CN115676901A - Preparation process of high-purity ferrous sulfate in production process of titanium dioxide by sulfuric acid method - Google Patents
Preparation process of high-purity ferrous sulfate in production process of titanium dioxide by sulfuric acid method Download PDFInfo
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- CN115676901A CN115676901A CN202211451609.1A CN202211451609A CN115676901A CN 115676901 A CN115676901 A CN 115676901A CN 202211451609 A CN202211451609 A CN 202211451609A CN 115676901 A CN115676901 A CN 115676901A
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- Prior art keywords
- ferrous sulfate
- solution
- sulfuric acid
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- titanium dioxide
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 235000003891 ferrous sulphate Nutrition 0.000 title claims abstract description 55
- 239000011790 ferrous sulphate Substances 0.000 title claims abstract description 55
- 229910000359 iron(II) sulfate Inorganic materials 0.000 title claims abstract description 55
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 title claims abstract 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000012535 impurity Substances 0.000 claims abstract description 38
- 229910052742 iron Inorganic materials 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 2
- 230000007062 hydrolysis Effects 0.000 abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 8
- 238000004321 preservation Methods 0.000 abstract description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 39
- 235000010215 titanium dioxide Nutrition 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a preparation process of high-purity ferrous sulfate in a sulfuric acid method titanium dioxide production process, and belongs to the technical field of ferrous sulfate impurity removal. The method comprises the following steps: 1) Reacting excessive iron sheet with a sulfuric acid solution, adjusting the pH value of the solution to 4 after the reaction is finished, hydrolyzing the impurity element precipitate with the pH value lower than 4, filtering, and separating to obtain a ferrous sulfate solution after primary impurity removal; 2) Adding iron sheet into the ferrous sulfate solution after the primary impurity removal, keeping the pH value of the solution at 4, heating the solution to 60 ℃, preserving the temperature, and separating out ferrous sulfate crystals. The method of the invention does not introduce new impurities, and has simple preparation process and low cost; the method improves the purity of the ferrous sulfate by adjusting the pH value of the solution twice, adjusts the pH value of the solution to be 4 for the first time, and precipitates impurity elements with the hydrolysis pH value lower than 4; the pH value of the solution is adjusted to 4 for the second time, and the heat preservation operation is assisted, so that the ferrous sulfate is efficiently extracted.
Description
Technical Field
The invention belongs to the technical field of ferrous sulfate impurity removal, and relates to a preparation process of high-purity ferrous sulfate in a sulfuric acid method titanium dioxide production process.
Background
At present, high-purity ferrous sulfate is mainly prepared by the reaction of reduced iron powder and sulfuric acid, but the method has high requirements on the quality of the reduced iron powder on one hand, and has high price and high production cost on the other hand. Considering the comprehensive production cost, the byproduct ferrous sulfate can be prepared in the production process of titanium white by a sulfuric acid method, but because the impurity content of the ferrous sulfate byproduct is high, the ferrous sulfate byproduct needs to be purified, and if an impurity removing agent is used in the purification process, a new impurity element is introduced.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation process of high-purity ferrous sulfate in the production process of titanium dioxide by a sulfuric acid method.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the preparation process of high-purity ferrous sulfate in the production process of titanium dioxide by a sulfuric acid method comprises the following steps:
1) Reacting excessive iron sheet with a sulfuric acid solution, adjusting the pH value of the solution to 4 after the reaction is finished, hydrolyzing the impurity element precipitate with the pH value lower than 4, filtering, and separating to obtain a ferrous sulfate solution after primary impurity removal; the concentration of the sulfuric acid solution is 40-60wt.%;
2) Adding iron sheet into the ferrous sulfate solution obtained in the step 1) after the primary impurity removal, keeping the pH value of the solution at 4, heating the solution to the temperature of 60 ℃, preserving heat, and separating out ferrous sulfate crystals.
Further, in step 1), the concentration of the sulfuric acid solution is 50-60wt.%.
Further, in the step 1), the pH value of the solution is adjusted by adjusting the dosage of the iron sheet.
Further, in the step 2), heat preservation is carried out for 2-3h.
Further, in the step 2), the impurity removal rate of ferrous sulfate crystals is not less than 99%.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method of the invention does not introduce new impurities, and has simple preparation process and low cost;
(2) The method improves the purity of the ferrous sulfate by adjusting the pH value of the solution twice, adjusts the pH value of the solution to 4 for the first time, and precipitates impurity elements with the hydrolysis pH value lower than 4; and adjusting the pH value of the solution to 4 for the second time, and extracting ferrous sulfate by heat preservation operation, further removing other impurities except the ferrous sulfate, purifying a titanium white byproduct ferrous sulfate, and providing data reference for industrial application.
Detailed Description
The invention is further described with reference to specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Modifications or substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and scope of the invention. In the following examples, the technical means used in the examples are conventional means well known to those skilled in the art, unless otherwise specified.
The ferrous sulfate heptahydrate in the following examples was obtained from Jiangsu Yuxing science and technology, inc.
Example 1
The preparation process of high-purity ferrous sulfate in the production process of titanium dioxide by a sulfuric acid method comprises the following steps:
1) Reacting excessive iron sheet with a sulfuric acid solution, wherein the concentration of the sulfuric acid solution is 50wt.%, adjusting the pH value of the solution to 4 by adjusting the using amount of the iron sheet after the reaction is finished, on one hand, on the basis of not introducing new impurity elements, precipitating impurity elements (such as Ti) with the hydrolysis pH value lower than 4, and on the other hand, fe is used as a reducing agent, and S is generated in the sulfuric acid reaction process 2- And Co with 2+ 、Ni 2+ 、Zn 2+ Forming insoluble matters, filtering and separating to obtain a ferrous sulfate solution after primary impurity removal;
2) To avoid Fe in ferrous sulfate solution after primary impurity removal 2+ Oxidized to produce Fe (OH) 3 Precipitating, adding iron sheet into the primarily impurity-removed ferrous sulfate solution, keeping pH 4, heating to 60 deg.C, maintaining for 2 hr, separating ferrous sulfate crystal, and reversely removing impurity elements (such as Mn) with hydrolysis pH higher than 4 2+ 、Mg 2+ )。
Comparative example 1
The preparation process of high-purity ferrous sulfate in the production process of titanium dioxide by a sulfuric acid method comprises the following steps:
1) Reacting excessive iron sheet with a sulfuric acid solution, wherein the concentration of the sulfuric acid solution is 50wt.%, adjusting the pH value of the solution to 2 by adjusting the using amount of the iron sheet after the reaction is finished, precipitating impurity elements with the hydrolysis pH value lower than 2, filtering, and separating to obtain a ferrous sulfate solution after primary impurity removal;
2) Adding iron sheet into the ferrous sulfate solution after the primary impurity removal, keeping the pH value of the solution at 2, heating the solution to 60 ℃, and keeping the temperature for 2 hours to separate out ferrous sulfate crystals.
Comparative example 2
The preparation process of high-purity ferrous sulfate in the production process of titanium dioxide by a sulfuric acid method comprises the following steps:
1) Reacting excessive iron sheet with a sulfuric acid solution, wherein the concentration of the sulfuric acid solution is 50wt.%, adjusting the pH value of the solution to 8 by adjusting the using amount of the iron sheet after the reaction is finished, precipitating impurity elements with the hydrolysis pH value lower than 8, filtering, and separating to obtain a ferrous sulfate solution after primary impurity removal;
2) Adding iron sheet into the ferrous sulfate solution after the primary impurity removal, keeping the pH value of the solution at 8, heating the solution to the temperature of 60 ℃, and preserving heat for 2 hours to separate out ferrous sulfate crystals.
Comparative example 3
The preparation process of high-purity ferrous sulfate in the production process of titanium dioxide by a sulfuric acid method comprises the following steps:
1) Reacting excessive iron sheet with a sulfuric acid solution, wherein the concentration of the sulfuric acid solution is 30wt.%, adjusting the pH value of the solution to 4 by adjusting the using amount of the iron sheet after the reaction is finished, precipitating impurity elements with the hydrolysis pH value lower than 4, filtering, and separating to obtain a ferrous sulfate solution after primary impurity removal;
2) Adding iron sheet into the ferrous sulfate solution after the primary impurity removal, keeping the pH value of the solution at 4, heating the solution to the temperature of 60 ℃, and preserving heat for 2 hours to separate out ferrous sulfate crystals.
Comparative example 4
The preparation process of high-purity ferrous sulfate in the production process of titanium dioxide by a sulfuric acid method comprises the following steps:
reacting excessive iron sheet with a sulfuric acid solution, wherein the concentration of the sulfuric acid solution is 50wt.%, adjusting the pH value of the solution to 4 by adjusting the using amount of the iron sheet after the reaction is finished, precipitating impurity elements with the hydrolysis pH value lower than 4, filtering, and separating to obtain a ferrous sulfate solution after primary impurity removal; heating the solution to 60 ℃ and keeping the temperature for 2h to separate out ferrous sulfate crystals.
The impurity content of the ferrous sulfate crystals precipitated in each example is shown in table 1 below:
TABLE 1
| w(Mn)％ | w(Ni)％ | w(Zn)％ | w(Mg)％ | w(Ti)％ | |
| Example 1 | 0.025 | 0.015 | 0.010 | 0.230 | 0.280 |
| Comparative example 1 | 0.029 | 0.019 | 0.016 | 0.252 | 0.315 |
| Comparative example 2 | 0.035 | 0.023 | 0.020 | 0.280 | 0.350 |
| Comparative example 3 | 0.031 | 0.019 | 0.017 | 0.254 | 0.333 |
| Comparative example 4 | 0.054 | 0.018 | 0.015 | 0.370 | 0.285 |
Claims (5)
1. The preparation process of high-purity ferrous sulfate in the production process of titanium dioxide by a sulfuric acid method is characterized by comprising the following steps of:
1) Reacting excessive iron sheet with a sulfuric acid solution, adjusting the pH value of the solution to 4 after the reaction is finished, hydrolyzing impurity element precipitates with the pH value lower than 4, filtering, and separating to obtain a ferrous sulfate solution after primary impurity removal; the concentration of the sulfuric acid solution is 40-60wt.%;
2) Adding iron sheet into the ferrous sulfate solution obtained in the step 1) after preliminary impurity removal, keeping the pH value of the solution at 4, heating the solution to 60 ℃, and preserving heat to separate out ferrous sulfate crystals.
2. The process for preparing high-purity ferrous sulfate in the process of producing titanium dioxide by a sulfuric acid method according to claim 1, wherein the concentration of the sulfuric acid solution in the step 1) is 50 to 60wt.%.
3. The process for preparing high-purity ferrous sulfate in the process of producing titanium dioxide by a sulfate process according to claim 1, wherein in the step 1), the pH value of the solution is adjusted by adjusting the dosage of the iron sheet.
4. The process for preparing high-purity ferrous sulfate in the production process of titanium dioxide by a sulfuric acid method according to claim 1, wherein in the step 2), the temperature is kept for 2-3h.
5. The process for preparing high-purity ferrous sulfate in the production process of titanium dioxide by a sulfate process according to claim 1, wherein in the step 2), the impurity removal rate of ferrous sulfate crystals is not less than 99%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211451609.1A CN115676901A (en) | 2022-11-18 | 2022-11-18 | Preparation process of high-purity ferrous sulfate in production process of titanium dioxide by sulfuric acid method |
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| CN202211451609.1A CN115676901A (en) | 2022-11-18 | 2022-11-18 | Preparation process of high-purity ferrous sulfate in production process of titanium dioxide by sulfuric acid method |
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| CN115676901A true CN115676901A (en) | 2023-02-03 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1269873A (en) * | 1969-04-10 | 1972-04-06 | M & T Chemicals Inc | Process for producing ferrous sulphate |
| CN102786099A (en) * | 2012-08-27 | 2012-11-21 | 上海华谊（集团）公司 | Device and method for producing ferrous sulfate solution |
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- 2022-11-18 CN CN202211451609.1A patent/CN115676901A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1269873A (en) * | 1969-04-10 | 1972-04-06 | M & T Chemicals Inc | Process for producing ferrous sulphate |
| CN102786099A (en) * | 2012-08-27 | 2012-11-21 | 上海华谊（集团）公司 | Device and method for producing ferrous sulfate solution |
Non-Patent Citations (1)
| Title |
|---|
| 陈琼: "工业硫酸亚铁的简易生产法", 广西师范大学学报（哲学社会科学版）, pages 50 - 52 * |
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