CN102765752A - Method for producing rutile type titanium dioxide through metatitanic acid direct diolame - Google Patents

Method for producing rutile type titanium dioxide through metatitanic acid direct diolame Download PDF

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CN102765752A
CN102765752A CN2012102936322A CN201210293632A CN102765752A CN 102765752 A CN102765752 A CN 102765752A CN 2012102936322 A CN2012102936322 A CN 2012102936322A CN 201210293632 A CN201210293632 A CN 201210293632A CN 102765752 A CN102765752 A CN 102765752A
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titanium dioxide
metatitanic acid
rutile type
type titanium
coating
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邹建新
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Panzhihua University
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Panzhihua University
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Abstract

The invention discloses a method for producing rutile type titanium dioxide through metatitanic acid direct diolame and belongs to the field of titanium dioxide production. The method comprises conducting surface diolame treatment on metatitanic acid, conducting calcination, particularly conducting brute force dispersion on the metatitanic acid, directly conducting the surface diolame treatment, removing acid-base salt left during diolame through water washing, entering a rotary kiln for calcinations, conducting airflow grinding after leaving the rotary kiln, and preparing rutile type titanium dioxide products. The method can lower equipment investment, reduce cost of production and have good economic benefits and social benefits. Performance of titanium dioxide pigments prepared by using the method is equal to or better than that of traditional titanium dioxide, performance indexes of the titanium dioxide all meet requirements for the titanium dioxide in the newest 'national titanium dioxide pigment government standard' (GB/T1706-2006).

Description

The method that the direct coating of metatitanic acid is produced Rutile type Titanium Dioxide
Technical field
The invention belongs to the titanium white production field, be specifically related to the method that the direct coating of a kind of metatitanic acid is produced Rutile type Titanium Dioxide.
Background technology
White titanium pigment is present widely used topmost white pigment, is widely used in fields such as coating, papermaking, printing ink, and its demand and GDP present proportional relationship.Present global white titanium pigment annual capacity is more than 5,000,000 tons, and domestic white titanium pigment annual capacity is more than 2,000,000 tons, and price is about 22000 yuan/ton of 15000 –.On working method, the warp understanding is domestic, and all the other all adopt sulfuric acid process to produce except that Jinzhou titanium powder plant adopts chlorination, and present domestic sulfate process titanium dioxide production capacity accounts for 99% of total titanium white production capacity.The comparison distinct issues that exist in the current sulfate process titanium dioxide production process, the one, environmental protection, the 2nd, cost.
The production technique of sulfate process titanium dioxide is to obtain titanium liquid (titanyl sulfate) after adopting titanium ore or titanium slag acidolysis both at home and abroad at present, after hydrolysis, obtains metatitanic acid, obtains TiO through high-temperature calcination again 2Powder is if produce the anatase titanium dioxide product, then to this TiO 2Powder can directly be dry grinded and promptly obtained the commodity titanium white, if produce the rutile type product, then needs this TiO 2Powder carries out aftertreatment (mainly being that surface-coating is handled) just can obtain the commodity titanium white.
The concrete technical process of conventional sulfuric acid Producing Titanium Dioxide is: with generating titanium liquid after titanium ore or the titanium slag acidolysis; Titanium liquid obtains purified dense titanium liquid through sedimentation, crystallization, after concentrating; Obtain purified metatitanic acid through hydrolysis, washing and bleaching again; Metatitanic acid gets into rotary kiln and calcines after supersalt is handled, after dry grinding, carry out aftertreatment again, and the aftertreatment idiographic flow is making beating dispersion, sand milling classification, coating, washing filtering, drying, comminution by gas stream.As shown in Figure 1 from the technical process that the metatitanic acid operation begins.
In the rutile titanium white last handling process; Need add the slurry that water makes it the liquefy shape to the titanium white first product of dry-powdered; Handle (being generally sial coating or zirconium aluminium coating) through coating after the sand mill wet-milling, after drying dehydration and comminution by gas stream make it to become the titanium white finished product of dry-powdered.In this drying process, consumed a large amount of heat and brought facility investment,, simultaneously, in this sand grinding process, also can consume a large amount of electricity and bring facility investment,, caused a series of problems such as environmental pollution thus like the anti-horizontal sand mill etc. of speeding like spray-dryer etc.
Tradition sulfate process titanium dioxide production technique is more stable basically in nearly recent decades; Carried out the repeatedly process modification of miniaturized during this time; Change ordinary-pressure hydrolysis into like pressurized hydrolysis, increase the wet-milling operation before the coating, the gap acidolysis changes continuous acidolysis etc. into; Each effectively improvement all can spontaneously promote the use of domestic even external most titanium powder plants in the short period of time.
Adopt the history of the existing last 100 years of Production By Sulfuric Acid Process titanium white both at home and abroad, in this process, production technique has been carried out countless research and development and technological improvement, finally formed the integrated artistic route of present comparative maturity.In recent years, domestic and international researchist mainly concentrates on four aspects to the research of sulfate process titanium dioxide.
The one, the research on different material is selected.What initial sulfate process titanium dioxide production was adopted is titanium ore, longer to the technical process of titanium ore, mainly shows the freezing and crystallizing operation of ferrous sulfate.Part factory adopted TiO afterwards 2The higher titanium slag of grade makes the freezing and crystallizing operation of ferrous sulfate be able to cancellation as raw material, mixture that factory adopts titanium slag and titanium ore is also arranged as raw material.This technology is part producer application at home at present.This achievement in research makes that the environmental issue of sulfate process titanium dioxide production technique is obviously alleviated.
The 2nd, each production process Parameter Optimization research.Comprise hydrolysis procedure, sedimentation operation, titanium liquid enrichment process, hydrolyzing process, salt treatment process, calcination process or the like.Through these research, make the quality of each intermediates be improved, the cost of each process link is able to descend; But fall is less; From integrated artistic, be mainly reflected in the titanium white product quality be improved significantly, particularly the gap of home products and external product is more and more littler.
The 3rd, the research of titanium white aftertreatment.Under the situation that the titanium white FEOL is mature on the whole, the titanium white product, particularly the quality of rutile titanium white product depends primarily on the aftertreatment coating process.In recent years the patent overwhelming majority about titanium white is the research of coating aspect, aspect aftertreatment research, carried out 30 abroad surplus year, and the domestic research of carrying out this respect also is nearly 10 years thing.Therefore, domestic titanium white product still is to have big gap with abroad comparing at present.The achievement in research of coating makes the quality of titanium white product further improve.
The 4th, the research of environmental issue.Mainly concentrating on spent acid concentrates and ferrous sulfate processing research two aspects.The main employing of external sulfur waste acid concentrates the recycling method processing, the domestic main at present mode that adopts the spent acid neutralizing treatment, because concentrated cost is bigger than normal, domestic only have minority producer to adopt concentrating means to handle spent acid.Ferrous sulfate mainly takes the titanium slag raw material route to eliminate at present abroad, domesticly mainly takes as fodder additives, water purification agent and produces method such as other industrial chemicals and handle.
Each concrete operation in the sulfate process titanium dioxide production technique conducts a research, and can reduce certain cost, but the reduction amplitude is less; To obviously reduce the Producing Titanium Dioxide cost, have only titanium white production technology is optimized improvement, even cancellation part operation; Make it to become short flow process friendly process; Could reduce production costs by a relatively large margin, this is the source of the new force of sulfate process titanium dioxide production technique acquisition from now on, also is one of development trend of sulfate process titanium dioxide process study.
In sum; Existing conventional sulfuric acid Producing Titanium Dioxide technology cost is higher, and each production process Parameter Optimization research is very limited to the reduction of cost, simultaneously; There is bigger environmental protection pressure in conventional sulfuric acid Producing Titanium Dioxide technology; Though adopt the spent acid concentrating means can reduce environmental pollution by a relatively large margin, the spent acid concentrating means can increase cost significantly, many enterprises are reluctant to adopt.
Summary of the invention
Technical problem to be solved by this invention provides the method that the direct coating of a kind of metatitanic acid that reduces production costs is produced Rutile type Titanium Dioxide.
The technical solution adopted for the present invention to solve the technical problems is: the method that the direct coating of metatitanic acid is produced Rutile type Titanium Dioxide, this method are that metatitanic acid carries out the surface-coating processing earlier, calcine and make the Rutile type Titanium Dioxide product.
Wherein, in the aforesaid method, after metatitanic acid disperses earlier, directly carry out surface-coating and handle, washing again, calcining is then calcined laggard promoting the circulation of qi stream and is pulverized, and can make the Rutile type Titanium Dioxide product.
Further, also comprise the salt processed steps, the salt treatment step carries out after washing, before the calcining, perhaps disperses back, surface-coating to carry out before handling at metatitanic acid.
Wherein, aforesaid method is warming up to 500~600 ℃ with material earlier when calcining, insulation 2~3h; Be warming up to 810~850 ℃ then, insulation 4~5h; Be warming up to 880~900 ℃ at last, insulation 2.5~3h accomplishes calcination process.
The invention has the beneficial effects as follows: the present invention carries out surface-coating with metatitanic acid earlier and handles, and calcines again, is specially the powerful dispersion of metatitanic acid, surface-coating, washing, calcining, comminution by gas stream; Finally make Rutile type Titanium Dioxide; Compare with conventional sulfuric acid titanium white production technology, reduced the operation of dry grinding, making beating, drying and dehydrating and wet-milling, thereby can reduce facility investment; Reduce production cost, have favorable economic benefit and social benefit; The titanium white powder pigment performance that the inventive method is produced and traditional commodities titanium white quite or be superior to the traditional commodities titanium white, the titanium white powder pigment performance index all meet in national up-to-date " TiO 2 pigment national standard " (GB/T 1706-2006) requirement to white titanium pigment.
Among the present invention, carry out coating earlier and handle, make nano level metatitanic acid particle surface deposit sial or zirconium al oxide, promptly the metatitanic acid particle surface is being coated by sial film or zirconium aluminium film; When heating up calcining gradually, TiO 2Crystal formation changes, and is converted into anatase titanium dioxide and then is converted into rutile-type by unformed gradually.On the one hand, grow up, make most of particle size change basically not quite because sial film or zirconium aluminium film have hindered the metatitanic acid agglomeration of particles; On the other hand, in temperature-rise period, the evaporation of sulfide gas and water vapour; Need to overflow through the space of oxide film, thereby can make sial film or zirconium aluminium film a small amount of pore occur, the appearance of pore makes small portion metatitanic acid particle surface expose; And then the gathering between the generation particle grows up, and reduced TiO 2Surface optical performance (TiO 2Pigment performance mainly by optical property decision).
But, because TiO 2Pigment performance except that depending on crystal formation, the more important thing is and depend on TiO 2Particle size, generally, size is more little, and optical property is good more.The white titanium pigment that traditional technology is produced, TiO 2Particle size about 0.5 μ m, and in the technology of the present invention, TiO 2The particle size major part remains on the primary particle size; Basically be equivalent to about 1/5 of traditional commodities titanium white; Although there is few part holes in particle surface; The contribution to optical property of small size advantage decision is enough to offset the imperfection of coating, thereby makes whole optical property of pigment and traditional commodities titanium white quite or be superior to the traditional commodities titanium white.
Description of drawings
Fig. 1 is for beginning to produce the process flow diagram of Rutile type Titanium Dioxide in the prior art from the metatitanic acid operation;
Fig. 2 is wherein a kind of process flow diagram of embodiment of the present invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further specified.
Method as shown in Figure 2, that the direct coating of metatitanic acid of the present invention is produced Rutile type Titanium Dioxide, this method are that metatitanic acid carries out the surface-coating processing earlier, calcine and make the Rutile type Titanium Dioxide product.
Preferably, in the aforesaid method, after metatitanic acid disperses earlier, directly carry out surface-coating and handle, washing again, calcining is then calcined laggard promoting the circulation of qi stream and is pulverized, and can make the Rutile type Titanium Dioxide product.
Further, aforesaid method also comprises the salt processed steps, and the salt treatment step carries out after washing, before the calcining, perhaps disperses back, surface-coating to carry out before handling at metatitanic acid.
Preferably, in calcination process, in order to reduce pore opening and void content, further improve the titanium white powder pigment performance, aforesaid method is warming up to 500~600 ℃ with material earlier when calcining, insulation 2~3h; Be warming up to 810~850 ℃ then, insulation 4~5h; Be warming up to 880~900 ℃ at last, insulation 2.5~3h accomplishes calcination process.
Do further description below in conjunction with the embodiment specific embodiments of the invention, but therefore protection scope of the present invention is not limited among the scope of embodiments.
Embodiment one
Traditional technology is produced Rutile type Titanium Dioxide (metatitanic acid is calcining earlier, again the sial coating):
1. be mixed with solution with 15ml dissolved in distilled water 0.9g Sodium hexametaphosphate 99, obtain dispersion agent, the Hydrocerol A of preparation 20wt%.Be ready to constant flow pump.
2. add in the metatitanic acid slurry and be equivalent to TiO 20.8% salt treatment agent ZnO of quality be equivalent to TiO 20.9% salt treatment agent Tai-Ace S 150 of quality is (with Al 2O 3Meter), after stirring,, after pulverizing again, get 200g TiO with the metatitanic acid calcining 2, add the 0.35L hot distilled water, add Sodium hexametaphosphate 99 dispersion agent (containing Sodium hexametaphosphate 99 0.9g), disperse about 10min.
3. move on to sand mill, sand milling 30min is released to the coating groove, again with the 0.65L distilled water diluting to 200g/L concentration.
4. with coating groove constant temperature to 85 ℃, transfer pH=12 with the NaOH solution of 5mol/L concentration, and stir, and then the Hydrocerol A that adds 20wt% is transferred pH=10.5.With 24g water glass obtain solution (with the dissolving of 100ml hot distilled water).
5. the sodium silicate solution of step preparation is measured the pH value therebetween at any time, and is used 50%H in 100min, adding 2SO 4Control pH value drops to 7, during additional zero(ppm) water.Keeping pH=7,85 ℃ of following aging slurries 45min.Be ready to 12g NaAlO between aging time 2, dissolve with the 120mL hot distilled water.
6. aging back adds the NaAlO of step preparation in 20min 2Solution, and measure the pH value at any time, and use H 2SO 4Keep PH=6~8, after reinforced the completion, adjustment pH=7, under agitation aging 20min.
7. filter, wash (using hot distilled water), dry, comminution by gas stream, make Rutile type Titanium Dioxide.
8. detect whiteness, reducing power, brightness, tone, blue phase spectral value, see table 1.
Embodiment two
Explained hereafter Rutile type Titanium Dioxide of the present invention (behind the metatitanic acid elder generation sial coating, calcining again):
1. obtain dispersion agent with 15ml dissolved in distilled water 0.9g Sodium hexametaphosphate 99 obtain solution, the Hydrocerol A of preparation 20wt%.Be ready to constant flow pump.
2. (estimation contains TiO to take by weighing the 420g metatitanic acid 2Be 200g), be ground to powdery, add the 0.35L hot distilled water, add Sodium hexametaphosphate 99 dispersion agent (containing Sodium hexametaphosphate 99 0.9g), disperse about 10min.Add the 0.65L distilled water diluting again to 200g/L concentration, continue to disperse about 10min.
3. with coating groove constant temperature to 85 ℃, transfer pH=12 with the NaOH solution of 5mol/L concentration, and stir, and then the Hydrocerol A that adds 20wt% is transferred pH=10.5.With 24g water glass obtain solution (with the dissolving of 100ml hot distilled water).
4. the sodium silicate solution of step preparation in 100min, adding, during measure the pH value at any time, and use 50%H 2SO 4Control pH value drops to 7, during additional zero(ppm) water.
5. keeping pH=7, T=85 ℃ of following aging slurries 45min.Be ready to 12g NaAlO between aging time 2, dissolve with the 120mL hot distilled water.
6. aging back adds the NaAlO of step preparation in 20min 2Solution, and measure the pH value at any time, and use H 2SO 4Keep pH=6~8, after reinforced the completion, adjustment pH=7, under agitation aging 20min.
7. precipitate, wash (using hot distilled water), redeposition, washing several times again, interpolation is equivalent to TiO in the post precipitation metatitanic acid slurry 20.8% salt treatment agent ZnO of quality be equivalent to TiO 20.9% salt treatment agent Tai-Ace S 150 of quality is (with Al 2O 3Meter), after stirring, filter and obtain filter cake, the crucible of packing into.Crucible is placed in the High Temperature Furnaces Heating Apparatus, be warming up to 600 ℃, insulation, 3h altogether with stove; Continuation is warming up to 850 ℃ with stove, insulation, 4h altogether; Continuation is warming up to 900 ℃ with stove, insulation, 3h altogether.Add up to 10h.
8. the white titanium pigment cooling, grinding, the comminution by gas stream that will obtain after will calcining make Rutile type Titanium Dioxide.
9. detect whiteness, reducing power, brightness, tone, blue phase spectral value, see table 1.
Embodiment three
Traditional processing technology is produced Rutile type Titanium Dioxide (metatitanic acid is calcining earlier, again zirconium aluminium coating):
1. obtain dispersion agent with 15ml water dissolution 0.45g Sodium hexametaphosphate 99 obtain solution.With 40ml water dissolution 5.8g zirconium sulfate Zr (SO 4) 4H 2O (is equivalent to 200g TiO 21% ZrO of base-material weight 2) be mixed with solution, for use.
2. add in the metatitanic acid slurry and be equivalent to TiO 20.8% salt treatment agent ZnO of quality be equivalent to TiO 20.9% salt treatment agent Tai-Ace S 150 of quality is (with Al 2O 3Meter), after stirring,, after pulverizing again, get 200g TiO with the metatitanic acid calcining 2, add 0.35L hot water, add the Sodium hexametaphosphate 99 dispersion agent of the 1st step preparation, disperse 10min.Move on to sand mill, sand milling 30min puts into the coating groove behind 325 mesh sieves excessively, is diluted to 200g/L concentration with 0.65L water again.
3. slurry temperature is raised to 45 ℃, measures slurry pH value, and use 25%H 2SO 4Regulate pH ≈ 5.
4. with joining zirconium sulfate solution in 15min, join in the slurries gradually, and stir.After adding zirconium sulfate, measure the pH value of slurries, transfer pH=8 with the NaOH solution of 5mol/L concentration.
5. aging slurries 15min under the gentle agitation stops to stir down aging 10min.Measure slurry pH value again after aging the completion, use 25%H 2SO 4Regulate slurries pH ≈ 5.
6. take by weighing 26.8g Tai-Ace S 150 and (be equivalent to 8g Al 2O 3, i.e. TiO 2Base-material weight 4%), be dissolved in the 100ml hot water for use.In 20min to TiO 2Add above-mentioned alum liquor in the slurries, stir, measure the pH value of solution value at any time, regulate slurries pH=8, regulate the pH=8 of slurry after reinforced the completion with the NaOH solution of 5mol/L concentration.Aging slurries 60min under the gentle agitation stops to stir aging slurries 2.5h down.
7. filter, wash (using hot distilled water), dry, comminution by gas stream, make Rutile type Titanium Dioxide.
8. detect whiteness, reducing power, brightness, tone, blue phase spectral value, see table 1.
Embodiment four
Explained hereafter Rutile type Titanium Dioxide of the present invention (behind the metatitanic acid elder generation zirconium aluminium coating, calcining again):
1. be mixed with solution with 15ml water dissolution 0.45g Sodium hexametaphosphate 99 and obtain dispersion agent.With 40ml water dissolution 5.8g zirconium sulfate Zr (SO 4) 4H 2O (is equivalent to 200g TiO 21% ZrO of base-material weight 2) be mixed with solution, for use.
2. (estimation contains TiO to take by weighing the 420g metatitanic acid 2Be 200g), be ground to powdery, add the 0.35L hot distilled water, add above-mentioned Sodium hexametaphosphate 99 dispersion agent, disperse about 10min.Add the 0.65L distilled water diluting again to 200g/L concentration, continue to disperse about 10min.
3. coating groove temperature is raised to 45 ℃, measures slurry pH value, and use 25%H 2SO 4Regulate pH ≈ 5.Joining 5.8g zirconium sulfate solution is joined in the slurries in 15min gradually, and stir.
4. after adding zirconium sulfate, measure the pH value of slurries, with the NaOH accent pH=8 of 5mol/L.Aging slurries 15min under the gentle agitation stops to stir down aging 10min.Measure slurry pH value again after aging the completion, transfer pH=8.
5. take by weighing the 13g sodium metaaluminate and (be equivalent to 8gAl 2O 3, i.e. TiO 2Base-material weight 4%), be dissolved in the 100ml hot water for use.In 20min to TiO 2Add above-mentioned sodium aluminate solution in the slurries, stir, measure the pH value of solution value at any time, use 25%H 2SO 4Regulate slurries pH=7.5~8.5, regulate the pH=8 of slurry after reinforced the completion.
6. aging slurries 60min under the gentle agitation stops to stir aging slurries 2.5h down.
7. precipitate, wash (using hot distilled water), redeposition, washing several times again, interpolation is equivalent to TiO in the post precipitation metatitanic acid slurry 20.8% salt treatment agent ZnO of quality be equivalent to TiO 20.9% salt treatment agent Tai-Ace S 150 of quality is (with Al 2O 3Meter), after stirring, filter and obtain filter cake, the crucible of packing into.Crucible is placed in the High Temperature Furnaces Heating Apparatus, be warming up to 500 ℃, insulation, 2h altogether with stove; Continuation is warming up to 810 ℃ with stove, insulation, 5h altogether; Continuation is warming up to 880 ℃ with stove, insulation, 2.5h altogether.Add up to 9.5h.
8. the white titanium pigment cooling, grinding, the comminution by gas stream that will obtain after will calcining make Rutile type Titanium Dioxide.
9. detect whiteness, reducing power, brightness, tone, blue phase spectral value, see table 1.
Table 1 embodiment white titanium pigment performance index value relatively
Can be known that by table 1 data during the sial coating, the whiteness value of product of the present invention is greater than traditional technology, reducing power is greater than traditional technology, brightness, the blue phase spectrum characteristic parameter of color harmony compare the traditional technology difference not quite, suitable basically.During zirconium aluminium coating, the whiteness value of product of the present invention and traditional technology are suitable basically, but a little less than traditional technology, and reducing power is greater than traditional technology, brightness, the blue phase spectrum characteristic parameter of color harmony compare the traditional technology difference not quite, suitable basically.In above-mentioned five indexs, the most important index of decision white titanium pigment performance is a reducing power, no matter is sial coating or zirconium aluminium coating, and technology of the present invention obtains the white titanium pigment reducing power all apparently higher than traditional technology.In addition, in table 1 data, no matter be the white titanium pigment that technology of the present invention or traditional technology obtain, the equal National standard of its pigment performance index.

Claims (4)

1. the direct coating of metatitanic acid is produced the method for Rutile type Titanium Dioxide, it is characterized in that: metatitanic acid carries out surface-coating earlier to be handled, and calcines and makes the Rutile type Titanium Dioxide product.
2. the method that the direct coating of metatitanic acid according to claim 1 is produced Rutile type Titanium Dioxide is characterized in that: after metatitanic acid disperses earlier, directly carry out surface-coating and handle; Washing again; Calcining is then calcined laggard promoting the circulation of qi stream and is pulverized, and can make the Rutile type Titanium Dioxide product.
3. the method that the direct coating of metatitanic acid according to claim 2 is produced Rutile type Titanium Dioxide; It is characterized in that: also comprise the salt processed steps; The salt treatment step carries out after washing, before the calcining, perhaps disperses back, surface-coating to carry out before handling at metatitanic acid.
4. the method for producing Rutile type Titanium Dioxide according to claim 1, the direct coating of 2 or 3 described metatitanic acids is characterized in that: during calcining, earlier material is warming up to 500~600 ℃, insulation 2~3h; Be warming up to 810~850 ℃ then, insulation 4~5h; Be warming up to 880~900 ℃ at last, insulation 2.5~3h accomplishes calcination process.
CN2012102936322A 2012-08-17 2012-08-17 Method for producing rutile type titanium dioxide through metatitanic acid direct diolame Pending CN102765752A (en)

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Cited By (4)

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CN103555001A (en) * 2013-10-31 2014-02-05 攀钢集团攀枝花钢铁研究院有限公司 Method for coating titanium dioxide
CN105017813A (en) * 2015-07-01 2015-11-04 攀枝花学院 Rutile titanium dioxide production method
CN108070280A (en) * 2016-11-11 2018-05-25 中国地质大学(北京) A kind of preparation method of silicon dioxide microsphere-titanium dioxide composite powder pigment
CN111233033A (en) * 2020-03-26 2020-06-05 华东理工大学 Process method for regulating particle size of titanium dioxide

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Publication number Priority date Publication date Assignee Title
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CN101298339A (en) * 2008-06-27 2008-11-05 中南大学 Surface modification method of nano-titanic oxide precursor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060204456A1 (en) * 2002-12-09 2006-09-14 Takashi Asakura Titanium oxide particles having useful properties and method for production thereof
CN101298339A (en) * 2008-06-27 2008-11-05 中南大学 Surface modification method of nano-titanic oxide precursor

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103555001A (en) * 2013-10-31 2014-02-05 攀钢集团攀枝花钢铁研究院有限公司 Method for coating titanium dioxide
CN105017813A (en) * 2015-07-01 2015-11-04 攀枝花学院 Rutile titanium dioxide production method
CN108070280A (en) * 2016-11-11 2018-05-25 中国地质大学(北京) A kind of preparation method of silicon dioxide microsphere-titanium dioxide composite powder pigment
CN108070280B (en) * 2016-11-11 2020-06-09 中国地质大学(北京) Preparation method of silicon dioxide microsphere-titanium dioxide composite powder pigment
CN111233033A (en) * 2020-03-26 2020-06-05 华东理工大学 Process method for regulating particle size of titanium dioxide
CN111233033B (en) * 2020-03-26 2021-01-01 华东理工大学 Process method for regulating particle size of titanium dioxide

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Application publication date: 20121107