonium persulphate2+Is Fe3+The reaction formula (c) is as follows:
the adding amount of ammonium persulfate is Fe in the oxidizing solution2+90-100% of the required theoretical amount.
The generation reaction of the ammonium jarosite is as follows:
the process conditions for precipitating alum are as follows: adding seed crystals, completing the reaction at the temperature of 90-boiling for 1-4 hours under stirring, adding a neutralizing agent to keep the pH of the reaction liquid at 1.5-2, precipitating alum, and finally adjusting the pH of the reaction liquid to 4-4.5 for half an hour. The secondary oxidation is to add potassium permanganate solution into the filtrate of the ammonioiarosite filtration to remove Mn by oxidation2+And Fe2+The main chemical reaction is as follows:
the process conditions of the secondary oxidation are as follows: the reaction is completed under stirring, the temperature is 60-70 ℃, the time is 40 minutes-1 hour, and the end point pH is controlled to be 4-4.5. The replacement is to add zinc powder into the filtrate for filtering manganese slag and iron slag to further purify the solution, and the main chemical reaction is as follows:
the process conditions of the replacement are as follows: the reaction is completed under stirring, the adding amount of the zinc powder is 1.5-2 times of the theoretical amount, the temperature is controlled to be 60-80 ℃, the final pH value of the solution is 5-5.4, and the time is 1.5-2 hours. Ammonium precipitation is to add ammonium carbonate saturated liquid into the filtrate of which the replacement slag is filtered off to obtain basic zinc carbonate, and the reaction formula is as follows:
the process conditions of ammonium precipitation are as follows: the reaction temperature is 40-50 ℃, the end point pH is controlled at 6.8-7.0, the temperature is raised to 70-75 ℃ and stirred for 1 hour, and finally the heat preservation and precipitation are carried out for 3-4 hours at 60 ℃. Drying is to dry the basic zinc carbonate filter cake obtained by filtering and washing to ensure that the water content is less than 2.5 percent, and calcining is to thermally decompose the basic zinc carbonate to obtain the active zinc oxide, wherein the reaction formula is as follows:
the calcination temperature is 450-500 ℃, and the calcination time is 2-3 hours. The crushing is to prepare the blocky active zinc oxide into a finished product.
4. Preparation of iron sesquioxide
The ferric oxide is prepared by taking ammoniojarosite obtained in the alum precipitation process as a raw material, and the process steps sequentially comprise drying, calcining and crushing, wherein the calcining temperature is 700-950 ℃, and the calcining time is 2-2.5 hours. The thermal decomposition reaction formula during calcination is as follows:
SO produced by calcination3And SO2Can be absorbed by ammonium carbonate solution to generate ammonium sulfate solution for preparing zinc-containing ammonium sulfate.
5. Preparation of zinc-containing ammonium sulfate
The preparation of the zinc-containing ammonium sulfate takes the filtrate generated by filtering and washing basic zinc carbonate and the solution formed by absorbing sulfur trioxide and sulfur dioxide generated by calcining ammonioiarosite by ammonium bicarbonate as raw materials, and the process steps are concentration, cooling crystallization and drying in sequence.
Besides the comprehensive utilization scheme, part of the basic zinc carbonate obtained in the ammonium precipitation step can be used for preparing active zinc oxide after being filtered, washed and dried, and part of the basic zinc carbonate can be used for preparing a finished product of the basic zinc carbonate. If the basic zinc carbonate finished product is prepared, the dried basic zinc carbonate is crushed according to the requirement.
In order to minimize environmental pollution, ammonium carbonate solution formed by absorbing carbon dioxide generated by calcining basic zinc carbonate with ammonia water can be used as a supplementary raw material for the ammonium precipitation process.
In the comprehensive utilization scheme, the seed crystal used in the heating hydrolysis process is prepared from ammonia water and titanium dioxide waste acid, and the addition amount of the seed crystal is 1-1.5% of the amount of titanium dioxide (converted) contained in the titanium dioxide waste acid; the zinc-containing oxide added in the leaching process is zinc calcine or zinc smoke dust or hot galvanizing ash subjected to calcination andalkaline leaching treatment; the neutralizing agent added in the neutralization step is ammonia water or the combination of ammonia water and any one of zinc calcine, zinc smoke dust, hot-dip galvanizing ash and calcium carbonate powder; the seed crystal added in the alum precipitation procedure is ammoniojarosite, and the neutralizer is ammonia water and/or basic zinc carbonate.
The invention has the following beneficial effects:
1. the provided method can comprehensively recover useful substances in the titanium white waste acid and prepare the useful substances into titanium yellow powder, active zinc oxide, ferric oxide, basic zinc carbonate and a zinc-containing ammonium sulfate compound fertilizer, and the product has the advantages of low cost, high quality and strong market competitive advantage.
2. The whole process flow is basically closed-loop circulation of a full wet method, and the problem of environmental pollution in the treatment of titanium white waste acid is effectively solved.
3. The zinc hydrometallurgy technology is mature, the equipment is conventional, and the industrial production is easy to realize.
Description of the drawings
FIG. 1 is a process flow diagram of the comprehensive utilization of titanium dioxide waste acid proposed by the present invention;
FIG. 2 is another process flow diagram of the comprehensive utilization method of titanium dioxide waste acid.
Fifth, detailed description of the invention
Example 1:
the process flow of the comprehensive utilization method of titanium white waste acid in the embodiment is shown in fig. 1, the titanium white waste acid is heated and hydrolyzed, metatitanic acid obtained by hydrolysis is used for preparing titanium yellow powder, and filtrate obtained by hydrolysis is used for preparing active zinc oxide and iron oxide red (Fe)2O3) And zinc-containing ammonium sulfate.
(1) Heating hydrolysis of titanium white waste acid
The components and the contents (weight percentage) of the components of the titanium white waste acid are as follows:
H2SO420.3 Fe 2.4
Mg 0.5 Ca 0.0037
TiO29.51 V 0.0009
Co 0.00095
the equipment is provided with heating and temperature control,A condensation reflux device and a reaction kettle of a stirrer. The process conditions are as follows: adding 1% of seed crystal (weight percentage) according to TiO2Calculating the content, wherein the seed crystal is prepared from ammonia water and titanium dioxide waste acid, and the adding amount of the ammonia water is limited by the fact that the terminal pH of the obtained titanium dioxide waste acid reaches 2-4; boiling at the temperature; the stirring speed is 120 r/min; the time is 2 hours.
(2) Preparing titanium yellow powder
Filtering metatitanic acid precipitate obtained by hydrolysis, washing with sulfuric acid acidified water with pH of 1.5 until no iron is detected, washing with pure water to obtain metatitanic acid filter cake, drying the filter cake at 110 deg.C, calcining at 650 deg.C, 800 deg.C, 850 deg.C for 2 hr, and pulverizing to obtain titanium yellow powder. TiO thereof2The contents are 93.6%, 98.07% and 99.26% (weight percentage) respectively, and the indexes of GB1706-93 and ZGB13004-90 of national standard and ministry of China are achieved.
(3) Preparation of activated Zinc oxide
Leaching, neutralizing, filtering and washing, precipitating alum, filtering and washing, secondary oxidizing, filtering and washing, replacing, filtering and washing, precipitating ammonium, filtering and washing, drying, calcining and crushing the filtrate obtained by hydrolysis to obtain the finished product of the active zinc oxide. Each of the above filtration and washing steps was washed with acidified water of sulfuric acid having a pH of 5. Zinc-containing oxidation added in leaching processThe material is a mixture of zinc flue powder and dust collecting white powder, and the composition (weight percentage) of the material is as follows:
| name (R) | Zinc flue powder | Dust collecting white powder | Mixture material (actual measurement value) | |||||
| Proportioning | 30％ | 70％ | ||||||
| Composition of | ZnO | Ge | In | Pb | Cl | Co | ZnO | ZnO |
| Content (%) | 55 | 0.02-0.04 | 0.3 | 8-10 | 0.4 | Micro-scale | 80 | 73.114 |
The process conditions and process parameters are as follows: zinc-containing oxide and titanium dioxide waste acid hydrolysis filtrate are 1: 7 (weight ratio); the temperature is 85 ℃; the time is 1 hour; the stirring speed is 120 r/min; the end point pH was 1.8.
The neutralizing agent added in the neutralization process is ammonia water and hot-dip galvanizing ash fine powder, and the final pH value is controlled to be 5.2.
The process conditions of the alum deposition procedure are as follows: the temperature is 95 ℃; zn2+103.9 g/l; sigma Fe 23.8 g/l; the adding amount of ammonium persulfate is 95 percent of the theoretical amount; the seed crystal is ammonium jarosite, and the addition amount is 150 g/L; controlling the pH value of the precipitated alum to be 1.8; the stirring speed is 120 r/min; the time is 4 hours; neutralizing agent basic zinc carbonate, and adjusting pH to 4 after 3.5 hours of alum precipitation.
The process conditions of the secondary oxidation process are as follows: the temperature is 60 ℃; the stirring speed is 120 r/min; oxidizing with 0.5% potassium permanganate solution for 1 hr, and controlling the pH value at the end point of the solution to 4.5.
The process conditions of the replacement procedure are as follows: the temperature is 60 ℃; the dosage of the zinc powder is 2 times of the theoretical quantity; the stirring speed is 120 r/min; the end point of the solution is pH5.4; the time is 1.5 hours.
The process conditions of the ammonium precipitation procedure are as follows: the ammonium precipitation temperature is 40 ℃; end point pH7.0; the adding amount of the ammonium bicarbonate saturated solution is limited by the pH value of the end point of the reaction solution reaching 7.0; when the pH of the reaction solution reaches 7.0, the temperature is raised to 70 ℃, the reaction solution is stirred for 1 hour, and finally the reaction solution is subjected to heat preservation and precipitation for 4 hours at the temperature of 60 ℃.
The drying temperature in the drying step was 105 ℃.
The calcination temperature in the calcination step was 500 ℃ and the calcination time was 2 hours. The active zinc oxide prepared by the embodiment reaches the index of national ministry standard HG/T2572-94.
(4) Preparation of iron Red (Fe)2O3)
Filtering and washing ammoniojarosite obtained in the alum precipitation step to form a filter cake, drying the filter cake at 110 ℃, calcining the filter cake at 700 ℃, 750 ℃, 800 ℃ and 850 ℃ for 2 hours, and crushing the filter cake to obtain Fe2O3The contents are 85.45%, 95.96%, 96.15% and 98.2% respectively, and all reach the indexes of national standard GB1863-89 and ministerial standard HG/T2574-94.
(5) Preparation of zinc-containing ammonium sulfate
And (3) concentrating, cooling, crystallizing and drying a solution formed by absorbing the filtrate generated by filtering and washing basic zinc carbonate and sulfur trioxide generated by calcining ammonioiarosite by using ammonium bicarbonate solution to obtain the zinc-containing ammonium sulfate. The ammonium sulfate prepared in this example contained 17.26% N, 1.52% ZnH, and a small amount of NH4Cl、MgCl2And MgSO4。
The amount of each product prepared in this example calculated for treating 1 ton of titanium dioxide waste acid was: 89kg of titanium yellow powder, 128kg of active zinc oxide and iron oxide red (Fe)2O3)35kg, zinc-containing ammonium sulfate 200 kg.
Example 2:
the process flow of the comprehensive utilization method of titanium dioxide waste acid in the embodiment is shown in fig. 2, the titanium dioxide waste acid is heated and hydrolyzed, metatitanic acid obtained by hydrolysis returns to the main flow of titanium dioxide production, and filtrate obtained by hydrolysis is used for preparing active zinc oxide, basic zinc carbonate and iron oxide red (Fe)2O3) And zinc-containing ammonium sulfate.
The present embodiment differs from embodiment 1 as follows:
(1) the metatitanic acid obtained by hydrolysis returns to the main flow of titanium dioxide production.
(2) The zinc-containing oxide added in the leaching process for preparing the basic zinc carbonate and the active zinc oxide is prepared by calcining hot galvanizing ash containing 77 percent of zinc and alkaline leaching. The calcination process conditions are as follows: the calcining temperature is 500 ℃, and the calcining time is 2 hours. The process conditions of alkaline leaching are as follows: calcined Zinc Ash: 2% (NaOH + Na)2CO3) Liquid is 1: 1 (weight ratio); the temperature is normal temperature; the time period was 6 hours. And (5) after the alkaline leaching is finished, filtering and washing for later use.
(3) Filtering, washing and drying the basic zinc carbonate obtained in the ammonium precipitation step, wherein the half of the basic zinc carbonate is used for preparing an active zinc oxide finished product, and the half of the basic zinc carbonate is directly crushed into the basic zinc carbonate finished product.
(4) And absorbing carbon dioxide generated by calcining the basic zinc carbonate filter cake with ammonia water to form ammonium bicarbonate solution as a supplementary raw material for the ammonium precipitation process.
(5) The neutralizing agents used in the neutralization step of this example were ammonia and calcium carbonate powders.
The amount of each product prepared in this example calculated for treating 1 ton of titanium dioxide waste acid was: 62kg of active zinc oxide, 91kg of basic zinc carbonate and iron oxide red (Fe)2O3)34kg, zinc-containing ammonium sulfate 202 kg.
Claims (8)
1. A comprehensive utilization method of titanium white waste acid is characterized in that:
(1) heating titanium white waste acid for hydrolysis, returning metatitanic acid obtained by hydrolysis to the main process of titanium white production or for preparing titanium yellow powder, leaching zinc-containing oxidation materials from filtrate obtained by hydrolysis to prepare active zinc oxide, ferric oxide and zinc-containing ammonium sulfate,
(2) the titanium white waste acid is heated and hydrolyzed by adding seed crystals under stirring, the temperature is controlled to ensure that the titanium white waste acid is boiled, the time is controlled to limit the completion of the hydrolysis reaction,
(3) the process for preparing titanium yellow powder from metatitanic acid sequentially comprises the steps of drying, calcining and crushing, wherein the drying, calcining and calcining are carried out on metatitanic acid filter cakes obtained by filtering and washing, the calcining temperature is 650-850 ℃, the calcining time is 2-3 hours, the crushing is carriedout, the titanium yellow is prepared into a powdery finished product,
(4) the process for preparing the active zinc oxide from the filtrate sequentially comprises the steps of leaching, neutralizing, filtering and washing, precipitating alum, filtering and washing, secondary oxidizing, filtering and washing, replacing, filtering and washing, ammonium precipitating, filtering and washing, drying, calcining and crushing, wherein the leaching comprises the steps of adding zinc-containing oxide into the filtrate, completing chemical reaction under stirring, controlling the temperature to be 80-90 ℃, controlling the final pH to be 1.5-1.8 and the time to be 1-2 hours, the neutralizing comprises the steps of adding a neutralizing agent into a mixed solution formed in the leaching process, controlling the final pH to be 5-5.4, precipitating alum, adding ammonium persulfate into the filtrate after primary impurity removal through filtering and washing, and leading Fe to be Fe2+Oxidation to Fe3+And producing ammoniojarosite, the amount of ammonium persulfate added being Fe in the oxidizing solution2+90-100% of the required theoretical amount, adding seed crystals in the reaction, completing the reaction under stirring, controlling the temperature at 90-boiling for 1-4 hours, adding a neutralizing agent to keep the pH of the reaction solution at 1.5-2, precipitating alum, adjusting the pH of the reaction solution to 4-4.5 in the last half hour, and performing secondary oxidation by adding a potassium permanganate solution into the filtrate of the ammonium jarosite to be filtered to remove Mn through oxidation2+And Fe2+The reaction is completed under stirring, the temperature is controlled to be 60-70 ℃, the reaction time is 40 minutes to 1 hour, the end point pH is controlled to be 4-4.5, the replacement is to add zinc powder into the filtrate from which the manganese slag and the iron slag are removed to purify the solution, the reaction is completed under stirring, the adding amount of the zinc powder is 1.5-2 times of the theoretical amount, the temperature is controlled to be 60-80 ℃, the end point pH of the solution is 5-5.4, the reaction time is 1.5-2 hours, the ammonium precipitation is to add ammonium carbonate saturated solution into the filtrate from which the replacement slag is removed, the reaction temperature is 40-50 ℃, the end point pH is controlled to be 6.8-7.0, the temperature is raised to 70-75 ℃, the stirring is performed for 1 hour, the basic zinc carbonate is finally subjected to heat preservation and precipitation at 60 ℃ for 3-4 hours to obtain the basic zinc carbonate, the drying is to dry the basic zinc carbonate filter cake obtained by filtering and washing, the calcination is to thermally decompose the basic zinc carbonate to obtain the, the crushing is to prepare the massive active zinc oxide into a finished product,
(5) the ferric oxide is prepared by drying and calcining an ammonium jarosite filter cake, the calcining temperature is 700-950 ℃, the calcining time is 2-2.5 hours, the blocky ferric oxide obtained by calcining is crushed into a finished product,
(6) the zinc-containing ammonium sulfate is prepared by concentrating, cooling, crystallizing and drying a solution formed by absorbing sulfur trioxide and sulfur dioxide generated by filtering and washing basic zinc carbonate and calcining ammonioiarosite by a ammonium bicarbonate solution.
2. The process of claim 1, wherein the basic zinc carbonate cake is crushed to produce a finished basic zinc carbonate product.
3. The comprehensive utilization method of titanium dioxide waste acid according to claim 1 or 2, characterized in that carbon dioxide generated by calcining basic zinc carbonate is absorbed by ammonia water to form ammonium bicarbonate solution as supplementary raw material for ammonium precipitation process.
4. The comprehensive utilization method of titanium dioxide waste acid according to claim 1 or 2, characterized in that the seed crystal used in the heating hydrolysis process is prepared from ammonia water and titanium dioxide waste acid, and the addition amount of the seed crystal is 1-1.5% of the amount of titanium dioxide contained in the titanium dioxide waste acid.
5. The comprehensive utilization method of titanium dioxide waste acid according to claim 3, characterized in that the seed crystal used in the heating hydrolysis process is prepared from ammonia water and titanium dioxide waste acid, and the addition amount of the seed crystal is 1-1.5% of the amount of titanium dioxide contained in the titanium dioxide waste acid.
6. The comprehensive utilization method of titanium dioxide waste acid according to claim 1 or 2, characterized in that the zinc-containing oxide added in the leaching process is zinc calcine or zinc dust or hot-dip galvanized ash subjected to calcination and alkaline leaching treatment.
7. The comprehensive utilization method of titanium dioxide waste acid according to claim 1 or 2, characterized in that the neutralizing agent added in the neutralization step is ammonia water or the combination of ammonia water and any one of zinc calcine, zinc soot, hot-dip galvanizing ash and calcium carbonate powder.
8. The comprehensive utilization method of titanium dioxide waste acid according to claim 1 or 2, characterized in that the seed crystal added in the alum precipitation process is ammoniojarosite, and the neutralizing agent is ammonia and/or basic zinc carbonate.
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| CN113213529B (en) * | 2021-05-26 | 2022-08-02 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for producing titanium dioxide by sulfuric acid process and recycling metatitanic acid in titanium dioxide waste acid |
| CN114540638A (en) * | 2022-01-11 | 2022-05-27 | 云南云铜锌业股份有限公司 | Zinc leachate purification method |
| CN114540638B (en) * | 2022-01-11 | 2024-02-27 | 云南云铜锌业股份有限公司 | Zinc leaching solution purifying method |
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