CN1078181C - Process for producing nanometre-grade titanic-schorl type titanium dioxide - Google Patents
Process for producing nanometre-grade titanic-schorl type titanium dioxide Download PDFInfo
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- CN1078181C CN1078181C CN97120161A CN97120161A CN1078181C CN 1078181 C CN1078181 C CN 1078181C CN 97120161 A CN97120161 A CN 97120161A CN 97120161 A CN97120161 A CN 97120161A CN 1078181 C CN1078181 C CN 1078181C
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Abstract
The present invention uses titanium sulfate, titanyl sulfate or metatitanic acid as raw materials, uses sodium carbonate as a precipitating agent and uses zinc sulfate as a dispersion transforming agent. The sodium carbonate is used for hydrolyzing the titanium sulfate, etc.; zinc carbonate hydroxide prepared by carbonizing the zinc sulphate coats positive metatitanic acid generated by hydrolysis; the positive metatitanic acid is calcined for 1 to 2 hours in advance under the condition of 500 to 650 degrees; zinc oxide is dissolved by 2 mol/L sulfuric acid; the metatitanic acid obtained by acid dissolution is delivered to a crystal form converter; and the metatitanic acid is heated for 2 hours for carrying out crystal form conversion at the temperature of 800 to 900 degrees to obtain spherical titanium dioxide powder products with the rutile content more than 95% and with the particle diameters of 20 to 50 nanometers.
Description
The invention belongs to the nanometre-grade titanic-schorl type titanium dioxide novel process, particularly disperse to be equipped with the nanometre-grade titanic-schorl type titanium dioxide Technology with hydrolysate legal systems such as transforming titanium sulfate with zn cpds.
The titanium sulfate hydrolytic process is an application technology technology (1) already in the sulfate process titanium dioxide powder craft, by the control hydrolysis condition, can prepare various types of titanium dioxides: as anatase titanium dioxide and rutile-type product.Because of the granularity of the titanium dioxide of above-mentioned explained hereafter can only reach micron order, so the product of this technology can only be applied to sugared porcelain, papermaking, paint is in the industries such as coating.Modern science proves, when the fine size of titanium dioxide during to nano level, it will have the characteristic of a series of excellences, and the research that therefore how to prepare the nano grade titanium white powder is extremely paid attention to.Document 2 is that raw material makes TiO (OH) with titanium sulfate and yellow soda ash earlier on the basis of sulfate process titanium dioxide technology
2Because of this product is difficult to filter and washing, so adopt centrifuge washing, use hydrochloric acid again under 60 ℃, be modulated into transparent solution, obtain transparent organic solution with this solution of organic extractant solution again, this solution is made gluey colloid through backflow and reduced pressure distillation, again with this colloid through vacuum-drying and 200 the degree temperature under thermal treatment obtain noncrystal spherical titanium dioxide particle, through 500 the degree heat anatase titanium dioxide, its median size is 8.50nm, as in 700 degree heating, can get the rutile titanium dioxide that mean particle size is 33.2nm.The loaded down with trivial details control difficulty of process is big, it is raw material that document (3) adopts titanyl sulfate, after formerly adding ethylene glycol monomethyl ether, be heated hydrolysis again, the filtration and selection performance of hydrolysate have been improved, by control hydrolysis and heating condition, preparing mean particle size is the rutile titanium dioxide powder of 38nm.This technology is simpler than document (2) technology, but the percent hydrolysis of its used titanyl sulfate can only reach 21%, and nearly titanyl sulfate of 80 percent can not utilize, and expends a large amount of ethylene glycol monomethyl ethers.The production cost height, wastage of material is big, embarrasses industrial production to accept in fact.In the above-mentioned nanometre-grade titanic-schorl type titanium dioxide powder preparing technology, all used organic agent, its purpose is to solve difficulty washing and the sad filter of titanium sulfate hydrolysate in following process, and the hard aggregation problem of the nanoparticle that very easily takes place when the crystal formation conversion is carried out in heating.Though the employing of above technology can solve these technical barriers to a certain extent, obviously improve on the workinprocess cost, make value of technology and use to be subjected to certain restriction.
At the above-mentioned problem that in nanometre-grade titanic-schorl type titanium dioxide preparation technology, exists, purpose of the present invention aims to provide a kind of difficulty washing that can solve the intermediates in the nanometre-grade titanic-schorl type titanium dioxide preparation, when transforming, crystal formation easily produces the technical barrier of hard aggregation, accomplish that again technology is simple, processing ease, the novel process that product cost is low.
In conjunction with the accompanying drawings 1, main contents of the present invention are presented below:
The present invention is the titanium sulfate that produces with in the sulfate process titanium dioxide technology, titanyl sulfate, or metatitanic acid is that main raw material is a precipitation agent with yellow soda ash or sodium bicarbonate, zn cpds is zinc sulfate or zinc halide etc.As being raw material with the metatitanic acid, main points of the present invention can be described below: acid is molten: metatitanic acid and sulfuric acid are injected sour molten still 1, it is molten to carry out acid under agitation condition, its objective is preparation titanium sulfate or titanyl sulfate solution, control reaction temperature is between the 70-80 degree, and titanium concentration is between the 100-200 grams per liter.Acid is molten finish after, solution is filtered in strainer 2, stand-by behind the removal impurity, in stillpot 3, add sodium carbonate solution, its concentration is at the 450-550 grams per liter, be heated to after the 40-60 degree, titanium sulfate solution in the molten still 1 of acid under agitation condition, is injected stillpot 3, at this moment, after titanium/sodium mol ratio is controlled between the 0.4-0.6, should maintain the temperature between the 30-60 degree in the precipitation process; After precipitation is finished, its pH value should be between 6.0-7.5, allow titanium sulfate wherein be hydrolyzed to positive metatitanic acid, continuing under the stirring condition, solution of zinc sulfate is injected stillpot 3, make it generate zinc subcarbonate on the titanic acid surfaces, the titanic acid particles is coated, the add-on of zinc sulfate will be controlled at the Zn/Ti mol ratio between 3 to 7; The positive metatitanic acid and the solution separating of zinc subcarbonate will coated, liquid is sent to and concentrates reclaim(ed) sulfuric acid sodium, and solids wash behind the sulfate radical-free ion in pre-calcination stove 5 between the 500-650 degree calcination 1-2 hour is converted into zinc oxide to zinc subcarbonate, and positive metatitanic acid is becoming metatitanic acid; With the powder behind the calcination in molten zinc still 6, dissolve away with the sulfuric acid liquid of 2Mol/L concentration zinc oxide the surface, solid-liquid is separated in strainer 7, fluid sulphuric acid zinc returns recycle in the stillpot 3, metatitanic acid is then delivered to asking of crystal formation converter 8 inherent 700-900 degree and was heated 2 hours, finishes the crystal formation conversion process of product.The particle of the nanometre-grade titanic-schorl type titanium dioxide for preparing under these conditions with above technology is spherical, and its median size is in the 10-60 nanometer, and rutile content is more than 95%.As being raw material with titanium sulfate or titanyl sulfate, can simplify technology of the present invention, sour molten process wherein to be removed, all the other are operated with above identical.Owing to adopt zn cpds that hydrolysate is coated among the present invention, the filtration of hydrolysate and the direct motion of washing have been guaranteed, the positive metatitanic acid that zinc subcarbonate is coated carries out pre-calcination, purpose is positive metatitanic acid is converted into metatitanic acid, except that for accomplishing that zinc does not run off in the later molten zinc process, the performance of metatitanic acid is changed, reduce invert point, when crystal formation transforms, can sintering, produce hard aggregation.
Adopt technology of the present invention,, can obtain following positively effect with above-mentioned feedstock production nanometre-grade titanic-schorl type titanium dioxide powder:
1. under the coating of zinc subcarbonate, the problem that the sulphuric acid hydrolysis product is difficult to filter and wash is satisfactorily resolved.
2. under zinc subcarbonate coats, the positive metatitanic acid of hydrolysate is carried out pre-calcination, make its metatitanic acid that is converted into metastable and easy conversion, the loss of the titanium when not only having solved molten zinc, and be that the crystal formation conversion of back lays the foundation.
3. can under the condition of 700-900 degree, realize rutilization through the metatitanic acid of pre-calcination, and can not produce poly-firmly admittedly phenomenon, reduce the cost of energy consumption and product.
4. the zinc salt in order to coat can recycle in technology, and the sulfate radical in the titanium sulfate combines generation sodium sulfate with sodium, can recycle, not to any threat of environment structure.
5. product pellet is sphere, and its particle dia is between the 10-60 nanometer, and rutile content can reach more than 95 percent.
Accompanying drawing and explanation thereof:
Fig. 1 prepares rutile type nano grade titanium dioxide powder fluid layer for zinc disperses conversion method.
(1) for sour molten still-in order to the dissolving metatitanic acid prepare titanyl sulfate solution.
(2) be strainer-acid solution is carried out solid-liquid separation remove impurity.
(3) be stillpot-, make it generate positive metatitanic acid in order to the hydrolysis titanyl sulfate, and at its surface precipitation zinc subcarbonate.
(4) for strainer-in order to carry out liquid-solid separation, liquid is sent between the sodium sulfate recovery vehicle, reclaim(ed) sulfuric acid sodium, standby after the solid phase prod drying.
(5) be pre-calcination stove-positive metatitanic acid that zinc subcarbonate coats is carried out preroasting, make it change into metastable metatitanic acid and zinc oxide at this.
(6) be molten zinc still-remove the zinc oxide on surface is molten with sulfuric acid, produce solution of zinc sulfate at this still.
(7) be strainer-zinc sulfate is separated with metatitanic acid, the recycle of zinc sulfate Returning process, metatitanic acid is delivered to the crystal formation converter and is carried out crystal formation and transform.
(8) be crystal formation converter-between this is with metatitanic acid in 700 to 900 degree, heated 1-2 hours, make it be converted into the Rutile type Titanium Dioxide product.
If when being raw material with titanium sulfate or titanyl sulfate, the operation of first road of flow process can be omitted, and other process is constant.Embodiment
Example 1. is got titanium sulfate 100 grams, be dissolved in 200 ml waters, getting 305 gram yellow soda ash is dissolved in 300 ml waters, after being heated to 45 degree, while stirring titanium sulfate solution is injected in the sodium carbonate solution, makes its hydrolysis generate positive metatitanic acid, afterwards more nearly 500 ml concns be 2Mol/L solution of zinc sulfate under agitation, be added in the hydrolyzed solution, form zinc subcarbonate in titanic acid surfaces precipitation: solid-liquid separation, liquid are used for reclaim(ed) sulfuric acid sodium, and solids wash is behind the sulfate radical-free ion, send pre-calcination stove under 550 degree temperature, to carry out pre-calcination 2 hours after the oven dry, the product of pre-calcination dissolves away with the sulfuric acid of the 2Mol/L zinc oxide with the surface, carries out solid-liquid separation again, and washs till the sulfate radical-free ion, solution of zinc sulfate is in order to the flow process recycle, after the solid phase prod drying, deliver in the crystal formation converter, under 800 degree temperature, heated 2 hours, product detects through transmission electron microscope and X light analysis, and the result shows, is rutile-type more than 98%, the particle outward appearance is a spherical powder, and particle diameter is between the 10-60 nanometer.
Example 2. is got in molten 200 ml waters of 100 gram titanium sulfates, 89 gram yellow soda ash are dissolved in 100 ml waters, after being heated to 45 degree, titanium sulfate liquid under agitation condition, is injected in the sodium carbonate solution, make the titanium sulfate hydrolysis form the titanic Acid precipitation, with 200 ml concns be then 1.5Mol/L sodium carbonate solution under agitation, be added in the hydrolyzed solution after, be that the solution of zinc sulfate of 2Mol/L is added in the above solution again with 500 ml concns, obtain the composite precipitation thing, other operation is identical with example 1.Product is checked by analysis, proves rutile titanium dioxide, and its particle outward appearance is spherical, and particle dia is in the 20-50 nanometer.
Example 3. throw out preparation process are with example 1, but pre-calcination temperature is 650 degree 1 hour, and other step is with example 1, and final product is a rutile titanium dioxide, and particle is the spherical powder of 20-50 nanometer, and rutile content is greater than 95%.
Example 4. sedimentary preparations are with example 1, but the crystal formation invert point is 700 degree, and the product analysis result is the rutile titanium dioxide of 20-40 nanometer, and its rutile content is 85%.
Example 5. sedimentary preparations are with example 1, and the crystal formation invert point is 900 degree, and the final product analytical results is that rutile content is that 99% particle dia is the titanium dioxide of 40-90 nanometer.
Example 6. is got 100 gram titanium sulfates and is dissolved in 400 ml waters, and other step is with example 1.Final product is that the rutile content of 10-30 nanometer is at the titanium dioxide more than 98%.
Example 7. is got 100 gram titanium sulfates and is dissolved in 100 ml waters, and other step is with example 1.Final product is the titanium dioxide of 30-60 nanometer, and rutile content is more than 98%.
Claims (1)
1. method for preparing nanometre-grade titanic-schorl type titanium dioxide, it is characterized in that: being main raw material with the metatitanic acid, is precipitation agent with yellow soda ash or sodium bicarbonate, zinc sulfate or zinc halide are for disperseing transforming agent; Concrete steps are as follows:
Acid is molten: metatitanic acid and sulfuric acid are injected sour molten still 1, and it is molten to carry out acid under agitation condition, and control reaction temperature is between the 70-80 degree, and titanium concentration is between the 100-200 grams per liter; Acid is molten finish after, solution is filtered in strainer 2, remove behind the impurity stand-byly, in stillpot 3, add sodium carbonate solution, its concentration is at the 450-550 grams per liter; Be heated to after the 40-60 degree, the titanium sulfate solution in the molten still 1 of acid is injected stillpot 3 under agitation condition, at this moment, titanium/sodium mol ratio is controlled between the 0.4-0.6; Should maintain the temperature between the 30-60 degree in the precipitation process; After precipitation was finished, its pH value should allow titanium sulfate wherein be hydrolyzed to positive metatitanic acid between 6.0-7.5; Continuing under the stirring condition solution of zinc sulfate to be injected stillpot 3, make it on the titanic acid surfaces, generate zinc subcarbonate, small titanic acid particles is coated, the add-on of zinc sulfate will be controlled at the Zn/Ti mol ratio between 3 to 7; The positive metatitanic acid and the solution separating of zinc subcarbonate will coated, liquid is sent to and concentrates reclaim(ed) sulfuric acid sodium, and solids wash behind the sulfate radical-free ion in pre-calcination stove 5 between the 500-650 degree calcination 1-2 hour is converted into zinc oxide to zinc subcarbonate, and positive metatitanic acid is becoming metatitanic acid; With the powder behind the calcination in molten zinc still 6, dissolve away in molten zinc still 6 with the sulfuric acid liquid of 2Mol/L concentration zinc oxide the surface, solid-liquid is separated in strainer 7, fluid sulphuric acid zinc returns recycle in the stillpot 3, metatitanic acid is then delivered between the crystal formation converter 8 inherent 700-900 degree and was heated 2 hours, finishes the crystal formation conversion process of product.
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Families Citing this family (11)
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| CN1102163C (en) * | 1999-06-12 | 2003-02-26 | 饶俊明 | Building paint containing silicon-based nanometer-level material |
| FR2803223B1 (en) * | 1999-12-30 | 2002-06-21 | Rhodia Chimie Sa | PROCESS FOR THE PREPARATION OF A MESOSTRUCTURE MATERIAL FROM PARTICLES OF NANOMETRIC DIMENSIONS |
| CN100408481C (en) * | 2004-04-27 | 2008-08-06 | 天津科技大学 | Technique for producing high purity nanometer titanium dioxide |
| CN100369818C (en) * | 2005-06-09 | 2008-02-20 | 江苏大学 | Process for preparing rutile-type nano TiO2 by meta titanic acid |
| CN101062780B (en) * | 2006-04-26 | 2010-05-12 | 四川大学 | Nano titanium oxide and mechanical force chemical reaction preparation method for its composite powder |
| CN104961157A (en) * | 2015-07-03 | 2015-10-07 | 燕山大学 | Synthetic method of rutile TiO2 |
| CN106115775B (en) * | 2016-06-29 | 2017-10-31 | 攀枝花学院 | Adulterate the preparation method of positive metatitanic acid |
| CN107163285A (en) * | 2017-05-25 | 2017-09-15 | 句容亿格纳米材料厂 | A kind of preparation and application for the improved composite Nano high polymer material of product of rubber and plastic mechanical property |
| CN107177542A (en) * | 2017-05-25 | 2017-09-19 | 句容亿格纳米材料厂 | A kind of optimization method for promoting culture medium GLN to dissolve |
| CN111320204B (en) * | 2020-02-24 | 2022-03-25 | 常州大学 | Preparation method of titanium dioxide microspheres with high specific surface area |
| CN114773882B (en) * | 2022-05-24 | 2022-12-06 | 天泰(福建)新材料科技有限公司 | Titanium dioxide for delustering chinlon chemical fiber and preparation method thereof |
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|---|---|---|---|---|
| US5045301A (en) * | 1988-07-01 | 1991-09-03 | Rhone-Poulenc Chimie | Moldable/extrudable titanium dioxide particulates |
| US5366938A (en) * | 1989-04-27 | 1994-11-22 | Degussa Ag | Shaped articles based on pyrogenically produced titanium dioxide |
| CN1114949A (en) * | 1994-07-09 | 1996-01-17 | 山东大学 | Preparation method of high-purity micro-fine rutile-type titanium dioxide |
| JPH08283022A (en) * | 1995-04-11 | 1996-10-29 | Ykk Kk | Titanium dioxide based composite superfine particle and its production |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5045301A (en) * | 1988-07-01 | 1991-09-03 | Rhone-Poulenc Chimie | Moldable/extrudable titanium dioxide particulates |
| US5366938A (en) * | 1989-04-27 | 1994-11-22 | Degussa Ag | Shaped articles based on pyrogenically produced titanium dioxide |
| CN1114949A (en) * | 1994-07-09 | 1996-01-17 | 山东大学 | Preparation method of high-purity micro-fine rutile-type titanium dioxide |
| JPH08283022A (en) * | 1995-04-11 | 1996-10-29 | Ykk Kk | Titanium dioxide based composite superfine particle and its production |
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