CN1038188C - Preparation method of high-purity micro-fine rutile-type titanium dioxide - Google Patents
Preparation method of high-purity micro-fine rutile-type titanium dioxide Download PDFInfo
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- CN1038188C CN1038188C CN94110679A CN94110679A CN1038188C CN 1038188 C CN1038188 C CN 1038188C CN 94110679 A CN94110679 A CN 94110679A CN 94110679 A CN94110679 A CN 94110679A CN 1038188 C CN1038188 C CN 1038188C
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- ilmenite
- hydrochloric acid
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000004408 titanium dioxide Substances 0.000 title abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000010936 titanium Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 22
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000049 pigment Substances 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 25
- 239000012074 organic phase Substances 0.000 claims description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- BAKALPNAEUOCDL-UHFFFAOYSA-N titanium hydrochloride Chemical compound Cl.[Ti] BAKALPNAEUOCDL-UHFFFAOYSA-N 0.000 claims description 7
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- -1 hexadecyl cinnamyl ether Chemical compound 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000009283 thermal hydrolysis Methods 0.000 claims description 2
- 239000011363 dried mixture Substances 0.000 claims 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims 1
- 230000000887 hydrating effect Effects 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract 2
- 235000011167 hydrochloric acid Nutrition 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 239000008346 aqueous phase Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 238000000605 extraction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010298 TiOSO4 Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910003781 PbTiO3 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010010 raising Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a method for preparing high-purity ultrafine rutile-type titanium dioxide, which belongs to the field of a fine chemical industry. The present invention is mainly characterized in that ilmenite and industrial chlorhydric acid are used as main raw materials, a titanium solution prepared with a certain concentration is added with two kinds of organic matter to carry out pyrohydrolysis at normal pressure, and rutile-type TiO2 with a particle size of 38 to 45 nm is prepared. The present invention solves the problems of complicated technology, large energy consumption and nonuniform granules of a TiO2 product in the prior art. The present invention has the advantage of simple technology, easy large-scale industrial production, and no environmental pollution. The crystal form of TiO2 prepared with the method is a rutile type, has the particle size of 38 to 45 nm, and has the advantages of good uniformity, and superior pigment performance and chemical activity.
Description
The invention relates to a preparation method of rutile titanium dioxide, in particular to a preparation method of high-purity ultrafine rutile titanium dioxide, belonging to the field of fine chemical engineering.
Ultrafine titanium dioxide (TiO)2) The ultraviolet screening capability is very strong, and the ultraviolet screening paint is widely applied to industries of skin care products, food packaging materials, woodware protection materials, natural and artificial fibers, transparent external durable finish paint and the like. Ultrafine TiO 22The base material used as electronic ceramic material is also large in dosage, and it also has white pigment with excellent pigment property, and in addition, superfine TiO2Has good weather resistance and thermal stability, good chemical stability, especially strong ultraviolet absorption capacity, and is a good effect pigment because of scattering and absorbing ultraviolet.
Currently, ultra-fine TiO is manufactured2The method comprises mechanical pulverization, gas phase hydrolysis, TiOSO4Liquid phase hydrolysis method, solution-gel method [ Zhi Zhong of color Material Association, 1984, 51(6)305 to 308, J.M.Sci.1987, (22)4307 to 4312 EpO 49986(3)]The mechanical crushing method is to crush common TiO2Pulverizing to 15-50 nm to obtain superfine TiO2The product is also unsatisfactory in terms of purity, particle size distribution and particle shape because mechanical crushing equipment is not well solved. The gas phase hydrolysis method is also called flame hydrolysis or water forming method, and P-25 of Dgaosha, Germany is produced by the method, in which TiCl is mixed with water4Gas in H2、O2Carrying out high-temperature hydrolysis in flame. The liquid phase hydrolysis method is also called liquid phase neutralization method, which is to hydrate TiO semi-finished product in the production of titanium sulfate2Adding sulfuric acid after washing to generate TiOSO4Adding alkali to the aqueous solution to neutralize and hydrolyze the aqueous solution to produce TiO (OH)2Calcining to form ultrafine TiO2. At present, the method is adopted by the imperial chemical company, the industrial company, the Tioxide company and the Finland Kamila company in Japan to produce the ultrafine TiO2. However, the method has the disadvantages of complex process, difficult control of reaction conditions, high energy consumption, environmental pollution and generated TiO2The particles are not uniform.
The invention aims to solve the problems of complex process, high energy consumption, environmental pollution and TiO existing in the prior art2The product granule isUniformity problem, and a new design scheme is provided.
The main content of the invention is as follows: high-purity ultrafine rutile titanium dioxide (TiO)2) The preparation method is characterized in that ilmenite and industrial hydrochloric acid are used as main raw materials, after a crude titanium hydrochloride solution is prepared, two organic matters are added for normal-pressure pyrohydrolysis, and rutile TiO with the particle size of 38-45 nm can be prepared2The preparation method comprises the following steps:
(1) firstly, industrial hydrochloric acid (with the concentration of 31 percent) and ilmenite are put into a reactor according to the weight ratio of ilmenite to hydrochloric acid of 1: 3-6, a small amount of phosphoric acid is added as a catalyst, the weight of the phosphoric acid is 0.5-1.2 percent of the weight of ilmenite, thenheating and acidolysis are carried out, the heating temperature is 40-90 ℃, the constant temperature time is 10-5 hours correspondingly, after the constant temperature is carried out for a plurality of hours, natural cooling is carried out to the room temperature to obtain crude titanium hydrochloride liquid,
(2) introducing HCl gas into the crude titanium hydrochloride solution until the concentration of free acid in the titanium solution is more than 9M, filtering, extracting with tributyl phosphate/benzene, washing the organic phase with 0.5M hydrochloric acid, wherein the volume ratio of the aqueous phase to the organic phase is (1.8-2.9) to 1, extracting titanium with the organic phase, the volume ratio of the organic phase to the aqueous phase is 1 to (0.8-1.3), back extracting the organic phase with 4M hydrochloric acid, the volume ratio of the aqueous phase to the organic phase is (1.3-2.1) to 1, concentrating the aqueous phase to obtain the refined titanium solution for thermal hydrolysis,
(3) adding refined titanium liquid into a reactor, heating the titanium liquid to 90-100 ℃ at the speed of 10-20 ℃/min, adding ethylene glycol monomethyl ether/triethanolamine (1: 1) in an amount of TiO in the titanium liquid20.5-1.2% of the content, then continuously heating to boiling at the speed of 1.5-2.5 ℃/min, cooling to room temperature at the speed of 20-30 ℃/min, and then cooling to obtain the final product
(4) Separating the hydrated TiO by centrifugation2Sequentially washing with purified 2MHCl three times of water twice, washing with Zn-hexadecyl lauryl ether complex emulsifier three times of water three times respectively, and then washing with purified 2MHCl three times of water three times respectively
(5) To hydrate TiO2Drying at 100-125 deg.c for 0.5-1.5 hr, setting in platinum crucible in mufflefurnaceHeating to 400-420 ℃ at a heating rate of 16-25 ℃/min, keeping the temperature for 0.4-0.6 h, continuously heating to 520-560 ℃ at a heating rate of 4-8 ℃/min, keeping the temperature for 1-2 h, and cooling to room temperature to obtain the high-purity ultrafine TiO2。
The acid solution of the crude titanium hydrochloride solution after titanium extraction by the organic solvent can be reused for acidolysis of ilmenite, and the organic benzene extraction agent can be recycled after being washed by 0.5M hydrochloric acid.
The Zn-hexadecyl cinnamyl ether complex can effectively hydrate TiO2The impurity ions in the water react chemically to form a new M-Zn hexadecyl cinnamyl ether complex which is washed away to hydrate TiO2The impurity ions are less than 0.1 PPm.
The ultrafine TiO prepared by the method of the invention2The crystal form is rutile, the particle appearance is spindle type, the size is 38-45 nm, the length-to-diameter ratio is 1.5: 1-1: 1, and the pigment has good pigment performance.
The preparation method of the invention is known to be an important link for preparing refined titanium liquid, and industrial TiCl can be used for preparing the titanium liquid except the method of the invention4The high-purity ultrafine TiO can be prepared by adding water to dilute the solution and then utilizing the preparation method of the invention2. TiO finally obtained by the preparation method of the invention2The pigment is rutile type, the particle appearance is spindle type, the size is 35-45 nm, the ratio of the length to the vacuum is 1.5: 1-1: 1, and the pigment has good pigment performance and chemical activity.
The preparation method provided by the invention belongs to the scope of a liquid phase hydrolysis method, but is different from any existing method, and has the advantages that crude titanium liquid obtained by acidolysis of ilmenite by industrial hydrochloric acid is subjected to extraction, back extraction and concentration steps to obtain refined titanium liquid for hydrolysis, an organic reagent is added to be used as a hydrolysis initiator, and the organic reagent simultaneously plays a role in controlling TiO2The shape and size of the product. TiO obtained by the method of the invention2The pigment is rutile type, has the granularity of 38-45 nm, the difference between the maximum particle radius and the minimum particle radius of only 7nm, has good uniformity and higher pigment performance and chemical activity, and is easy to realize large-scale productionAnd (4) industrial production.
Another characteristic of the invention is that besides ilmenite in the whole preparation process, other reagents can be recycled, only HCl is lost, because TiO2The Fe in the solution reacts with HCl to generate FeCl2Other impurity cations also consume some of the HCl, such as Cr, Mn, etc. Another characteristic of the invention is that no environmental pollution is generated, which is caused by the liquid phase preparation of TiO2Is very difficult to obtain. Another feature of the present invention is the hydration of TiO2The calcining temperature is very low, and ideal rutile type high-purity ultrafine TiO can be obtained only at 520-560 DEG C2Using the TiO2It is also possible to prepare e.g. PbTiO3、BaTiO3And titanium-based fine ceramic materials.
In a word, the method has simple process, convenient operation, easy large-scale industrial production and no environmental pollution, and the obtained TiO2The crystal form is rutile type, and has high pigment performance and chemical activity.
Example 1, 100g of ilmenite (titanium content in TiO)250.2g of industrial hydrochloric acid and 29.1g of Fe, 400ml of industrial hydrochloric acid and 5g of phosphoric acid are added into a 500ml three-neck flask, stirred and heated, the temperature rise speed is 1.0 ℃/min, the temperature is raised to 80 ℃, then heat preservation is carried out for 6 hours, (98.3% of Ti enters a liquid phase after analysis), HCl gas is introduced until the free HCl concentration in an acidolysis solution is 10.2M after the temperature of the Ti is reduced to room temperature, then the temperature is reduced to 0 ℃, decantation and filtration are carried out to obtain 423ml of filtrate, the filtrate is extracted by 450mg of tributyl phosphate/benzene (80% of tributyl phosphate), the volume of an organic phase is 462ml after separation, the water phase is 408ml, and the free acidity is 9.6M. The organic phase was back-washed twice with 470ml 4MMHCl, yielding 482ml of aqueous phase containing titanium (as TiO), 449ml of organic phase2Calculated) was 98g/l, the free acid concentration was 4.3M, and the concentrate was concentrated to a volume of 121ml, a Ti content of 168g/l and an acidity of 5.3M. 44.9ml of the organic phase were washed three times with 900ml of 10.5MHCl, the elution rate of Fe being 96%. Putting the above concentrated 221ml titanium solution into 500ml four-necked bottle, heating, refluxing, stirring, adding 5ml ethylene glycol monomethyl ether/triethanolamine (1: 1) when the temperature rises to 90 deg.C at a rate of 16 deg.C/min, heating to boil at a rate of 6 deg.C/min, and keepingBoiling for 2.5h, cooling to room temperature at a rate of 2.5 deg.C/min, and centrifuging at high speed to separate out hydrated TiO2The mother liquor was 202ml, and the acidity was 5.3M. Hydrated TiO2The weight of the detergent is 73g, the detergent is washed with purified 2MHCl and water for three times respectively, and washed with0.1 MZn-hexadecyl lauryl ether complex emulsifier and water for three times respectively, and the dosage of the detergent and the hydrated TiO are used for one time2The weight ratio of (A) to (B) is 1: 1. To hydrate TiO2Drying at 110 ℃ for 1 hour, and calcining in a platinum crucible at the following temperature condition, wherein the particle size is 38-42 nm. The obtained ultrafine TiO2The weight is 43g, the average particle diameter is 39nm, and the particle diameter range is 38-42 nm.
Example 2, using 408ml of 9.6M hydrochloric acid and 80g of ilmenite in example 1, 6g of phosphoric acid in a 1000ml three-necked flask, stirring and heating, raising the temperature at a speed of 1.2 ℃/min, keeping the temperature for 6 hours after the temperature is raised to 85 ℃ (98.6% of Ti enters into a liquid phase by analysis), cooling the temperature of the Ti to room temperature, introducing HCl gas until the concentration of free HCl in an acid hydrolysis solution is 10.6M, then lowering the temperature to 0 ℃, decanting and filtering to obtain 432ml of filtrate, 449ml of cleaned organic phase (tributyl phosphate/benzene) in example 1 is used for extracting, and 480ml of 4MHCl solution is prepared by using 5.8M and concentrated HCl in example 1, and then the organic phase is backwashed; the procedure of example 1 was followed to obtain ultrafine TiO particles237g，TiO2The average particle size of the particles is 40nm, and the particle size range is 39-44 nm. After the above one cycle, 447ml of tributyl phosphate/benzene, 417ml of hydrochloric acid with acidity of 9.8M and 202ml of hydrochloric acid with acidity of 5.8M were obtained as the organic phase. Used for the next cycle (see example 3).
EXAMPLE 3A 1000ml three-necked flask was charged with 417ml of 9.8M hydrochloric acid and 828 ilmenite of example 2, 6g of phosphoric acid, heated with stirring at a rate of 10 ℃/min and at 60 ℃ for 8.5 hours, the Ti liquid was cooled to room temperature and filtered, extracted with tributyl phosphate/benzene at a ratio of organic to aqueous phases of 1: 1 (volume ratio), the organic phase was washed with 0.5M HCl gas, and then HCl gas was introduced into the aqueous phase until the free acidity became more than 9M, followed byThen the organic phase after washing Fe is used for extraction, and 492ml of 4MHCl solution is prepared by using the hydrochloric acid with the acidity of 5.8M and concentrated HCl, and then the organic phase is back extracted. The procedure of example 1 was followed to obtain ultrafine TiO particles232g，TiO2The average particle size of the particles is 41nm, and the particle size range is 38-43 nm.
Claims (4)
1. High-purity ultrafine rutile titanium dioxide (TiO)2) The preparation method is characterized in that ilmenite and industrial hydrochloric acid are used as main raw materials, after a crude titanium hydrochloride solution is prepared, two organic matters are added for normal-pressure pyrohydrolysis, and rutile TiO with the granularity of 38-45 nm can be prepared2The preparation method comprises the following steps:
(1) firstly, industrial hydrochloric acid (with the concentration of 31 percent) and ilmenite are put into a reactor according to the weight ratio of ilmenite to hydrochloric acid of 1: 3-6, a small amount of phosphoric acid is added as a catalyst, the weight of the phosphoric acid is 0.5-1.2 percent of the weight of ilmenite, then heating and acidolysis are carried out, the heating temperature is 40-90 ℃, the constant temperature time is 10-5 hours correspondingly, after the constant temperature is carried out for a plurality of hours, natural cooling is carried out to the room temperature to obtain crude titanium hydrochloride liquid,
(2) introducing HCl gas into the crude titanium hydrochloride solution until the concentration of free acid in the titanium solution is more than 9M, filtering, extracting with tributyl phosphate/benzene, washing the organic phase with 0.5M hydrochloric acid until the volume ratio of the water phase to the organic phase is (11.8-2.9) to 1, extracting titanium with the organic phase until the volume ratio of the organic phase to the water phase is 1 to (0.8-1.3), back extracting the organic phase with 4M hydrochloric acid until the volume ratio of the water phase to the organic phase is (1.3-2.1) to 1, concentrating the water phase to obtain the refined titanium solution for thermal hydrolysis,
(3) adding refined titanium liquid into a reactor, heating the titanium liquid to 90-100 ℃ at the speed of 10-20 ℃/min, adding ethylene glycol monomethyl ether/triethanolamine (1: 1) in an amount of TiO in the titanium liquid20.5-1.2% of the content, then continuously heating to boiling at the speed of 1.5-2.5 ℃/min, cooling to room temperature at the speed of 20-30 ℃/min, and then cooling to obtain the final product
(4) Separating the hydrated TiO by centrifugation2In turn using purified 2MWashing with HCl water twice, washing with Zn-hexadecyl lauryl ether complex emulsifier three times, and washing with water three times, and mixing with the above water solution
(5) To hydrate TiO2Drying at the temperature of 100-125 ℃ for 0.5-1.5 hours, putting the dried mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating to 400-420 ℃ at the heating rate of 16-25 ℃/min, keeping the temperature for 0.4-0.6 hour, then continuously heating to 520-560 ℃ at the heating rate of 4-8 ℃/min, keeping the temperature for 1-2 hours, and then cooling to room temperature to obtain the high-purity ultrafine TiO2。
2. The process as claimed in claim 1, wherein the acid solution obtained by extracting titanium from the crude titanyl hydrochloride solution with organic solvent is reused for acidolysis of ilmenite, and the organic benzene-extracting agent is washed with 0.5M hydrochloric acid and recycled.
The method according to claim 1, wherein the Zn-hexadecyl cinnamyl ether complex is effective in hydrating TiO2The impurity ions in the water react chemically to form a new M-Zn hexadecyl cinnamyl ether complex which is washed away to hydrate TiO2The impurity ion is less than 0.1 ppm.
4. Ultrafine TiO produced by the process of claim 12Characterized by ultra-fine TiO2The crystal form of (A) is rutile type, the particle appearance is spindle type, the size is 38-45 nm, the length-to-diameter ratio of the crystal form is 1.5: 1-1: 1, and the pigment performance is good.
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| CN94110679A CN1038188C (en) | 1994-07-09 | 1994-07-09 | Preparation method of high-purity micro-fine rutile-type titanium dioxide |
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| CN94110679A CN1038188C (en) | 1994-07-09 | 1994-07-09 | Preparation method of high-purity micro-fine rutile-type titanium dioxide |
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| CN1056395C (en) * | 1998-07-03 | 2000-09-13 | 吉林大学 | Preparation of nanometer Tio/ore powder composite titanium dioxide |
| WO2010016835A1 (en) * | 2008-08-06 | 2010-02-11 | E. I. Du Pont De Nemours And Company | Processes for producing titanium dioxide |
| RU2518860C2 (en) * | 2009-09-02 | 2014-06-10 | ША Лилинь | Titanium-enriched ilmenite residue, its application and method of obtaining titanium pigment |
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| CN102102149B (en) * | 2009-12-21 | 2014-09-10 | 沙立林 | Leaching solution for leaching ilmenite, hydrochloric acid leaching method and application of leaching residues |
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| CN103771510B (en) * | 2014-02-11 | 2015-06-17 | 济南大学 | A kind of spindle-shaped rutile TiO Preparation method and resulting product |
| CN104071830B (en) * | 2014-04-30 | 2015-12-09 | 淄博晟钛复合材料科技有限公司 | Method for preparing high-purity rutile or anatase nano-titanium dioxide |
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| CN1040771A (en) * | 1988-08-19 | 1990-03-28 | 株式会社抽出研究所 | The manufacture method of titanium oxide |
| EP0440406A2 (en) * | 1990-01-29 | 1991-08-07 | Solex Research Corporation of Japan | Process for producing titanium dioxide |
| CN1063665A (en) * | 1990-11-20 | 1992-08-19 | C·M·莱特达 | Preparation of titanium dioxide from upgraded anatase concentrate using liquid sulfuric acid sulfation |
-
1994
- 1994-07-09 CN CN94110679A patent/CN1038188C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040771A (en) * | 1988-08-19 | 1990-03-28 | 株式会社抽出研究所 | The manufacture method of titanium oxide |
| EP0440406A2 (en) * | 1990-01-29 | 1991-08-07 | Solex Research Corporation of Japan | Process for producing titanium dioxide |
| CN1063665A (en) * | 1990-11-20 | 1992-08-19 | C·M·莱特达 | Preparation of titanium dioxide from upgraded anatase concentrate using liquid sulfuric acid sulfation |
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| CN1114949A (en) | 1996-01-17 |
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