CN100448781C - Method for mixed acid hydrolysis of acid-soluble titanium slag and ilmenite - Google Patents
Method for mixed acid hydrolysis of acid-soluble titanium slag and ilmenite Download PDFInfo
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- CN100448781C CN100448781C CNB2006100383517A CN200610038351A CN100448781C CN 100448781 C CN100448781 C CN 100448781C CN B2006100383517 A CNB2006100383517 A CN B2006100383517A CN 200610038351 A CN200610038351 A CN 200610038351A CN 100448781 C CN100448781 C CN 100448781C
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Abstract
The present invention relates to a method for acid hydrolysis by using acid soluble titanium slag as raw material in the process of producing sulfuric acid process titanium pigment. The method comprises the steps that the pulverized acid soluble titanium slag and titanic iron ore is weighed according to a proportion of 7:3 to 4:1; according to a proportion of 1:1.68 to 1:1.75 of mineral powder to the concentrated sulphuric acid, the pulverized acid soluble titanium slag and titanic iron ore are added into concentrated sulphuric acid, sufficiently stirred and uniformly mixed, and then the mixed concentrated sulphuric acid solution is simultaneously stirred and heated; when the temperature rises to 130 DEG C to 150DEGC, the temperature is stopped from rising; finally, a solid mixture is generated; after the solid mixture is cured for four to six hours under the condition of 140 DEG C to 220 DEG C, the solid mixture is crushed, and water is added to dissolve the mixture; the temperature is maintained to be from about 60 DEG C to 95 DEG C until the solid mixture is basically clarified; a flocculating agent is added to make solid impurities settle so as to remove the impurities, and the solution is filtered to obtain a titanium sulfat solution. The method has the advantages that the titanium sulfat solution which meets the quality requirements of subsequent steps can be produced under the condition of not reforming the existing acid hydrolysis production device; freezing crystallization and separation of ferrous sulfate heptahydrate are not needed; steps are simplified, energy resources are saved, and productivity is increased.
Description
Technical field
The present invention relates to use in a kind of sulfuric acid method titanium pigment production process acid-dissolved titanium slag to be the method that raw material carries out acidolysis, refer in particular to, prepare the method for the intermediates in its production process-----titanyl sulfate solution acid-dissolved titanium slag and ilmenite mixing acidolysis.
Background technology
Titanium dioxide is a kind of white pigment of performance brilliance, can be widely used in fields such as coating, plastics, papermaking, printing ink, catalyzer and the cosmetics of super quality.The method of producing titanium dioxide mainly contains sulfuric acid process and chlorination process, and its use worldwide respectively accounts for 50%, and sulfuric acid process can be used in the production of making rutile-type and anatase thpe white powder, and the chlorination rule is mainly used in the production of Rutile type Titanium Dioxide.
It mainly is ilmenite and acid-dissolved titanium slag that sulfuric acid method titanium pigment is produced used raw material.Content of titanium dioxide in the ilmenite is about 45～52%, and grade is lower, and acid-dissolved titanium slag is a kind of raw material of artificial enrichment, and content of titanium dioxide can reach 75～80%, and is of high grade, and foreign matter content is few, is the development trend of current international titanium material demand.Use acid-dissolved titanium slag to compare with using ilmenite, can omit freezing and crystallizing, ferrous sulfate separation and titanium liquid enrichment process, shorten the production cycle, reduce production costs as raw material.Yet, the composition of acid-dissolved titanium slag and ilmenite is formed marked difference, cause the characteristic of the titanyl sulfate solution of making after the acidolysis different fully, what the acidolysis of use acid-dissolved titanium slag obtained is the solution with reduction characteristic, need to add oxygenant and reduce its reductibility, otherwise, what the use ilmenite obtained then is the solution with oxidation characteristic, need to add reductive agent and reduce oxidisability, the corrosion-proof lining of the equipment of acidolysis such as acidolysis still correspondingly, pipeline, pump and valve should be selected the material of resistance to reduction solution or oxidation-resistance solution respectively for use, particularly for use ilmenite to carry out as raw material for the factory of acidolysis always, the material of its original production unit can't satisfy the production requirement of acid-dissolved titanium slag.Simultaneously, use the quality index of the titanyl sulfate solution of acid-dissolved titanium slag acidolysis preparation, as iron titanium ratio, titanouses etc. have than big-difference with the titanyl sulfate solution of ilmenite acidolysis preparation, this species diversity can influence the production technique of postorder operation largely, as adjust improperly, will cause titanium dioxide final product quality performance decrease.
Summary of the invention
The objective of the invention is to produce on the technology and Equipment Foundations of titanium dioxide for the raw material sulphuric acid method with the ilmenite existing, the increase acid-dissolved titanium slag is a main raw material, a kind of acid-dissolved titanium slag and ilmenite mixing acid hydrolysis method are proposed, the intermediates--method of----titanyl sulfate solution during the preparation sulfuric acid method titanium pigment is produced.
The technical scheme that realizes above-mentioned purpose is:
Take by weighing acid-dissolved titanium slag and the ilmenite of having pulverized in 7: 3～4: 1 ratios, add in 1: 1.68～1: 1.75 the vitriol oil and fully stir, mix, stir on one side then, heat up on one side, when temperature rises to 130～150 ℃, stop to heat up, reaction will spontaneously be carried out, generate solid-state mixture at last, mixture placed under 140 ℃～220 ℃ the condition slaking 4～6 hours, and was dissolved in water, keep solvent temperature about 60 ℃～95 ℃ molten substantially clear until solid mixt.Add flocculation agent and make the solid impurity sedimentation, remove settled impurity and after further filtering, obtain titanyl sulfate solution.
The invention has the advantages that the method for using acid-dissolved titanium slag and iron iron ore mixing acidolysis, can be under the condition of existing acidolysis production equipment not being transformed, produce and satisfy the titanyl sulfate solution that the postorder process quality requires, index when its quality index and independent use ilmenite acidolysis is close, do not separate with ferrous sulfate but do not need to carry out freezing and crystallizing, thus simplification, the saving of the energy and the raising of production capacity of realization operation.
Embodiment
Comparative Examples 1
Measure 175ml concentration and be about 88% the vitriol oil in the 1000ml beaker, take by weighing the ilmenite that 180g crushes, add in the vitriol oil and stirred 10 minutes, stir on one side then, heat up on one side, temperature stops heating when rising to 100 ℃, react spontaneous carrying out, generate solid mixt, mixture is placed 140 ℃ baking oven slaking 2 hours, taking out and add water to volume reaches 650ml and dissolves, keep about 70 ℃ of solvent temperature, add the 15g iron powder after 30 minutes and reduce, after iron powder reaction end and solid mixt dissolve fully, add the small amount of flocculant polyacrylamide and make the solid impurity sedimentation, separate, again gained solution is carried out freezing and crystallizing, when temperature drops to 13 ℃, take out, the ferrous sulfate of separating out is separated and solution is further carried out vacuum concentration after the clarification, obtain to carry out TiO after evaporating 150ml water
2H
2The titanyl sulfate mixing solutions that O produces.
Comparative Examples 2
Measure 175ml concentration and be about 96% the vitriol oil in the 1000ml beaker, take by weighing the acid-dissolved titanium slag that 180g crushes, add in the vitriol oil and stirred 10 minutes, stir on one side then, heat up on one side, temperature stops heating when rising to 140 ℃, react spontaneous carrying out, generate solid mixt, mixture is placed 180 ℃ baking oven slaking 5 hours, take out and add water to volume and reach 720ml and dissolve, keep about 85 ℃ of solvent temperature, solid mixt dissolves fully after 120 minutes, and gradation adding 5g SODIUMNITRATE is carried out the Ti in the oxidation reduction solution
3+Content, add the small amount of flocculant polyacrylamide then and make solid impurity sedimentation, separation, further clarify, obtain carrying out TiO
2H
2The titanyl sulfate mixing solutions that O produces.
Example 1
In the ratio of breeze and 100% vitriol oil of reaction is 1: 1.68 preparation ore deposit and sulfuric acid.Measure 171ml concentration and be about 96% the vitriol oil in the 1000ml beaker, take by weighing the ilmenite that acid-dissolved titanium slag that 126g crushes and 54g crush, both ratios are 7: 3, add simultaneously in the vitriol oil and stirred 10 minutes, stir on one side then, heat up on one side, temperature stops heating when rising to 130 ℃, react spontaneous carrying out, generate solid mixt, mixture is placed 140 ℃ baking oven slaking 4 hours, take out and add water to volume and reach 640ml and dissolve, keep about 60 ℃ of solvent temperature, solid mixt dissolves fully after 120 minutes, add the small amount of flocculant polyacrylamide then and make the solid impurity sedimentation, separate, further clarify, obtain to carry out TiO
2H
2The titanyl sulfate mixing solutions that O produces.
Example 2
In the ratio of breeze and 100% vitriol oil of reaction is 1: 1.70 preparation ore deposit and sulfuric acid.Measure 177ml concentration and be about 94% the vitriol oil in the 1000ml beaker, take by weighing the ilmenite that acid-dissolved titanium slag that 126g crushes and 54g crush, both ratios are 7: 3, add simultaneously in the vitriol oil and stirred 10 minutes, stir on one side then, heat up on one side, temperature stops heating when rising to 150 ℃, react spontaneous carrying out, generate solid mixt, mixture is placed 180 ℃ baking oven slaking 4 hours, take out and add water to volume and reach 640ml and dissolve, keep about 85 ℃ of solvent temperature, solid mixt dissolves fully after 120 minutes, add the small amount of flocculant polyacrylamide then and make the solid impurity sedimentation, separate, further clarify, obtain to carry out TiO
2H
2The titanyl sulfate mixing solutions that O produces.
Example 3
In the ratio of breeze and 100% vitriol oil of reaction is 1: 1.72 preparation ore deposit and sulfuric acid.Measure 175ml concentration and be about 96% the vitriol oil in the 1000ml beaker, take by weighing the ilmenite that acid-dissolved titanium slag that 126g crushes and 54g crush, both ratios are 7: 3, add simultaneously in the vitriol oil and stirred 10 minutes, stir on one side then, heat up on one side, temperature stops heating when rising to 140 ℃, react spontaneous carrying out, generate solid mixt, mixture is placed 220 ℃ baking oven slaking 4 hours, take out and add water to volume and reach 640ml and dissolve, keep about 75 ℃ of solvent temperature, solid mixt dissolves fully after 120 minutes, add the just solid impurity sedimentation of small amount of flocculant polyacrylamide then, separate, further clarify, obtain to carry out TiO
2H
2The titanyl sulfate mixing solutions that O produces.
Example 4
In the ratio of breeze and 100% vitriol oil of reaction is 1: 1.72 preparation ore deposit and sulfuric acid.Measure 172ml concentration and be about 98% the vitriol oil in the 1000ml beaker, take by weighing the ilmenite that acid-dissolved titanium slag that 135g crushes and 45g crush, both ratios are 7.5: 2.5, add simultaneously in the vitriol oil and stirred 10 minutes, stir on one side then, heat up on one side, temperature stops heating when rising to 140 ℃, react spontaneous carrying out, generate solid mixt, mixture is placed 160 ℃ baking oven slaking 4 hours, take out and add water to volume and reach 650ml and dissolve, keep about 95 ℃ of solvent temperature, solid-state mixed platform thing dissolves fully after 120 minutes, add the small amount of flocculant polyacrylamide then and make the solid impurity sedimentation, separate, further clarify, obtain to carry out TiO
2H
2The titanyl sulfate mixing solutions that O produces.
Example 5
In the ratio of breeze and 100% vitriol oil of reaction is 1: 1.75 preparation ore deposit and sulfuric acid.Measure 178ml concentration and be about 96% the vitriol oil in the 1000ml beaker, take by weighing the ilmenite that acid-dissolved titanium slag that 135g crushes and 45g crush, both ratios are 7.5: 2.5, add simultaneously in the vitriol oil and stirred 10 minutes, stir on one side then, heat up on one side, temperature stops heating when rising to 150 ℃, react spontaneous carrying out, generate solid mixt, mixture is placed 180 ℃ baking oven slaking 6 hours, take out and add water to volume and reach 650ml and dissolve, keep about 85 ℃ of solvent temperature, solid mixt dissolves fully after 120 minutes, add the small amount of flocculant polyacrylamide then and make the solid impurity sedimentation, separate, further clarify, obtain to carry out TiO
2H
2The titanyl sulfate mixing solutions that O produces.
Example 6
In the ratio of breeze and 100% vitriol oil of reaction is 1: 1.72 preparation ore deposit and sulfuric acid.Measure 175ml concentration and be about 96% the vitriol oil in the 1000ml beaker, take by weighing the ilmenite that acid-dissolved titanium slag that 144g crushes and 36g crush, both ratios are 4: 1, add simultaneously in the vitriol oil and stirred 10 minutes, stir on one side then, heat up on one side, temperature stops heating when rising to 130 ℃, react spontaneous carrying out, generate solid mixt, mixture is placed 180 ℃ baking oven slaking 4 hours, take out and add water to volume and reach 650ml and dissolve, keep about 85 ℃ of solvent temperature, solid mixt dissolves fully after 120 minutes, add the small amount of flocculant polyacrylamide then and make the solid impurity sedimentation, separate, further clarify, obtain to carry out TiO
2H
2The titanyl sulfate mixing solutions that O produces.
Example 7
In the ratio of breeze and 100% vitriol oil of reaction is 1: 1.72 preparation ore deposit and sulfuric acid.Measure 184ml concentration and be about 92% the vitriol oil in the 1000ml beaker, take by weighing the ilmenite that acid-dissolved titanium slag that 144g crushes and 36g crush, both ratios are 4: 1, add simultaneously in the vitriol oil and stirred 10 minutes, stir on one side then, heat up on one side, temperature stops heating when rising to 150 ℃, react spontaneous carrying out, generate solid mixt, mixture is placed 180 ℃ baking oven slaking 6 hours, take out and add water to volume and reach 650ml and dissolve, keep about 85 ℃ of solvent temperature, solid mixt dissolves fully after 120 minutes, add the small amount of flocculant polyacrylamide then and make the solid impurity sedimentation, separate, further clarify, obtain to carry out TiO
2H
2The titanyl sulfate mixing solutions that O produces.
The effect of above-mentioned Comparative Examples and example is as shown in the table, and acid-dissolved titanium slag acidolysis patent is relevant, and to be suitable for the quality index of the titanyl sulfate solution that the postorder operation uses as follows:
TiO
2Content: 195-220g/l iron titanium ratio: 0.6-1.0 F value: 1.65-2.10 Ti
3+: 0.5-5.0g/l
The quality of the titanyl sulfate mixing solutions that Comparative Examples and example are prepared
Claims (1)
1. the method for acid-dissolved titanium slag and ilmenite mixing acidolysis, it is characterized in that taking by weighing acid-dissolved titanium slag and the ilmenite of having pulverized in 7: 3～4: 1 ratios, adding is fully to stir in 1: 1.68～1: 1.75 the vitriol oil by the ratio of the total amount of the described acid-dissolved titanium slag of having pulverized and ilmenite and the vitriol oil, mix, stir on one side then, heat up on one side, when temperature rises to 130～150 ℃, stop to heat up, generate solid-state mixture, mixture placed under 140 ℃～220 ℃ the condition slaking 4～6 hours, be dissolved in water, it is molten substantially clear until solid mixt to keep 60 ℃～95 ℃ of solvent temperatures, adds the flocculation agent polyacrylamide and makes the solid impurity sedimentation, removes settled impurity and obtain titanyl sulfate solution after further filtering.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050487B (en) * | 2010-12-31 | 2012-09-05 | 攀钢集团重庆钛业有限公司 | Acidolysis method in titanium dioxide production technology adopting sulfuric acid process |
| CN104045109B (en) * | 2013-12-03 | 2015-11-18 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method and application thereof of producing acidolysis titanium liquid |
| CN103936064B (en) * | 2014-04-02 | 2016-02-03 | 济南裕兴化工有限责任公司 | A kind of method adopting titanium ore to produce titanium dioxide |
| CN104528818B (en) * | 2015-01-07 | 2016-12-14 | 攀钢集团攀枝花钢铁研究院有限公司 | The characterizing method of slag ore deposit mixed proportion |
| CN107774284B (en) * | 2017-11-10 | 2020-01-10 | 纳琦环保科技有限公司 | Preparation method of aqueous nano antibacterial photocatalytic titanium oxide composite sol |
| CN108675344A (en) * | 2018-06-08 | 2018-10-19 | 龙蟒佰利联集团股份有限公司 | A kind of sulfate process titanium dioxide acidolysis production technology |
| CN114162875A (en) * | 2021-12-31 | 2022-03-11 | 龙佰集团股份有限公司 | Preparation method and preparation device of ferrous sulfate solution for iron oxide pigment and iron oxide pigment |
| CN114368781B (en) * | 2022-01-18 | 2023-10-27 | 武定国钛金属有限公司 | Method for effectively recycling titanium in titanium-containing slag and improving value of byproducts |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4304758A (en) * | 1979-12-21 | 1981-12-08 | Bayer Aktiengesellschaft | Hydrolyzable titanyl sulphate solutions by decomposition of ternary raw material mixtures |
| US4313913A (en) * | 1979-12-21 | 1982-02-02 | Bayer Aktiengesellschaft | Production of hydrolyzable titanyl sulphate solution |
| CN1038324C (en) * | 1993-02-06 | 1998-05-13 | 宁甲保 | Method for enriching titanium dioxide by using titanium ore as raw material |
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2006
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4304758A (en) * | 1979-12-21 | 1981-12-08 | Bayer Aktiengesellschaft | Hydrolyzable titanyl sulphate solutions by decomposition of ternary raw material mixtures |
| US4313913A (en) * | 1979-12-21 | 1982-02-02 | Bayer Aktiengesellschaft | Production of hydrolyzable titanyl sulphate solution |
| CN1038324C (en) * | 1993-02-06 | 1998-05-13 | 宁甲保 | Method for enriching titanium dioxide by using titanium ore as raw material |
Non-Patent Citations (2)
| Title |
|---|
| 酸溶性钛渣酸解工艺研究. 张树立等.钢铁钒钛，第24卷第1期. 2003 |
| 酸溶性钛渣酸解工艺研究. 张树立等.钢铁钒钛，第24卷第1期. 2003 * |
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