CN111485102A - Process for full-recycling titanium white waste acid - Google Patents
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Abstract
The invention relates to a process for fully utilizing titanium white waste acid, which specifically comprises the following steps: 1) reducing and leaching manganese oxide ore by using titanium white waste acid and ferrous sulfate to prepare an iron oxide normal-temperature desulfurizer; 2) magnesium soap extraction is carried out on the leached manganese ferric sulfate solution to separate manganese iron; 3) and treating with an organic phase extractant to recover vanadium, titanium, iron and scandium respectively. The invention has the advantages that: the P204/507 is adopted to extract vanadium-titanium-scandium ions of the titanium white-enriched waste acid, so that the titanium white waste acid is utilized in a full resource manner in a real sense, no new three wastes are generated, the energy-saving and environment-friendly concept is met, and the method has a good popularization prospect in the technical field.
Description
Technical Field
The invention relates to the technical field of environment-friendly processes, in particular to a process for fully recycling titanium white waste acid.
Background
The method is characterized in that a solid phase method is a main method for preparing commercial lithium iron phosphate, but a divalent iron source is high in cost and difficult to store, the synthesized lithium iron phosphate has large particle size (D is more than 1 mu m), poor uniformity and other defects and is difficult to meet the requirements of a power lithium ion battery, Barker applies a carbothermic reduction method to L iFePO4 preparation, ferric iron with low cost and stable performance is adopted to replace divalent iron to serve as an iron source when the carbothermic reduction method is used for synthesizing L iFePO4, excessive carbon is added into the raw materials, Fe3+ is reduced into Fe2+ by the carbon at high temperature to prepare L iFePO4, the residual carbon plays a role as a conductive agent in L iFePO4 products, the iron source for preparing the lithium iron phosphate by the carbothermic reduction method is mainly a carbon source, but the iron phosphate is not suitable for preparing the iron phosphate sold on the iron phosphate market, the iron phosphate has large and uneven particle size and large difference in crystallinity, the particle size is large and uneven, so that the particle size of the synthesized lithium iron phosphate is not suitable for preparing a nano-scale lithium iron phosphate precursor CN, the nano-scale lithium iron phosphate is not suitable for preparing a nano-scale lithium iron phosphate, the nano-scale lithium iron phosphate with the non-scale active material with the non-scale active carbon nano-size, the non-particle size, the nano-size of the CN-size, the CN-size of the method for preparing the nano-size active lithium iron phosphate is not suitable for preparing the nano-size of the nano-size lithium iron phosphate is disclosed in the nano-size active lithium iron phosphate is not suitable for preparing the nano-size active lithium iron phosphate, the nano-size of the nano-size active lithium iron phosphate, the nano-size lithium iron phosphate is not suitable for preparing the nano-size active lithium iron phosphate
The ecological environment capability of the manganese ore industry development analyzes and utilizes manganese resources to promote economic rapid development, and besides the relationship between the utilization efficiency of the manganese resources and the industrial benefit, the relationship of the resource stock to the environmental stress game also exists. While the ecological environment quality index is gradually reduced, the manganese ore industry coordination is gradually improved, which shows that the dependence of the Guangxi manganese ore industry development on the ecological environment is gradually reduced. The development of circular economy, the construction of ecological parks, the implementation of green industry can gradually reduce the damage to the ecological environment.
Titanium dioxide production enterprises adopt a sulfuric acid method to produce titanium dioxide, and the sulfuric acid method for producing titanium dioxide can produce a large amount of titanium dioxide waste acid. If not properly treated, the titanium white waste acid can cause serious pollution to the local environment. At present, the titanium white waste acid treatment modes are roughly divided into two modes, wherein the first mode is to neutralize the waste acid and quicklime to generate calcium sulfate precipitation and then stack neutralized slag into a slag yard; the second mode is that the waste acid is heated by steam to be concentrated in vacuum, the concentration of the waste acid is increased to 70%, and then the waste acid is mixed with 98% concentrated sulfuric acid to be returned to the titanium dioxide acidolysis section for use. The first treatment mode can generate a large amount of sulfate slag, and the sulfate slag can only be discarded and stacked due to high impurity content and no recycling value, and occupies a large amount of land resources. The second treatment method is complex in process and high in recovery cost, so that not all titanium dioxide production enterprises have conditional application. Therefore, each titanium dioxide production enterprise needs to find a more economic and reasonable titanium dioxide waste acid recovery treatment method, so that waste materials can be changed into valuable materials, and resources can be reused.
Disclosure of Invention
The invention aims to provide a process for fully recycling titanium dioxide waste acid so as to solve the problems in the background technology.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a process for full-recycling titanium white waste acid specifically comprises the following steps:
1) reducing and leaching manganese oxide ore by using titanium white waste acid and ferrous sulfate to prepare the iron oxide normal-temperature desulfurizer: adopting manganese oxide ore to oxidize iron ions in the titanium white waste acid, simultaneously reducing and leaching manganese ions in the manganese oxide ore by utilizing the titanium white waste acid and ferrous sulfate, carrying out solid-liquid separation after leaching to obtain solid leaching slag and a leached ferric manganese sulfate solution, adding ferrous sulfate lime into the solid leaching slag, mixing, extruding into strips for forming, and drying to obtain the ferric oxide normal-temperature desulfurizer;
2) performing magnesium soap extraction on the leached manganese ferric sulfate solution to separate manganese iron: the method comprises the steps of saponifying an extractant by using magnesium oxide by using a magnesium oxide saponification extractant technology for leached iron-manganese sulfate solution, filtering the saponified extractant, separating saponification slag, converting the extractant from magnesium soap into manganese soap by using a manganese sulfate solution, and mixing the manganese soap with the leached iron-manganese sulfate solution for extraction to remove iron; controlling the pH value of the manganese sulfate solution after the residual iron extraction to be 1.9-2.2, introducing hydrogen sulfide into the manganese sulfate solution for sulfurizing and depositing lead, then adjusting the pH value to be 5.5, adding 5-40% fluosilicic acid for removing calcium, then aging for 24 hours, and then filtering and separating to obtain a refined manganese sulfate solution; carrying out MVR evaporation concentration on the refined manganese sulfate solution, and carrying out hydrothermal precipitation in a high-pressure anticorrosion container at the temperature of 180 ℃ and 200 ℃ to obtain battery-grade manganese sulfate monohydrate slurry; then, reducing the pressure to 0.3MPa to normal pressure through three-stage pressure reduction and two-stage flash evaporation, discharging the obtained product into a centrifugal machine for solid-liquid separation, then sending the obtained product into a flash evaporation dryer for drying, and packaging the obtained product to obtain commercial battery grade manganese sulfate monohydrate;
3) and (3) treating an organic phase extractant to respectively recover vanadium, titanium, iron and scandium: firstly, backwashing an organic phase extracting agent by 3 mol of sulfuric acid to remove metal ions, and respectively recovering titanium and vanadium from a water phase by hydrolyzing and precipitating titanium and vanadium by ammonium salt; carrying out back extraction on the organic phase extractant by using 6-8 mol of hydrochloric acid to obtain a liquid ferric trichloride solution after the back extraction, precipitating high-purity ferric phosphate dihydrate by using ammonium phosphate in one part of the liquid ferric trichloride solution after the back extraction, and drying and packaging to obtain a battery-grade ferric phosphate product; neutralizing and precipitating iron with at least one of calcium oxide, magnesium oxide, liquid ammonia and ammonia water to produce iron oxide pigment in the other part of ferric trichloride solution as iron-removing solution; evaporating and crystallizing the liquid after iron precipitation by using MVR to produce salts corresponding to the iron precipitation agent; carrying out back extraction of scandium on the organic phase extractant after iron stripping by using 2 mol of sodium hydroxide solution, then carrying out oil-water separation, adding oxalic acid into the solution after scandium stripping, precipitating to obtain scandium oxalate, and calcining the scandium oxalate to recover high-purity scandium oxide; and (3) washing the organic phase extractant subjected to scandium back extraction by deionized water to remove sodium ions, and then repeatedly using the organic phase extractant to carry out water treatment on the washed sodium ions.
As a preferable scheme, the extracting agents are all P204, and the organic phase extracting agents are all organic phase P204.
Preferably, the extracting agents are all P507, and the organic phase extracting agents are all organic phase P507.
The invention has the advantages that: the P204/507 is adopted to extract vanadium-titanium-scandium ions of the titanium white-enriched waste acid, so that the titanium white waste acid is utilized in a full resource manner in a real sense, no new three wastes are generated, the energy-saving and environment-friendly concept is met, and the method has a good popularization prospect in the technical field.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is illustrated below by means of specific examples, without being restricted thereto.
Example 1
A process for full-recycling titanium white waste acid specifically comprises the following steps:
1) reducing and leaching manganese oxide ore by using titanium white waste acid and ferrous sulfate to prepare the iron oxide normal-temperature desulfurizer: adopting manganese oxide ore to oxidize iron ions in the titanium white waste acid, simultaneously reducing and leaching manganese ions in the manganese oxide ore by utilizing the titanium white waste acid and ferrous sulfate, carrying out solid-liquid separation after leaching to obtain solid leaching slag and a leached ferric manganese sulfate solution, adding ferrous sulfate lime into the solid leaching slag, mixing, extruding into strips for forming, and drying to obtain the ferric oxide normal-temperature desulfurizer;
2) performing magnesium soap extraction on the leached manganese ferric sulfate solution to separate manganese iron: the method comprises the steps of saponifying P204 with magnesium oxide by adopting a magnesium oxide saponification P204 technology for a leached iron manganese sulfate solution, filtering the saponified P204, separating out saponification slag, converting the P204 from magnesium soap into manganese soap with a manganese sulfate solution, and mixing the manganese soap with the leached iron manganese sulfate solution for extraction and iron removal; controlling the pH value of the manganese sulfate solution after the residual iron extraction to be 1.9-2.2, introducing hydrogen sulfide into the manganese sulfate solution for sulfurizing and depositing lead, then adjusting the pH value to be 5.5, adding 5-40% fluosilicic acid for removing calcium, then aging for 24 hours, and then filtering and separating to obtain a refined manganese sulfate solution; carrying out MVR evaporation concentration on the refined manganese sulfate solution, and carrying out hydrothermal precipitation in a high-pressure anticorrosion container at the temperature of 180 ℃ and 200 ℃ to obtain battery-grade manganese sulfate monohydrate slurry; then, reducing the pressure to 0.3MPa to normal pressure through three-stage pressure reduction and two-stage flash evaporation, discharging the obtained product into a centrifugal machine for solid-liquid separation, then sending the obtained product into a flash evaporation dryer for drying, and packaging the obtained product to obtain commercial battery grade manganese sulfate monohydrate;
3) and (3) treating an organic phase P204 to respectively recover vanadium, titanium, iron and scandium: firstly, backwashing the organic phase P204 by 3 mol of sulfuric acid to remove metal ions, and respectively recovering titanium and vanadium from the water phase by hydrolyzing and precipitating titanium and vanadium by ammonium salt; carrying out back extraction on the organic phase P204 by using 6-8 mol of hydrochloric acid to obtain a liquid ferric trichloride solution after the back extraction, precipitating high-purity ferric phosphate dihydrate by using ammonium phosphate in one part of the liquid ferric trichloride solution after the back extraction, and drying and packaging to obtain a battery-grade ferric phosphate product; neutralizing and precipitating iron with at least one of calcium oxide, magnesium oxide, liquid ammonia and ammonia water to produce iron oxide pigment in the other part of ferric trichloride solution as iron-removing solution; evaporating and crystallizing the liquid after iron precipitation by using MVR to produce salts corresponding to the iron precipitation agent; carrying out scandium back-extraction on the organic phase P204 after iron back-extraction by using 2 mol of sodium hydroxide solution, then carrying out oil-water separation, adding oxalic acid into the solution after scandium back-extraction, precipitating to obtain scandium oxalate, and calcining the scandium oxalate to recover high-purity scandium oxide; and (3) washing the organic phase P204 subjected to scandium back extraction by deionized water to remove sodium ions, and then repeatedly using the washed sodium ions to perform water treatment.
Example 2
A process for full-recycling titanium white waste acid specifically comprises the following steps:
1) reducing and leaching manganese oxide ore by using titanium white waste acid and ferrous sulfate to prepare the iron oxide normal-temperature desulfurizer: adopting manganese oxide ore to oxidize iron ions in the titanium white waste acid, simultaneously reducing and leaching manganese ions in the manganese oxide ore by utilizing the titanium white waste acid and ferrous sulfate, carrying out solid-liquid separation after leaching to obtain solid leaching slag and a leached ferric manganese sulfate solution, adding ferrous sulfate lime into the solid leaching slag, mixing, extruding into strips for forming, and drying to obtain the ferric oxide normal-temperature desulfurizer;
2) performing magnesium soap extraction on the leached manganese ferric sulfate solution to separate manganese iron: the method comprises the following steps of (1) saponifying P507 with magnesium oxide by adopting a magnesium oxide saponification P507 technology for a leached iron manganese sulfate solution, filtering the saponified P507, separating saponification slag, converting the P507 from a magnesium soap into a manganese soap with a manganese sulfate solution, and mixing the manganese soap with the leached iron manganese sulfate solution for extraction and iron removal; controlling the pH value of the manganese sulfate solution after the residual iron extraction to be 1.9-2.2, introducing hydrogen sulfide into the manganese sulfate solution for sulfurizing and depositing lead, then adjusting the pH value to be 5.5, adding 5-40% fluosilicic acid for removing calcium, then aging for 24 hours, and then filtering and separating to obtain a refined manganese sulfate solution; carrying out MVR evaporation concentration on the refined manganese sulfate solution, and carrying out hydrothermal precipitation in a high-pressure anticorrosion container at the temperature of 180 ℃ and 200 ℃ to obtain battery-grade manganese sulfate monohydrate slurry; then, reducing the pressure to 0.3MPa to 0.6MPa through three-stage pressure reduction and two-stage flash evaporation, discharging the obtained product into a centrifuge for solid-liquid separation, then sending the obtained product into a flash evaporation dryer for drying, and packaging the obtained product to obtain commercial battery grade manganese sulfate monohydrate;
3) and (3) treating an organic phase P507 to recover vanadium, titanium, iron and scandium respectively: firstly, backwashing the organic phase P507 by 3 mol of sulfuric acid to remove metal ions, and respectively recovering titanium and vanadium from the water phase by hydrolyzing and precipitating titanium and vanadium by ammonium salt; carrying out back extraction on the organic phase P507 by using 6-8 mol of hydrochloric acid to obtain a liquid ferric trichloride solution after the back extraction, precipitating high-purity ferric phosphate dihydrate by using ammonium phosphate in one part of the liquid ferric trichloride solution after the back extraction, and drying and packaging to obtain a battery-grade ferric phosphate product; neutralizing and precipitating iron with at least one of calcium oxide, magnesium oxide, liquid ammonia and ammonia water to produce iron oxide pigment in the other part of ferric trichloride solution as iron-removing solution; evaporating and crystallizing the liquid after iron precipitation by using MVR to produce salts corresponding to the iron precipitation agent; carrying out scandium back extraction on the organic phase P507 after iron back extraction by using 2 mol of sodium hydroxide solution, then carrying out oil-water separation, adding oxalic acid into the solution after scandium back extraction, precipitating to obtain scandium oxalate, and calcining the scandium oxalate to recover high-purity scandium oxide; and (3) washing the organic phase P507 subjected to scandium back extraction by deionized water to remove sodium ions, and then repeatedly using the washed sodium ions to perform water treatment.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (3)
1. A process for full-recycling titanium white waste acid is characterized by comprising the following steps:
1) reducing and leaching manganese oxide ore by using titanium white waste acid and ferrous sulfate to prepare the iron oxide normal-temperature desulfurizer: adopting manganese oxide ore to oxidize iron ions in the titanium white waste acid, simultaneously reducing and leaching manganese ions in the manganese oxide ore by utilizing the titanium white waste acid and ferrous sulfate, carrying out solid-liquid separation after leaching to obtain solid leaching slag and a leached ferric manganese sulfate solution, adding ferrous sulfate lime into the solid leaching slag, mixing, extruding into strips for forming, and drying to obtain the ferric oxide normal-temperature desulfurizer;
2) performing magnesium soap extraction on the leached manganese ferric sulfate solution to separate manganese iron: the method comprises the steps of saponifying an extractant by using magnesium oxide by using a magnesium oxide saponification extractant technology for leached iron-manganese sulfate solution, filtering the saponified extractant, separating saponification slag, converting the extractant from magnesium soap into manganese soap by using a manganese sulfate solution, and mixing the manganese soap with the leached iron-manganese sulfate solution for extraction to remove iron; controlling the pH value of the manganese sulfate solution after the residual iron extraction to be 1.9-2.2, introducing hydrogen sulfide into the manganese sulfate solution for sulfurizing and depositing lead, then adjusting the pH value to be 5.5, adding 5-40% fluosilicic acid for removing calcium, then aging for 24 hours, and then filtering and separating to obtain a refined manganese sulfate solution; carrying out MVR evaporation concentration on the refined manganese sulfate solution, and carrying out hydrothermal precipitation in a high-pressure anticorrosion container at the temperature of 180 ℃ and 200 ℃ to obtain battery-grade manganese sulfate monohydrate slurry; then, reducing the pressure to 0.3MPa to normal pressure through three-stage pressure reduction and two-stage flash evaporation, discharging the obtained product into a centrifugal machine for solid-liquid separation, then sending the obtained product into a flash evaporation dryer for drying, and packaging the obtained product to obtain commercial battery grade manganese sulfate monohydrate;
3) and (3) treating an organic phase extractant to respectively recover vanadium, titanium, iron and scandium: firstly, backwashing an organic phase extracting agent by 3 mol of sulfuric acid to remove metal ions, and respectively recovering titanium and vanadium from a water phase by hydrolyzing and precipitating titanium and vanadium by ammonium salt; carrying out back extraction on the organic phase extractant by using 6-8 mol of hydrochloric acid to obtain a liquid ferric trichloride solution after the back extraction, precipitating high-purity ferric phosphate dihydrate by using ammonium phosphate in one part of the liquid ferric trichloride solution after the back extraction, and drying and packaging to obtain a battery-grade ferric phosphate product; neutralizing and precipitating iron with at least one of calcium oxide, magnesium oxide, liquid ammonia and ammonia water to produce iron oxide pigment in the other part of ferric trichloride solution as iron-removing solution; evaporating and crystallizing the liquid after iron precipitation by using MVR to produce salts corresponding to the iron precipitation agent; carrying out back extraction of scandium on the organic phase extractant after iron stripping by using 2 mol of sodium hydroxide solution, then carrying out oil-water separation, adding oxalic acid into the solution after scandium stripping, precipitating to obtain scandium oxalate, and calcining the scandium oxalate to recover high-purity scandium oxide; and (3) washing the organic phase extractant subjected to scandium back extraction by deionized water to remove sodium ions, and then repeatedly using the organic phase extractant to carry out water treatment on the washed sodium ions.
2. The process for full resource utilization of titanium white waste acid according to claim 1, wherein the process comprises the following steps: the extracting agents are all P204, and the organic phase extracting agents are all organic phase P204.
3. The process for full resource utilization of titanium white waste acid according to claim 1, wherein the process comprises the following steps: the extracting agents are all P507, and the organic phase extracting agents are all organic phase P507.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115259118A (en) * | 2021-04-30 | 2022-11-01 | 中国科学院过程工程研究所 | Method for separating phosphorus from phosphorus-containing fluorine-containing substance |
| CN115535983A (en) * | 2022-06-27 | 2022-12-30 | 桂林理工大学 | Method for preparing spherical high-density iron phosphate by oxidizing pure manganese dioxide |
| CN115974128A (en) * | 2022-12-29 | 2023-04-18 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling scandium from molten salt chlorination comprehensive utilization by-product by using titanium dioxide waste acid |
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| CN115259118A (en) * | 2021-04-30 | 2022-11-01 | 中国科学院过程工程研究所 | Method for separating phosphorus from phosphorus-containing fluorine-containing substance |
| CN115535983A (en) * | 2022-06-27 | 2022-12-30 | 桂林理工大学 | Method for preparing spherical high-density iron phosphate by oxidizing pure manganese dioxide |
| CN115974128A (en) * | 2022-12-29 | 2023-04-18 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling scandium from molten salt chlorination comprehensive utilization by-product by using titanium dioxide waste acid |
| CN115974128B (en) * | 2022-12-29 | 2024-05-14 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling scandium from fused salt chlorination comprehensive utilization byproducts by utilizing titanium white waste acid |
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Application publication date: 20200804 |