CN1079374C - Preparation of titanic-schorl type titanium white by hydrochloric -acid process - Google Patents
Preparation of titanic-schorl type titanium white by hydrochloric -acid process Download PDFInfo
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- CN1079374C CN1079374C CN98113128A CN98113128A CN1079374C CN 1079374 C CN1079374 C CN 1079374C CN 98113128 A CN98113128 A CN 98113128A CN 98113128 A CN98113128 A CN 98113128A CN 1079374 C CN1079374 C CN 1079374C
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Abstract
The present invention comprises the following steps: adding diluted hydrochloric acid to a reaction vessel resisting hydrochloric acid, simultaneously adding pulverized ilmenite and a reductant under the condition that the hydrolysis crystal seeds of metatitanic acid exist, and maintaining a temperature at 108 to 110 DEG C; keeping the existence of a small amount of reductant in the entire process of ilmenite decomposition and metatitanic acid hydrolysis; separating the metatitanic acid the mother liquor by filtration after the decomposition and the hydrolysis are finished, and washing the metatitanic acid; separating the unhydrolyzed minerals with bigger sizes from the metatitanic acid by adopting a gravity separation method, and removing the SiO2 from the metatitanic acid by adding HF; bleaching and salinizing the metatitanic acid, caclining the metatitanic acid at a temperature of 850 to 900 DEG C, and thereby obtaining the titanic-schorl type titanium white. The obtained titanic-schorl type titanium white with a whiteness which is approximate or equal to that of the imported titanic-schorl type titanium white.
Description
The invention belongs to the preparation method of pigment Rutile type Titanium Dioxide.
Titanium dioxide has two kinds of production methods at present, and a kind of is sulfuric acid process, and this method Production Flow Chart is long, and serious three wastes has downtrending in the ratio of whole output, and another kind is a chlorination process, is characterized in that the Rutile type Titanium Dioxide quality is good, and the three wastes are few.Titanium tetrachloride t technical difficulty in chlorination process is produced is big, and China yet there are no the report of success so far through the development test of decades.China's Panzhihua Region is being contained billions of tons titanium resource, this ilmenite is to belong to primary ore, be characterized in that ferric iron content is low, content of titanium dioxide is on the low side, and magnesium calcium contents height, if produce artificial rutile with electric heating process, the magnesium calcium contents height in the artificial rutile then, unsuitable chlorination producing titanium tetrachloride t 5 bx, have only and just be convenient to chlorating with the artificial rutile of removing magnesium calcium of dilute hydrochloric acid manufactured and carry out, if can directly decompose ilmenite and hydrolysis simultaneously goes out metatitanic acid with dilute hydrochloric acid, is not the technology of producing Rutile type Titanium Dioxide like this simpler? because hydrolysis generates metatitanic acid and easily form rutile titanium dioxide when calcining under hydrochloric acid medium, therefore the many R﹠D institutions of China have carried out the technology of salt acid system development Rutile type Titanium Dioxide, promptly produce titanium liquid with the hydrochloric acid decomposition ilmenite of concentration 34%, after reduction, filter, freezing and crystallizing separates ferrous chloride, add the hydrolysis of metatitanic acid hydrolysis crystal seed and go out metatitanic acid, use common washing again, bleaching, salt is handled, calcining is pulverized and is produced Rutile type Titanium Dioxide (for to distinguish mutually with this law, this paper claims that this method is the concentrated hydrochloric acid method), the problem that this method exists is a flow process and sulfuric acid process length about the same, simultaneously in the concentrated hydrochloric acid medium, decompose ilmenite, reduction, filter, freezing and crystallizing separates ferrous chloride, when adding operation such as crystal seed hydrolysis, hydrochloric acid is difficult for solving to the etching problem of equipment.According to above situation, we study the technology that successfully adopts preparation of titanic-schorl type titanium white by hydrochloric-acid process finally through exploring for a long time.
Method for making of the present invention is such, in the reactor of salt tolerant acid, concentration is that 19% dilute hydrochloric acid is preheating to 100 ℃, add metatitanic acid hydrolysis crystal seed, ilmenite, the muriate of titanous or the sulfate liquor of titanous through pulverizing, continuous elevated temperature in the time of reinforced, material finishes the back temperature maintenance at 108 °-110 ℃, ilmenite constantly is decomposed and continuous hydrolysis goes out metatitanic acid, in whole decomposition and hydrolytic process, trivalent titanium ion constantly is consumed, need constantly to replenish, in entire reaction course, must keep the concentration of titanium ion 0.3～0.5g/l at a low price.Count reaction end in about 6 hours from reinforced finishing, after filtration, will contain chlorination ferrous spent acid mother liquor separately after the cooling, metatitanic acid is through washing, remove remaining iron protochloride, from metatitanic acid, isolate the mineral that decompose without thoroughly through the stage division of gravity concentration.According to SiO in the metatitanic acid
2Content adds the HF of respective amount, will generate corresponding SiF
4Gas and with SiO
2Remove, then calcined about 1 hour through routine bleaching and salt processing then, produce the commodity Rutile type Titanium Dioxide through surface treatment and pulverizing again at 850 °～900 ℃.Iron protochloride spent acid mother liquor can adopt torch firing regeneration hydrochloric acid and pair product ferric oxide, and regeneration hydrochloric acid retrieval system is decomposed ilmenite, pays the product ferric oxide and can make low-grade pigment or its usefulness.Iron protochloride spent acid mother liquor also can be produced the raw material of red iron oxide as wet method.The processing of iron protochloride spent acid mother liquor and the surface treatment of titanium dioxide all have sophisticated technology.
Go out metatitanic acid because the present invention adopts the dilute hydrochloric acid limit of concentration 19% to decompose ilmenite limit hydrolysis, lack than sulfuric acid process and concentrated hydrochloric acid method operation, equipment is few, and cost has also reduced.It is similar that the BCA legal system of the operation of this law fore portion and technical maturity is got artificial rutile, all is to adopt about 20% dilute hydrochloric acid decomposition ilmenite, filtration, washing, can not cause serious corrosion to equipment.While reduces the discharging of the three wastes because the spent acid mother liquor can adopt torch firing regeneration hydrochloric acid and pair product ferric oxide or wet method to produce the raw material of red iron oxide.
This law preferably adopts ferric iron content low, does not have the primary ilmenite of weathering alteration or seldom weathering alteration to make raw material.
Example: in the reactor of salt tolerant acid, when the dilute hydrochloric acid of adding 19% is preheating to 100 ℃, add the metatitanic acid hydrolysis crystal seed, ilmenite and the muriate of titanous or the sulfate liquor of titanous through pulverizing, improve constantly temperature in the time of reinforced, behind reinforced the finishing, temperature maintenance is at 108 °～110 ℃, in the whole process of ilmenite decomposition and metatitanic acid hydrolysis, the content that remains the titanous acid ion is 0.3～0.5g/l, the reinforced back that finishes was decomposed in about 6 hours and hydrolysis finishes, filtration separates metatitanic acid with iron protochloride spent acid mother liquor, metatitanic acid is washed, and the mineral that adopt the shale shaking table that end in the metatitanic acid is thoroughly decomposed are separated, after the metatitanic acid slurrying, according to SiO in the metatitanic acid
2Content adds an amount of HF with SiO
2Remove.Bleaching and salt acid treatment then is at last 850 °～900 ℃ calcinings about 1 hour, through the last surface treated Rutile type Titanium Dioxide of broken acquisition.
Figure of description is seen in technical process
Claims (1)
1, the method of preparation of titanic-schorl type titanium white by hydrochloric-acid process, this method is a kind of method of getting the pigment Rutile type Titanium Dioxide with the hydrochloric acid legal system, it is characterized in that in the reactor of salt tolerant acid, adding concentration is 19% dilute hydrochloric acid, when being warmed up to 100 ℃, add the metatitanic acid hydrolysis crystal seed, add ilmenite and the muriate of titanous or the sulfate liquor of titanous simultaneously through pulverizing, material finishes the back temperature maintenance at 108-110 ℃, keeping at a low price in whole process, titanium ion concentration is 0.3～0.5g/l, material finishes back reaction in about 6 hours to be finished, cooled and filtered is separated metatitanic acid with iron protochloride spent acid mother liquor, metatitanic acid is through washing, adopt the stage division of gravity concentration that the mineral that thoroughly do not decompose in the metatitanic acid are separated, then will be according to SiO in the metatitanic acid
2Content add HF and remove SiO
2Then handle through routine bleaching and salt, at last 850 °～900 ℃ calcinings about 1 hour, obtain not surface treated Rutile type Titanium Dioxide through pulverizing, iron protochloride spent acid mother liquor is through torch firing regeneration hydrochloric acid and ferric oxide, regeneration hydrochloric acid retrieval system is decomposed ilmenite, and ferric oxide is made low-grade iron oxide pigment, and the spent acid mother liquor also can be used as the raw material that wet method is produced red iron oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113128A CN1079374C (en) | 1998-02-24 | 1998-02-24 | Preparation of titanic-schorl type titanium white by hydrochloric -acid process |
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| Application Number | Priority Date | Filing Date | Title |
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| CN98113128A CN1079374C (en) | 1998-02-24 | 1998-02-24 | Preparation of titanic-schorl type titanium white by hydrochloric -acid process |
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| CN1217298A CN1217298A (en) | 1999-05-26 |
| CN1079374C true CN1079374C (en) | 2002-02-20 |
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| CN98113128A Expired - Fee Related CN1079374C (en) | 1998-02-24 | 1998-02-24 | Preparation of titanic-schorl type titanium white by hydrochloric -acid process |
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| CN101116785B (en) * | 2007-08-31 | 2010-12-15 | 乐昌市银星化工有限公司 | Floating ball self-sucking titanium liquid-cleaning technique |
| CN101935063B (en) * | 2009-09-02 | 2012-01-25 | 沙立林 | High titanium hydrochloric acid leaching slag and application thereof |
| CN103741263B (en) * | 2014-01-15 | 2016-04-20 | 辽宁石油化工大学 | A kind of high-ratio surface porous TiO 2the preparation method of nanofiber |
| CN104192898B (en) | 2014-09-11 | 2016-03-02 | 福建坤彩材料科技股份有限公司 | The preparation method of titanium dioxide is directly synthesized from the rich titanium organic phase prepared by ilmenite |
| CN105271396A (en) * | 2015-10-23 | 2016-01-27 | 云南千盛实业有限公司 | Acidolysis method of titanium dioxide by hydrochloric acid method |
| CN108002434A (en) * | 2017-11-30 | 2018-05-08 | 广西雅照钛白有限公司 | A kind of method that titanium dioxide is prepared with sulfuric acid |
| CN108316926B (en) * | 2017-12-29 | 2019-06-04 | 四川江铜稀土有限责任公司 | A kind of method of differentiation explosion hydraulic mining fine-structure mesh arteries and veins REE mineralization rock |
| CN108149015B (en) * | 2018-01-15 | 2020-01-14 | 东北大学 | Method for extracting valuable components from vanadium-titanium magnetite through oxygen-enriched selective leaching |
| CN108300874B (en) * | 2018-01-15 | 2020-09-29 | 东北大学 | Method for selectively leaching and upgrading high-titanium slag |
| CN108300875B (en) * | 2018-01-15 | 2020-10-16 | 东北大学 | Preparation of high-purity TiO by selectively leaching titanium concentrate in oxygen-enriched manner2Method (2) |
| CN108217722A (en) * | 2018-03-02 | 2018-06-29 | 茂名粤桥集团矿业有限公司 | A kind of raising Reductive leaching synthetic rutile TiO2The process of grade |
| CN109467123A (en) * | 2018-11-23 | 2019-03-15 | 宜宾天原集团股份有限公司 | A kind of artificial rutile mether liquor comprehensive resource utilizes method |
| CN113371750B (en) * | 2021-06-08 | 2023-07-28 | 龙佰集团股份有限公司 | Method for preparing barium sulfate by combining titanium white waste acid with chlorination method and titanium white waste acid with sulfuric acid method |
| CN115974144A (en) * | 2021-11-27 | 2023-04-18 | 四川省有色矿冶科技有限公司 | Production process for preparing titanium dioxide by hydrochloric acid method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1017338B (en) * | 1985-05-21 | 1992-07-08 | 白奥格尔药物工厂 | The method of the preparation medical cross-linked glucan particles polymkeric substance that has improved |
| CN1114949A (en) * | 1994-07-09 | 1996-01-17 | 山东大学 | Preparation method of high-purity micro-fine rutile-type titanium dioxide |
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1998
- 1998-02-24 CN CN98113128A patent/CN1079374C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1017338B (en) * | 1985-05-21 | 1992-07-08 | 白奥格尔药物工厂 | The method of the preparation medical cross-linked glucan particles polymkeric substance that has improved |
| CN1114949A (en) * | 1994-07-09 | 1996-01-17 | 山东大学 | Preparation method of high-purity micro-fine rutile-type titanium dioxide |
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| CN1217298A (en) | 1999-05-26 |
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