CN107857304A - The method of purification of saltouing of byproduct ferrous sulfate of titanium dioxide - Google Patents
The method of purification of saltouing of byproduct ferrous sulfate of titanium dioxide Download PDFInfo
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- CN107857304A CN107857304A CN201711128162.3A CN201711128162A CN107857304A CN 107857304 A CN107857304 A CN 107857304A CN 201711128162 A CN201711128162 A CN 201711128162A CN 107857304 A CN107857304 A CN 107857304A
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- ferrous sulfate
- titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The invention discloses a kind of method of purification of saltouing of byproduct ferrous sulfate of titanium dioxide, belong to chemical technology field.Present invention solves the technical problem that it is to provide a kind of New Method of Purification of high, the simple to operate byproduct ferrous sulfate of titanium dioxide of impurities removing efficiency.A kind of method of purification of saltouing of byproduct ferrous sulfate of titanium dioxide, comprises the following steps：Salting-out agents are added into ferrous sulfate saturated solution, lasting stirring is no less than 6h, filtering drying.The inventive method can effectively reduce the impurity such as Mn, Mg, Ti in byproduct ferrous sulfate of titanium dioxide, removal of impurity is high, and higher yield can be obtained under normal temperature, the problem of oxidation of ferrous ion is avoided, a kind of new approach is provided for byproduct ferrous sulfate of titanium dioxide.
Description
Technical field
The invention belongs to chemical technology field, and in particular to a kind of purification side of saltouing of byproduct ferrous sulfate of titanium dioxide
Method.
Background technology
Titanium dioxide is considered as a kind of current best Chinese white of performance in the world, is widely used in coating, plastics, makes
The industry such as paper, printing-ink, chemical fibre, rubber, cosmetics.The production method of titanium dioxide mainly has sulfuric acid process and chloridising, sulfuric acid
Method because production technology is relatively easy, it is relatively low to the grade requirement of ilmenite concentrate the advantages that, adopted by most of titanium white production enterprises
With domestic larger titanium white production enterprise all uses Titanium White Production By Sulfuric Acid Process substantially at present, and accounting is up to 98%.
Substantial amounts of ferrous sulfate byproduct, according to incompletely statistics, sulphur can be produced during sulfuric acid process reproduction titanium dioxide
Sour ferrous yield will be up to 500~7,500,000 tons/year, because it contains TiO2+、Mn2+、Mg2+、Al3+Can not be by Deng impurity element
Directly utilize, stacked as solid waste for a long time, so substantial amounts of ferrous sulfate accessory substance not only have impact on ring
Border, and waste is caused to iron resource, largely constrain the development of titanium dioxide industry.Ferrous sulfate is main at present
Make water purification agent, feed addictive, fertilizer, coating etc., but be required for that ferrous sulfate purify to meet to require, therefore such as
The purity what improves ferrous sulfate is the top priority for solving byproduct ferrous sulfate of titanium dioxide.
The method of existing purification byproduct ferrous sulfate of titanium dioxide is concentrated mainly on two classes：Hydrolysis methods and crystallization
Method.The technique of hydrolysis methods is similar, and difference is the precipitating reagent difference used, and precipitating reagent is in the process used
The difference of the impurity of middle entrainment and the impurity itself introduced is to errous sulfate crystal product quality, technological process complexity
And yield has significant impact.Different from the precipitation method, crystallisation purification ferrous sulfate will not only introduce impurity, and technique
It is simple easily operated, but existing crystallisation is all by the way of evaporation and concentration-decrease temperature crystalline, and the clearance of impurity is relatively low.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of high, the simple to operate by-product of white titanium pigment sulfuric acid of impurities removing efficiency is sub-
The New Method of Purification of iron.
The present invention solves the technical scheme that above-mentioned technical problem uses and there is provided a kind of byproduct ferrous sulfate of titanium dioxide
Method of purification of saltouing, this method comprises the following steps：
Byproduct ferrous sulfate of titanium dioxide is added to the water, untill having part of sulfuric acid ferrous iron insoluble in solution, filtering
Remove clear liquid, as ferrous sulfate saturated solution；Salting-out agents are added into ferrous sulfate saturated solution, lasting stirring is no less than
6h, filtering, filter cake dry to obtain errous sulfate crystal.
Wherein, in the above method, the impurity weight/mass percentage composition of the byproduct ferrous sulfate of titanium dioxide is Mn：0.1~
5%th, Mg：0.1~5%, Ti：0.01~10%.
Wherein, in the above method, the purity of the water is not less than deionized water.
Wherein, in the above method, the addition of the salting-out agents is：In every liter of ferrous sulfate saturated solution add 0.1~
0.5kg salting-out agents.
Wherein, in the above method, the salting-out agents are at least one of ammonium sulfate or ammonium hydrogen sulfate.
Preferably, in the above method, the time persistently stirred is 6~24h.
Wherein, in the above method, when errous sulfate crystal can not meet purity requirement, purification operations are repeated.
Beneficial effects of the present invention：
The invention provides it is a kind of be different from traditional evaporation and concentration-lowering temperature crystallization saltout method of purification to purify titanium white
Powder by-product ferrous sulfate, be not required to add precipitating reagent, be not introduced into metal impurities, it becomes possible to effectively reduce ferrous sulfate in Mn, Mg,
The impurity such as Ti, this method technique is simple, reaction time is short, economic and environment-friendly, removal of impurity is high, and under normal temperature can obtain compared with
High yield, the problem of oxidation of ferrous ion is avoided, one kind is provided newly for the purification of byproduct ferrous sulfate of titanium dioxide
Approach；Gained errous sulfate crystal of the invention can be used for synthesizing iron ammonium sulfate, ferric phosphate, the former material of LiFePO 4
Material, has widened the application field of byproduct ferrous sulfate of titanium dioxide.
Embodiment
Specifically, a kind of method of purification of saltouing of byproduct ferrous sulfate of titanium dioxide, this method comprise the following steps：
Byproduct ferrous sulfate of titanium dioxide is added to the water, untill having part of sulfuric acid ferrous iron insoluble in solution, filtering
Remove clear liquid, as ferrous sulfate saturated solution；Salting-out agents are added into ferrous sulfate saturated solution, lasting stirring is no less than
6h, filtering, filter cake dry to obtain errous sulfate crystal.
In the inventive method, the preparation of ferrous sulfate saturated solution and purification of saltouing, it can carry out at normal temperatures, temperature one
As be 20~30 DEG C.
Byproduct ferrous sulfate of titanium dioxide contains TiO because of it2+、Mn2+、Mg2+It can not be used directly Deng impurity element,
Its impurity weight/mass percentage composition is generally Mn：0.1~5%, Mg：0.1~5%, Ti：0.01~10%.All it is to make for a long time
Stacked for solid waste, so substantial amounts of ferrous sulfate accessory substance not only have impact on environment, and cause wave to iron resource
Take, largely constrain the development of titanium dioxide industry, therefore the purity for how improving ferrous sulfate is that solve titanium dioxide pair
The top priority of product ferrous sulfate.
Ferrous sulfate saturated solution can be prepared by the following method：Under normal temperature (generally 20~30 DEG C), into water, side is stirred
Mix side and add byproduct ferrous sulfate of titanium dioxide, untill having part of sulfuric acid ferrous iron insoluble in solution, filter to take lower clear liquid, i.e.,
For ferrous sulfate saturated solution.
In order to avoid introducing additional impurities, errous sulfate crystal purity is improved, the purity of the water is not less than deionized water.
The inventive method is using ammonium sulfate or ammonium hydrogen sulfate as salting-out agents.Ammonium sulfate or ammonium hydrogen sulfate are in the solution
Solubility is far longer than ferrous sulfate, is 2~3 times of ferrous sulfate, and be influenced by temperature it is relatively low, therefore by certain mass
Ammonium sulfate or ammonium hydrogen sulfate are added in ferrous sulfate saturated solution, on the one hand can improve ferrous sulfate in the solution effective
Concentration, another aspect dissolving and heat absorbing can reduce the solubility of ferrous sulfate in the solution, and double action can make ferrous sulfate
Spontaneous crystallization separates out in a manner of homogeneous nucleation；But ammonium sulfate or ammonium hydrogen sulfate add excessively, impurity may be caused to separate out, and influence
Errous sulfate crystal purity, while if ammonium sulfate or ammonium hydrogen sulfate can not be completely dissolved in the solution, can also influence sulfuric acid Asia
Iron crystal purity；In order to ensure the yield of errous sulfate crystal, while impurity in errous sulfate crystal is reduced to greatest extent and is contained
Amount, the addition of salting-out agents are：Every liter of ferrous sulfate saturated solution adds 0.1~0.5kg salting-out agents；The salting-out agents are sulfuric acid
At least one of ammonium or ammonium hydrogen sulfate.
In the inventive method salting-out crystallization purge process, it is necessary to persistently stir 6~24h, it is ensured that errous sulfate crystal it is pure
Degree and yield.
Because requirement of the ferrous sulfate to ferrous sulfate purity of different purposes is different, byproduct ferrous sulfate of titanium dioxide warp
The purity requirement of corresponding uses may be not met by by crossing impurity content in errous sulfate crystal obtained by a purification step, this
When, errous sulfate crystal can be repeated purification operations of saltouing, until the errous sulfate crystal of final gained meets corresponding purity
It is required that.
Optimization, a kind of method of purification of saltouing of byproduct ferrous sulfate of titanium dioxide, this method comprises the following steps：
By byproduct ferrous sulfate of titanium dioxide, (its impurity content is：Mn：0.108%th, Mg：0.640%th, Ti：0.213%)
It is added to the water, untill having part of sulfuric acid ferrous iron insoluble in solution, filters to take lower clear liquid, as ferrous sulfate saturated solution；
Salting-out agents are added into ferrous sulfate saturated solution, persistently stir 6~24h, filtering, filter cake dries to obtain errous sulfate crystal；Institute
The addition for stating salting-out agents is：Every liter of ferrous sulfate saturated solution adds 0.1~0.5kg salting-out agents；The salting-out agents are sulfuric acid
At least one of ammonium or ammonium hydrogen sulfate.
The present invention is described in further detail below by embodiment, but therefore not limited the scope of the present invention
Among described scope of embodiments.
Ferrous sulfate saturated solution used in the embodiment of the present invention is prepared by the following method：Take by-product of white titanium pigment sulphur
Sour ferrous, its impurity content is Mn after testing：0.108%th, Mg：0.640%th, Ti：0.213%, at normal temperatures (20~30 DEG C),
Add byproduct ferrous sulfate of titanium dioxide while stirring into deionized water, part of sulfuric acid ferrous iron is insoluble to be until having in solution
Only, lower clear liquid, as ferrous sulfate saturated solution are filtered to take, impurity content is Mn in ferrous sulfate saturated solution after testing：
0.539g/L、Mg：1.844g/L、Ti：0.901g/L.
Embodiment 1
500mL ferrous sulfate saturated solutions are measured, add 50g ammonium sulfate while stirring, it is 6h to continue mixing time, mistake
Filter, filter cake dry to obtain errous sulfate crystal, and the impurity content in errous sulfate crystal is Mn after testing：0.026%th, Mg：
0.246%th, Ti：0.008%, the yield 46.35% of iron.
Embodiment 2
500mL ferrous sulfate saturated solutions are measured, add 100g ammonium sulfate while stirring, it is 12h to continue mixing time, mistake
Filter, filter cake dry to obtain errous sulfate crystal, and the impurity content in errous sulfate crystal is Mn after testing：0.034%th, Mg：
0.255%th, Ti：0.009%, the yield 55.72% of iron.
Embodiment 3
500mL ferrous sulfate saturated solutions are measured, add 250g ammonium sulfate while stirring, it is 24h to continue mixing time, mistake
Filter, filter cake dry to obtain errous sulfate crystal, and the impurity content in errous sulfate crystal is Mn after testing：0.022%th, Mg：
0.212%th, Ti：0.007%, the yield 67.51% of iron.
Embodiment 4
500mL ferrous sulfate saturated solutions are measured, add 200g ammonium hydrogen sulfates while stirring, it is 12h to continue mixing time,
Filtering, filter cake dry to obtain errous sulfate crystal, and the impurity content in errous sulfate crystal is Mn after testing：0.019%th,
Mg：0.198%th, Ti：0.008%, the yield 68.36% of iron.
From embodiment 1~4, the inventive method can effectively reduce Mn, Mg, Ti etc. in byproduct ferrous sulfate of titanium dioxide
Impurity, technique is simple, reaction time is short, economic and environment-friendly, removal of impurity is high, and can obtains higher iron recovery under normal temperature
Rate；It is not added with precipitating reagent, is not introduced into metal impurities, and avoid the problem of oxidation of ferrous ion, is by-product of white titanium pigment sulphur
Sour ferrous iron provides a kind of new approach.
Claims (7)
1. the method for purification of saltouing of byproduct ferrous sulfate of titanium dioxide, it is characterised in that：Comprise the following steps：
Byproduct ferrous sulfate of titanium dioxide is added to the water, untill having part of sulfuric acid ferrous iron insoluble in solution, filtered to take down
Clear liquid, as ferrous sulfate saturated solution；Salting-out agents are added into ferrous sulfate saturated solution, lasting stirring is no less than 6h, mistake
Filter, filter cake dry to obtain errous sulfate crystal.
2. the method for purification of saltouing of byproduct ferrous sulfate of titanium dioxide according to claim 1, it is characterised in that：The titanium
The impurity weight/mass percentage composition of white powder by-product ferrous sulfate is Mn：0.1~5%, Mg：0.1~5%, Ti：0.01~10%.
3. the method for purification of saltouing of byproduct ferrous sulfate of titanium dioxide according to claim 1, it is characterised in that：The water
Purity be not less than deionized water.
4. the method for purification of saltouing of byproduct ferrous sulfate of titanium dioxide according to claim 1, it is characterised in that：The salt
Analysis agent addition be：0.1~0.5kg salting-out agents are added in every liter of ferrous sulfate saturated solution.
5. the method for purification of saltouing of the byproduct ferrous sulfate of titanium dioxide according to any one of Claims 1 to 4, its feature exist
In：The salting-out agents are at least one of ammonium sulfate or ammonium hydrogen sulfate.
6. the method for purification of saltouing of byproduct ferrous sulfate of titanium dioxide according to claim 1, it is characterised in that：It is described to hold
The time of continuous stirring is 6~24h.
7. the method for purification of the byproduct ferrous sulfate of titanium dioxide according to any one of claim 1~6, it is characterised in that：
When errous sulfate crystal can not meet purity requirement, purification operations are repeated.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112938922A (en) * | 2021-04-21 | 2021-06-11 | 超彩环保新材料科技有限公司 | Method for preparing battery-grade iron phosphate from titanium dioxide byproduct ferrous sulfate |
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| CN101723458A (en) * | 2009-12-01 | 2010-06-09 | 南阳西成科技有限公司 | Method for cleanly extracting vanadium pentexide from vanadium containing material |
| CN101973587A (en) * | 2010-10-19 | 2011-02-16 | 河南佰利联化学股份有限公司 | Method for purifying ferrous sulfate heptahydrate byproduct in titanium white production |
| CN104512939A (en) * | 2013-09-28 | 2015-04-15 | 天津市大港华明化工厂 | Method for purifying ferrous sulfate by by-product of titanium dioxide |
| CN106745219A (en) * | 2016-12-13 | 2017-05-31 | 山东东佳集团股份有限公司 | A kind of ferrous sulfate purifies the method for comprehensive utilization of removal of impurities discarded object |
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- 2017-11-15 CN CN201711128162.3A patent/CN107857304A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723458A (en) * | 2009-12-01 | 2010-06-09 | 南阳西成科技有限公司 | Method for cleanly extracting vanadium pentexide from vanadium containing material |
| CN101973587A (en) * | 2010-10-19 | 2011-02-16 | 河南佰利联化学股份有限公司 | Method for purifying ferrous sulfate heptahydrate byproduct in titanium white production |
| CN104512939A (en) * | 2013-09-28 | 2015-04-15 | 天津市大港华明化工厂 | Method for purifying ferrous sulfate by by-product of titanium dioxide |
| CN106745219A (en) * | 2016-12-13 | 2017-05-31 | 山东东佳集团股份有限公司 | A kind of ferrous sulfate purifies the method for comprehensive utilization of removal of impurities discarded object |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112938922A (en) * | 2021-04-21 | 2021-06-11 | 超彩环保新材料科技有限公司 | Method for preparing battery-grade iron phosphate from titanium dioxide byproduct ferrous sulfate |
| CN112938922B (en) * | 2021-04-21 | 2023-09-29 | 超彩环保新材料科技有限公司 | Method for preparing battery-grade ferric phosphate from titanium white byproduct ferrous sulfate |
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