CN1169956A - Manufacture of black titanium oxide - Google Patents
Manufacture of black titanium oxide Download PDFInfo
- Publication number
- CN1169956A CN1169956A CN 96116418 CN96116418A CN1169956A CN 1169956 A CN1169956 A CN 1169956A CN 96116418 CN96116418 CN 96116418 CN 96116418 A CN96116418 A CN 96116418A CN 1169956 A CN1169956 A CN 1169956A
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- CN
- China
- Prior art keywords
- titanium
- low price
- organic acid
- acid salt
- black oxidation
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
A thermal decomposition process for preparing black titanium oxide includes such steps as chloride of low-valence Ti on biatomic organic carboxylic acid to obtain the organic acid's salt of low-valence titanium, filtering, washing, baking and thermal decomposition under the protection of inertial gas, and features low cost, high quality and easily controlling technological conditions. The black titanium oxide can be used as high-quality non-toxic pigment for cosmetics or as external paint of high-grade car and liquid crystal display.
Description
The present invention relates to prepare the technology of black oxidation titanium, further relate to the method that makes black oxidation titanium with the organic acid salt thermolysis of low price titanium with the pyrolysated method.
Black oxidation titanium, Ti
nO
2n-1(≤n≤10) are a kind of titanium suboxides.Of many uses.Especially in building materials and cosmetic industry as the high-grade black pigment.For example in cosmetic industry, make the black pigment that eyebrow pencil and Jie Mao cream are used, because of it directly contacts with human body, so except chromaticness was pure, security was first important.In view of present used black pigment is carbon black and iron oxide black, carbon black and water are difficult for soaking into, and contain 3,4-benzopyrene (carcinogenic substance); Iron black carrying magnetic, the back chromaticness poor performance of being heated is with red during color is black.Black oxidation titanium is as black pigment, though cost an arm and a leg, because of its safe and reliable nontoxicity, chromaticness is pure, and resistance toheat is good, with water infiltration and sintering character, higher activity and be widely adopted preferably.
Up to the present, all be both at home and abroad adopt metallic titanium powder in vacuum (or at TiCl
4Atmosphere) under the condition, or use NH
3, H
2, high temperature reduces superfine Ti O more than 600 ℃ under the CO gas shiled
2Powder (granularity＜0.1 micron) prepares black oxidation titanium (Japanese Patent Jp63-56324; 62-212207; 61-146714; 57-205327), keep such high temperature and cost dearly, in addition, because solid-solid reaction can not be complete, necessary repeated multiple times, energy consumption is very high.
Be to adopt superfine Ti O just as Japanese Patent (Jp63-206315)
2Powder (granularity is the 0.02-0.04 micron) under the protection of hydrogen and nitrogen mixture body, reductase 12-3 hour under the 700-1100 ℃ of high temperature, can make chemical formula is Ti
nO
2n-1(n=1-4), granularity is the black oxidation titanium of 0.02-0.03 micron (behind ball milling).But the superfine Ti O that this method is used
2Costing an arm and a leg of raw material, the temperature height of reduction reaction, time are long, so energy consumption is also high, and this solid-solid reaction to cause unstable product quality (be that product is formed Ti
nO
2n-1The n value change greatly).In order to allow quality product tend towards stability, must repeated multiple times repeat this reduction reaction, caused can't change high for the cost of product.
In addition, Japanese Patent (Jp63-206314) is to be the superfine Ti O of 0.01-0.04 micron with granularity
2Join in the special device with the stirring rod of metal titanium and the stirring ball that differs in size that metal titanium is made, (needing metallic titanium plate to make liner) uses N in 600-1000 ℃ of high temperature
2And H
2Mixed gas protected, the reaction times is 2-3 hour, makes chemical formula Ti
nO
2n-1(n=1-4), granularity is the black oxidation titanium of 0.02-0.03 micron (behind ball milling).Though the black oxidation titanium that this method makes is more more satisfied than the color that preceding a kind of method makes,, this method is harsh especially to the requirement of equipment configuration; And same high raw materials cost and the energy consumption that exists; Gas-solid reaction incomplete etc. makes the price costliness very of product.
The purpose of this invention is to provide a kind of high quality less energy-consumption, and simple to operate easy to control, equipment do not had the preparation method of the black oxidation titanium of special requirement.
The present invention is achieved in that by thermolysis makes black oxidation titanium to low price titanium organic acid salt.The titanium organic acid salt is muriate and the organic di-carboxylic acid (C by the low price titanium at a low price
2-C
6) reaction at normal temperatures and pressures, generate titanium acylate solution at a low price, after filtration, washing, oven dry (80-90 ℃) make solid titanium organic acid salt at a low price.Then above-mentioned solid low price titanium organic acid salt is placed in the tube furnace, under the inert gas atmosphere protection, 600-750 ℃ was carried out thermolysis 15-30 minute, and made black oxidation titanium of the present invention.
Advantage of the present invention is:
(1) because low price titanium such as Ti (II) easily generate complex compound with organic di-carboxylic acid; and they are under controlled atmosphere; easily thermolysis becomes black oxidation titanium at a low price; the muriate of the low price titanium that present method adopts and organic di-carboxylic acid cost of material is low, the source wide and short energy consumption of pyrolysis time is low is so greatly reduce production cost.
(2) the selected processing condition of the present invention are simple, and therefore easy and simple to handle on the one hand, control is not high to the requirement of equipment on the other hand yet easily.
(3) overcome gas-solid, the incomplete shortcoming of solid-solid reaction with method generation low price titanium organic acid salt of the present invention, reaction is relatively fully complete, and the product composition is stablized, and quality is also high.
The present invention is further described by the following embodiment.
Embodiment 1.
7 gram pentanedioic acids are dissolved in 400 ml distilled waters, with the PH=7 of ammoniacal liquor regulator solution.At N
2Protection is following stirs, and the limit adds 20 milliliters 1.5mol/L TiCl
3Solution; Suction filtration; Wash with water for several times; Throw out is placed 80-90 ℃ of oven dry in the baking oven; Solid low price titanium organic acid salt with oven dry is placed in the tube furnace then, at N
2Under the protection, 600-750 ℃ was carried out thermolysis 15-30 minute, and making chemical formula of the present invention is Ti
4O
7Black oxidation titanium.
Embodiment 2.
Get 30 gram TiCl
4, add 2.5 gram titanium valves, add 140 milliliter 20% oxalic acid solution then while stirring, use ammoniacal liquor regulator solution PH=4 then, suction filtration washes with water for several times, and precipitation is placed 80-90 degree oven dry in the baking oven; Be placed on then in the tube furnace, at N
2Under the protection, 600-750 ℃ was carried out thermolysis 15-30 minute, and making chemical formula of the present invention is Ti
4O
7Black oxidation titanium.
Through X-ray diffraction analysis, above-mentioned two routine black oxidation titaniums are by TiO
2And Ti
2O two phase composites, product is through asking mill after 48 hours, and granularity is less than 0.5 micron, and specific surface area is 25m
2/ g, resistivity is 10
4Ω .cm.
Claims (2)
1. method for preparing black oxidation titanium, it is characterized in that: muriate and organic di-carboxylic acid of titanium react at normal temperatures and pressures at a low price earlier, generate titanium organic acid salt precipitation at a low price, after filtration, washing, oven dry (80-90 ℃) make solid titanium organic acid salt at a low price; Then above-mentioned solid low price titanium organic acid salt is placed in the tube furnace, under the inert gas atmosphere protection, 600-750 ℃ was carried out thermolysis 15-30 minute, and made black oxidation titanium.
2. a kind of method for preparing black oxidation titanium according to claim 1 is characterized in that: wherein as pyrolysated at a low price the titanium organic acid salt be muriate and organic di-carboxylic acid (C by the low price titanium
2-C
6) at normal temperatures and pressures the reaction make.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96116418 CN1169956A (en) | 1996-07-08 | 1996-07-08 | Manufacture of black titanium oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96116418 CN1169956A (en) | 1996-07-08 | 1996-07-08 | Manufacture of black titanium oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1169956A true CN1169956A (en) | 1998-01-14 |
Family
ID=5123523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96116418 Pending CN1169956A (en) | 1996-07-08 | 1996-07-08 | Manufacture of black titanium oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1169956A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100348821B1 (en) * | 1999-01-25 | 2002-08-17 | 주식회사 태평양 | A Method for preparing black titanium oxide powder |
| CN101983929A (en) * | 2010-11-29 | 2011-03-09 | 四川大学 | Preparation method of low-valence titanium oxide powder |
| CN102249300A (en) * | 2011-05-12 | 2011-11-23 | 陕西鸿禧新材料有限公司 | Preparation method of black titanium dioxide |
| CN107352580A (en) * | 2017-08-01 | 2017-11-17 | 中国科学院合肥物质科学研究院 | One kind prepares black TiO using bean dregs2The method of nano material |
-
1996
- 1996-07-08 CN CN 96116418 patent/CN1169956A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100348821B1 (en) * | 1999-01-25 | 2002-08-17 | 주식회사 태평양 | A Method for preparing black titanium oxide powder |
| CN101983929A (en) * | 2010-11-29 | 2011-03-09 | 四川大学 | Preparation method of low-valence titanium oxide powder |
| CN101983929B (en) * | 2010-11-29 | 2012-04-25 | 四川大学 | Preparation method of low-valence titanium oxide powder |
| CN102249300A (en) * | 2011-05-12 | 2011-11-23 | 陕西鸿禧新材料有限公司 | Preparation method of black titanium dioxide |
| CN102249300B (en) * | 2011-05-12 | 2013-03-06 | 陕西鸿禧新材料有限公司 | Preparation method of black titanium dioxide |
| CN107352580A (en) * | 2017-08-01 | 2017-11-17 | 中国科学院合肥物质科学研究院 | One kind prepares black TiO using bean dregs2The method of nano material |
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| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
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