CN103172115B - Method for removing ferric iron ion contained in metatitanic acid by adopting electrolytic reduction - Google Patents
Method for removing ferric iron ion contained in metatitanic acid by adopting electrolytic reduction Download PDFInfo
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- CN103172115B CN103172115B CN201310097086.XA CN201310097086A CN103172115B CN 103172115 B CN103172115 B CN 103172115B CN 201310097086 A CN201310097086 A CN 201310097086A CN 103172115 B CN103172115 B CN 103172115B
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- metatitanic acid
- titanous
- sulfuric acid
- acid
- ferric
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Abstract
The invention relates to the technical field of preparation of titanium dioxide pigments, and particularly relates to a method for preparing titanous ions by acidifying and then electrolytically reducing metatitanic acid. The method comprises the following steps of: firstly acidifying the metatitanic acid; then electrolyzing to prepare a titanous solution; and finally adding the obtained titanous solution to the raw material metatitanic acid to reduce ferric iron into ferrous iron, and then washing. Compared with the traditional method, the method disclosed by the invention is unnecessary to add the aluminum powder, reduces the usage amount of sulfuric acid, simplifies the production process, saves the production cost and has the advantages of environment protection, safety, easiness for operation, low content of aluminum contained in products and product quality enhancement.
Description
Technical field
The present invention relates to TiO 2 pigment preparing technical field, be specifically related to a kind of method adopting electrolytic reduction to remove ferric ion in metatitanic acid.
Background technology
Titanium dioxide is commonly called as titanium dioxide, because have good optical property, so be best white pigment, is widely used in the fields such as coating, papermaking, plastics.At present, the production technology mainly two large cores of titanium dioxide, one is give TiO 2 pigment performance, and two is the purification of titanium dioxide production process and the removal of impurity, and maximum impurity is exactly iron, when the content of iron is more than 30ppm, the naked eyes of people just can see yellow tone, have impact on the pigment indexs such as the whiteness of titanium dioxide and glossiness degree, and when high-temperature calcination, iron is easily decomposed into the ferric oxide of microlitic structure identical with titanium dioxide, affects the crystalline structure of titanium dioxide.So in sulfuric acid method titanium pigment production process, the removal of iron is quite crucial.In current sulfuric acid method titanium pigment production process, the mode mainly by washing, bleaching, reduction, rinsing carries out removal of impurity iron.Washing can only remove the ferrous ion of solubility, and pH value must remain on less than 2.When PH is greater than after 2, the iron ion of divalence is very easily oxidized the ironic hydroxide generating trivalent.Therefore, in sulfuric acid method titanium pigment production process, in order to remove ferric ion, have employed bleaching and reduction two kinds of modes carry out ferric removal.Metatitanic acid is under agitation added quantitative industrial sulphuric acid by bleaching exactly, makes the sulfuric acid concentration of slurries at about 80g/L, leads to and is steam heated to 70 DEG C, make the ironic hydroxide in metatitanic acid be dissolved in sulfuric acid, generates ferric sulphate solution.The add-on of aluminium powder is that metatitanic acid is (with TiO
2meter) 0.5%-1.0%.Aluminium powder is pressed powder, for making aluminium powder can be evenly dispersed in metatitanic acid, should first by after aluminium powder water furnishing pulpous state, and gradation adds.Aluminium powder can with the ferric sulphate generation chemical reaction in slurry, again can with the effect of sulfuric acid of slurry and release hydrogen ion, make in slurry, to produce a large amount of bubble, slowly must add people for this reason, cause slurry splash or emit pot to avoid reaction too violent.After adding aluminium powder, continue heating, make temperature be incubated 1.5-2h at 80-90 DEG C, make ferric sulphate all be reduced into ferrous sulfate, titanium sulfate is reduced to titanous and makes slurry be lavender.Sampling and measuring titanous content is that 0.3-0.5g/L(is with TiO
2meter), be reduction and terminate.By metatitanic acid slurry good for reduction bleaching, filter with leaf filter, then use deionized water wash metatitanic acid, wash away ferrous sulfate further, by the Fe in metatitanic acid
20
3washing is qualified to being less than 30ppm.
Chemical equation is: Fe (OH)
3+ 3H
2sO
4→ Fe
2(SO
4)
3+ 6H
2o
H
2TiO
3+H
2SO
4→Ti(SO
4)
2+2H
2O
3H
2SO
4+2Al→Al
2(SO
4)
3+6[H]
Fe
2(SO
4)
3+2[H]→2FeSO
4+H
2SO
4
2Ti(SO
4)
2+2[H]→Ti
2(SO
4)
3+H
2SO
4
2[H]→H
2
But after adding aluminium powder and sulfuric acid, although the iron ion removing that can will remain in metatitanic acid preferably, turn increase aluminum ion and sulfuric acid, the aluminum ion causing the finished product raises, and quality product fluctuation strengthens, and production cost is higher.Till now, this problem is not also resolved.
Summary of the invention
The object of this invention is to provide a kind of method adopting electrolytic reduction to remove ferric ion in metatitanic acid, this method reduce production cost, improve the quality of products, and Environmental Safety, simple to operate.
Employing electrolytic reduction of the present invention removes the method for ferric ion in metatitanic acid, comprises the following steps:
(1) metatitanic acid is spent ion water making for becoming slurry;
(2) slurry sulfuric acid dissolution is titanium sulfate solution;
(3) titanium sulfate solution is added in electrolyzer, the time controlling electrolysis 1-3 hour, temperature 40-60 DEG C, voltage at 0.8-1.5V, carry out electrolytic preparation containing the solution of titanous;
(4) solution containing titanous is joined in raw material metatitanic acid to reduce ferric iron be ferrous iron, then carry out washing, be less than 30ppm to reach ferric oxide, meet the requirement of pigment-level titanium dioxide.
In described slurry, metatitanic acid massfraction is 40-70%.
The add-on of described sulfuric acid and TiO
2mass ratio be 3:1-6:1.
Described anodes in electrolytic cells adopts Graphite Electrodes, and negative electrode adopts the one in copper electrode, Ti electrode or lead electrode.
Adopt ionic membrane in described electrolyzer, ionic membrane is conventional ionic membrane, is the one in anionic membrane or cationic membrane, preferred anionic film of the present invention.
Described electrolytic preparation titanous reduces ferric method and the Direct Electrolysis in traditional literature and reduces compared with ferric method, employing medium is different, Traditional Method adopts sulfuric acid and the reacted titanium liquid of titanium ore, sulfuric acid titanium also has a large amount of impurity such as iron, calcium, magnesium outward, and content is high, the side reaction of electrolysis is many; And the present invention adopts the titanium sulfate solution after metatitanic acid and sulfuric acid reaction, foreign matter content is low, and side reaction is few, as long as and have titanous to exist just to meet processing requirement.
Beneficial effect of the present invention is as follows:
The present invention by by after first for a small amount of metatitanic acid acidifying again electrolytic preparation containing the solution of titanous, finally the solution containing titanous to be joined in raw material metatitanic acid thus is ferrous iron by the ferric iron back in raw material metatitanic acid effectively.Not only do not introduce tramp material, and ferric removal effect is excellent.
The present invention and traditional bleaching are reduced and are removed compared with ferric method, do not need to add the preparation that aluminium powder carries out titanous, thus decrease the consumption of sulfuric acid, saved production cost, simplified production technique; The present invention has stopped the Hazard Factor after adding aluminium powder in traditional processing technology, and its Environmental Safety is simple to operate; Aluminium content in product is low, improves quality product.
Accompanying drawing explanation
Fig. 1 is conventional process flow figure;
Fig. 2 is present invention process schema;
Fig. 3 is present invention process electrolyzer schematic diagram.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Comparative example 1
Adopt traditional method that 100g metatitanic acid is under agitation added 50g industrial sulphuric acid, lead to after being steam heated to 70 DEG C, add aluminium powder 0.8g.After adding aluminium powder, continue heating, make temperature be incubated 1.5-2h at 80-90 DEG C, make ferric sulphate all be reduced into ferrous sulfate, titanium sulfate is reduced to titanous and makes slurry be lavender.With the Fe in the metatitanic acid slurry that deionized water wash reduction bleaching is good
2o
3.
Embodiment 1
The preparation of the metatitanic acid 0.5L deionized water of 100g is become the slurry of 200g/L, after stirring, slowly add sulfuric acid, the add-on of sulfuric acid is according to mass ratio H
2sO
4: TiO
2=5:1 adds.Continue to stir and be heated to material boiling, making it be dissolved as titanium sulfate solution.Be cooled to by titanium sulfate solution 50 DEG C to join in electrolyzer, control the time of electrolysis at 1 hour, voltage, at 0.8V, carries out electrolytic preparation titanous, makes titanous be greater than 90% than titanic ratio; Trivalent titanium solution after electrolysis being joined in raw material metatitanic acid and reducing its ferric iron be mingled with is that ferrous iron washs again, is less than 30ppm, meets the requirement of pigment-level titanium dioxide to reach ferric oxide.
Embodiment 2
The preparation of the metatitanic acid 0.5L deionized water of 100g is become the slurry of 200g/L, after stirring, slowly add sulfuric acid, the add-on of sulfuric acid is according to mass ratio H
2sO
4: TiO
2=4:1 adds.Continue to stir and be heated to material boiling, making it be dissolved as titanium sulfate.Be cooled to by titanium sulfate solution 40 DEG C to join in electrolyzer, control the time of electrolysis at 1.5 hours, voltage, at 1.0V, carries out electrolytic preparation titanous, makes titanous be greater than 90% than titanic ratio; Trivalent titanium solution after electrolysis being joined in raw material metatitanic acid and reducing its ferric iron be mingled with is that ferrous iron washs again, is less than 30ppm, meets the requirement of pigment-level titanium dioxide to reach ferric oxide.
Embodiment 3
The preparation of the metatitanic acid 0.5L deionized water of 100g is become the slurry of 200g/L, after stirring, slowly add sulfuric acid, the add-on of sulfuric acid is according to mass ratio H
2sO
4: TiO
2=6:1 adds.Continue to stir and be heated to material boiling, making it be dissolved as titanium sulfate.Be cooled to by titanium sulfate solution 60 DEG C to join in electrolyzer, control the time of electrolysis at 2 hours, voltage, at 1.1V, carries out electrolytic preparation titanous, makes titanous be greater than 90% than titanic ratio; Being joined by the solution of the titanous after electrolysis in raw material metatitanic acid and reducing its ferric iron be mingled with is that ferrous iron washs again, is less than 30ppm, meets the requirement of pigment-level titanium dioxide to reach ferric oxide.
Embodiment 4
The preparation of the metatitanic acid 0.5L deionized water of 100g is become the slurry of 200g/L, after stirring, slowly add sulfuric acid, the add-on of sulfuric acid is according to mass ratio H
2sO
4: TiO
2=3:1 adds.Continue to stir and be heated to material boiling, making it be dissolved as titanium sulfate.Be cooled to by titanium sulfate solution 50 DEG C to join in electrolyzer, control the time of electrolysis at 3 hours, voltage, at 1.2V, carries out electrolytic preparation titanous, makes titanous be greater than 90% than titanic ratio; Trivalent titanium solution after electrolysis being joined in raw material metatitanic acid and reducing its ferric iron be mingled with is that ferrous iron washs again, is less than 30ppm, meets the requirement of pigment-level titanium dioxide to reach ferric oxide.
Testing method: the metatitanic acid after embodiment 1-4 and the prepared washing of comparative example 1 is positioned in the ceramic crucible cleaned, be positioned in retort furnace, by low-temperature-rise to 400 DEG C, constant temperature dewaters for 1 hour, then continue to be warming up to 600 DEG C, constant temperature 2 hours, carry out removing sulfate radical, then, continue to be warming up to 830 DEG C, constant temperature 1 hour, then take out after naturally cooling to room temperature, be put into spectroscopically pure shredder and carry out grind away, sample fineness is reached after 325 orders pass through, by dry powder blancometer test pigment index.Test result is as table 1.L represents the brightness of pigment, and a represents the red green degree of pigment, and b represents the champac degree of pigment, and Wh represents the dry powder whiteness of pigment.
Table 1 table with test results
| Sample | Fe 2O 3/ppm | Al 2O 3/ppm | L | a | b | Wh |
| Comparative example 1 | 42 | 236 | 97.5 | 2.95 | 1.62 | 96.59 |
| Embodiment 1 | 16 | 10 | 98.3 | 2.12 | 0.42 | 97.12 |
| Embodiment 2 | 21 | 9 | 98.1 | 2.24 | 0.36 | 97.09 |
| Embodiment 3 | 19 | 8 | 97.9 | 2.09 | 0.13 | 97.21 |
| Embodiment 4 | 13 | 11 | 98.4 | 2.33 | 0.42 | 97.54 |
As can be seen from upper table 1, embodiment 1-4 obtains the Fe of product
2o
3concentration be all less than Fe in comparative example 1
2o
3concentration, meet the requirement of pigment-level titanium dioxide, and embodiment 1-4 obtains the Al of product
2o
3concentration be Al in comparative example 1
2o
3concentration about 5%.This has absolutely proved, adopts the present invention not introduce additional impurity, and Fe
2o
3content is low, improves the quality of product.
Claims (1)
1. the method adopting electrolytic reduction to remove ferric ion in metatitanic acid, it is characterized in that comprising the following steps: the slurry preparation of the metatitanic acid 0.5L deionized water of 100g being become 200g/L, after stirring, slowly add sulfuric acid, the add-on of sulfuric acid is according to mass ratio H
2sO
4: TiO
2=3:1 adds; Continue to stir and be heated to material boiling, making it be dissolved as titanium sulfate; Be cooled to by titanium sulfate solution 50 DEG C to join in electrolyzer, control the time of electrolysis at 3 hours, voltage, at 1.2V, carries out electrolytic preparation titanous, makes titanous be greater than 90% than titanic ratio; Trivalent titanium solution after electrolysis being joined in raw material metatitanic acid and reducing its ferric iron be mingled with is that ferrous iron washs again, is less than 30 ppm to reach ferric oxide.
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| CN103172115B true CN103172115B (en) | 2015-07-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103553123B (en) * | 2013-10-18 | 2015-09-30 | 中国有色集团（广西）平桂飞碟股份有限公司 | The bleaching method of metatitanic acid in a kind of Titanium White Production By Sulfuric Acid Process |
| CN103668302A (en) * | 2013-12-11 | 2014-03-26 | 中国科学院过程工程研究所 | Method for preparing high-concentration low-valent titanium aqueous solution through electrolytic reduction |
| CN103708538B (en) * | 2013-12-20 | 2016-03-09 | 攀枝花东方钛业有限公司 | A kind of preparation method of trivalent titanium solution |
| CN105271399A (en) * | 2015-12-01 | 2016-01-27 | 山东东佳集团股份有限公司 | Method for acidolysis and reduction of ferric iron by titanium dioxide to improve quality of titaniferous solution through sulfuric acid method |
| CN107986325B (en) * | 2017-10-16 | 2019-12-06 | 河北麦森钛白粉有限公司 | method for removing Fe2O3 from metatitanic acid in titanium dioxide as decorative base paper by sulfuric acid process |
| CN113818037A (en) * | 2021-09-16 | 2021-12-21 | 山东晟融泰新材料科技有限责任公司 | Electrolysis device for electrolyzing trivalent titanium from titanium white by sulfuric acid process |
| CN113697854A (en) * | 2021-09-16 | 2021-11-26 | 山东晟融泰新材料科技有限责任公司 | Process for electrolyzing trivalent titanium from titanium white by sulfuric acid method |
| CN113929132A (en) * | 2021-09-24 | 2022-01-14 | 东华工程科技股份有限公司 | Sulfuric acid method titanium dioxide metatitanic acid bleaching method and system |
| CN115504504B (en) * | 2022-11-07 | 2023-07-28 | 攀钢集团研究院有限公司 | Reducing impurities in meta-titanic acid method for copper element content |
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| CN1295976A (en) * | 2000-11-29 | 2001-05-23 | 南宁市达科钛酸钡中试厂 | Method for producing high-activity super fine grain barium titanate |
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