阅读说明：本技术 一种化妆品用钛黑颜料的生产方法 (Production method of titanium black pigment for cosmetics ) 是由 邓科 唐红梅 阳丽 高原 海萍 于 2019-02-21 设计创作，主要内容包括：本发明公开了一种以工业TiCl<Sub>4</Sub>为原料生产化妆品用钛黑颜料的方法,它是将工业TiCl<Sub>4</Sub>除钒后经过Na<Sub>2</Sub>S与活性炭脱除重金属后,再经过6~9级精馏精制,得到含量为99.99%的且重金属含量低于50ppm的高纯TiCl<Sub>4</Sub>。精制的高纯TiCl<Sub>4</Sub>与后端还原尾气水洗得到的氨水进行氨中和水解,分离收集NH<Sub>4</Sub>Cl副产品,并对水解不溶物经过洗涤、煅烧后用H<Sub>2</Sub>/NH<Sub>3</Sub>还原,还原产物冷却后即可得到可作为化妆品颜料的钛黑成品。(The invention discloses a method for preparing industrial TiCl 4 The method for producing the titanium black pigment for cosmetics by using industrial TiCl as a raw material comprises the following steps 4 Removing vanadium and passing through Na 2 Removing heavy metals from the S and the activated carbon, and then rectifying and refining the S and the activated carbon by 6-9 stages to obtain high-purity TiCl with the content of 99.99 percent and the content of the heavy metals of less than 50ppm 4 . Refined high purity TiCl 4 Ammonia neutralization hydrolysis is carried out on the ammonia water obtained by washing the tail gas of the rear end reduction, NH is separated and collected 4 Cl byproduct, and washing and calcining the hydrolysis insoluble substance with H 2 /NH 3 Reducing, namely cooling a reduction productTo obtain the titanium black finished product which can be used as a cosmetic pigment.)

1. A process for preparing titanium black used as the pigment of cosmetics features that industrial TiCl is used₄High-purity TiCl which is taken as a raw material and is obtained by removing heavy metal and refining through multi-stage rectification₄Neutralizing with ammonia water, TiCl₄Washing, calcining and reducing the insoluble substance obtained by hydrolysis to obtain the titanium black finished product which can be used as a cosmetic pigment.

2. The method according to claim 1, wherein Na is used₂S and active carbon on industrial TiCl₄And (4) removing heavy metals.

3. The method as claimed in claim 1, wherein the TiCl is rectified by 6-9 stages₄And (4) refining.

4. The process of claim 1, characterized in that it consists in reacting TiCl₄The temperature for ammonia neutralization reaction is 90-100 ℃, wherein the concentration of ammonia water is 18-20%, and the ammonia water comes from the water washing liquid of the reduction tail gas.

5. The process of claim 1, characterized in that it consists in reacting TiCl₄The calcining reaction temperature of the hydrolysis insoluble substance is 950-1050 ℃.

6. The method according to claim 1, wherein TiO is added to the calcined product₂The reducing gas of (2) is H₂Or NH₃Or H in any proportion₂And NH₃The mixed gas of (1).

7. The method according to claim 1, characterized in that the reduction gas H is reduced by means of a calcination off-gas pair₂/NH₃Preheating to about 600 ℃, wherein the temperature of the reduction reaction is 750-850 ℃.

8. The method of claim 1, wherein the reduction product is at N₂Cooling under the protection of (1).

Technical Field

The invention relates to a method for preparing industrial TiCl₄A method for producing titanium black pigment used for cosmetics by using raw materials, belonging to the field of titanizing industry. It is prepared from industrial TiCl₄After heavy metal removal, refining to obtain high-purity TiCl₄Then, howeverPost high purity TiCl₄Neutralizing with ammonia water, washing and calcining insoluble substance, and adding H₂/NH₃Reducing, and cooling the reduction product to obtain the titanium black finished product which can be used as a cosmetic pigment.

Background

The titanium black is black titanium suboxide or titanium oxynitride powder, is an environment-friendly inorganic pigment with pure blackness, has high thermal stability, particularly good hydrophilicity and lipophilicity, has good dispersion performance in water and resin, and has the characteristics of high temperature resistance, environmental protection, no toxicity and edibility; and can provide resistance values in different ranges, and can be used as a black pigment for coatings, paints, cosmetics, printing ink and plastic colorants for food industry, and can also be used as an excellent conductive material and an antistatic material.

The titanium black product is prepared by heating and reducing titanium dioxide serving as a main raw material in a reducing medium, and the color tone of the titanium black product can be cyan black, purple black and the like according to different reducing degrees. In the past, carbon black is used as a main raw material of black cosmetics, and has high blackness and strong tinting strength; however, carbon black is hydrophobic, is difficult to disperse in water, and contains carcinogens. In Japan, titanium dioxide is firstly reduced to prepare low-valence titanium oxide and titanium oxynitride black powder pigment to replace carbon black in black cosmetics, the treated high-purity titanium dioxide is used as a raw material, and the titanium oxynitride black pigment can be obtained by reduction in ammonia gas, is safe and nontoxic in the production process, and can be used as a black pigment in cosmetics (such as mascara, eyebrow pencil, eye shadow and the like). The black cosmetic taking titanium black as a raw material can play a role in ultraviolet protection and safe makeup, and is popular with consumers.

In the seventies of the last century, a method of mixing titanium dioxide and metallic titanium powder and heating the mixture in vacuum to prepare titanium black was first reported in japan, and other preparation methods were subsequently reported. SUMD in Japan₂/N₂Reducing titanium dioxide micropowder in a mixed gas atmosphere, carrying out the whole reaction in a titanium tube reactor, controlling the temperature to be 600-1000 ℃, and filling a titanium ball with the diameter of 0.01-9 mm and a propeller in the reactor to prepare the titanium dioxide micropowderMake out a chemical formula of Ti_nO_(2n-1)The titanium suboxide micro powder (the general particle diameter is less than 0.1 micron and called as ultra-fine particle) with n being more than or equal to 1 and less than or equal to 10 has good dispersibility, good thermal stability when the temperature is up to 50 ℃, 4.5 relative density and 50m specific surface area²(ii) in terms of/g. In addition, there are also a method of reducing titanium dioxide powder with ammonia gas and methylamine as reducing agents to obtain a titanium suboxide black product, and a method of reducing titanium dioxide in a plasma atmosphere of a reducing gas to obtain a titanium black product.

As a titanium black product for a cosmetic pigment, the heavy metal content of the product is required to be lower than 50ppm, the titanium dioxide needs to be purified in the conventional titanium black production process for reducing by taking the titanium dioxide as a raw material, but the impurity removal process efficiency of solid titanium dioxide is low, and the cost is high, so that the heavy metal content of the finally obtained titanium black product cannot meet the use requirement of cosmetics.

Titanium resources in China are very rich, titanizers, particularly titanium dioxide, have a large scale, but the preparation of titanium black products, particularly titanium black products used in the field of cosmetics, is rarely reported; with the increasing living standard of people, the requirement on the safety of cosmetic products is higher and higher, so that the titanium black for cosmetics has wide prospect as a deep processing product of titanium chemical industry.

Disclosure of Invention

The invention uses the prior industrial TiCl₄Is used as raw material, and is purified and purified by H₂/NH₃Reducing to obtain the titanium black finished product which can be used as a cosmetic pigment.

The purpose of the invention is realized as follows: firstly, a small amount of aluminum powder is added into industrial TiCl₄Heating to 130-150 ℃ and preserving the heat for 3-5 h to remove the industrial TiCl₄VOCl in (1)₃Reduced to precipitated VOCl₂Separating the precipitate to obtain TiCl₄Adding Na sequentially thereto₂S and activated carbon, converting heavy metal ions in the S into sulfide salt to be adsorbed in the activated carbon, separating the activated carbon to obtain TiCl₄Then rectifying in a 6-9 grade titanium material rectifying tower to obtain the product with low purityHigh-purity TiCl with less than 99.99% and heavy metal content below 50ppm₄。

Adding ammonia water with the concentration of about 20 percent, which is obtained by three-stage countercurrent washing of the reduction tail gas by deionized water, into the high-purity TiCl prepared by the purification and impurity removal₄Subjecting it to ammonolysis to obtain hydrated TiO₂Ultra-fine particle and by-product NH₄Cl, controlling the temperature to be 950-1050 ℃ for hydrating TiO₂Calcining the ultrafine particles; calcination tail gas to reducing gas H₂/NH₃(can be mixed in any proportion) preheating to about 600 ℃ and H after preheating₂/NH₃In a reduction furnace with the calcined TiO₂Carrying out reduction reaction on the ultrafine particles at the temperature of 750-850 ℃, and controlling the reduction reaction according to the requirement of the product to obtain different products with reduction purity; after the reaction is finished, at N₂The reduction product is cooled under the protection of the above step to obtain a titanium black finished product.

The invention has the beneficial effects that: by applying to industrial TiCl₄The impurity removal and purification process designed by the invention can prepare high-purity TiCl with the purity of not less than 99.99 percent and the heavy metal content of less than 50ppm₄The problems of difficult impurity removal, high cost and the like of titanium dioxide used as a raw material in the preparation of the titanium black product for cosmetics are solved; at the same time, TiCl₄The ammonolysis uses the washing of the reduction tail gas to recover ammonia water, and realizes secondary utilization of ammonia gas in the reduction tail gas; in the reduction reaction, the reducing gas H is adjusted₂/NH₃The titanium black products with different reduction purities can be obtained by controlling different reaction times according to the proportion.

Drawings

FIG. 1 is a schematic process flow diagram of the present invention for preparing titanium black pigment for cosmetics.

Detailed Description

The present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited to these examples.