CN102923767B - Method for producing titanium dioxide from alkali molten salt without intermediate caking - Google Patents

Method for producing titanium dioxide from alkali molten salt without intermediate caking Download PDF

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CN102923767B
CN102923767B CN201110231146.3A CN201110231146A CN102923767B CN 102923767 B CN102923767 B CN 102923767B CN 201110231146 A CN201110231146 A CN 201110231146A CN 102923767 B CN102923767 B CN 102923767B
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sodium hydroxide
titanium dioxide
titanium material
intermediate product
rich
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CN102923767A (en
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初景龙
王东
齐涛
王丽娜
薛天艳
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Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
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Abstract

The invention relates to a method for producing titanium dioxide from an alkali molten salt without intermediate caking. The method comprises the following steps: 1, heating a sodium hydroxide solution to 100-150DEG C, adding a titanium rich material to the sodium hydroxide solution, and carrying out a desilication reaction to obtain a silicate-free titanium rich material, wherein the weight part ratio of the sodium hydroxide solution to the titanium rich material is 2-4:1; 2, uniformly mixing the silicate-free titanium rich material with sodium peroxide powder to obtain a mixture, wherein the weight part ratio of the silicate-free titanium rich material to the sodium peroxide powder is 1:5-50; 3, adding the mixture to the molten sodium hydroxide having a temperature of 350-400DEG C, reacting for 1-5h, continuously heating to 450-550DEG C, and reacting for 1-3h to obtain a loose molten salt reaction intermediate, wherein the weight part ratio of the mixture to sodium hydroxide is 1:0.8-1.2; and 4, carrying out water washing, acid dissolving, reducing, hydrolyzing and calcining of the intermediate to obtain anatase or rutile titanium dioxide. The method has the advantages of overcoming of a problem of intermediate caking in the reaction of the titanium rich material and the molten sodium hydroxide, and simple and convenient operation.

Description

A kind of method that alkaline process fused salt of anti-intermediate product caking is produced titanium dioxide
Technical field
The invention belongs to the process for processing field of titanium dioxide, be specifically related to a kind of method of alkaline process fused salt production titanium dioxide of anti-intermediate product caking.
Background technology
Titanium dioxide is commonly called as titanium dioxide, it is a kind of important source material in chemical industry, nontoxic, be harmless to the health, it is most important white pigment, accounts for 80% of whole white pigment usage quantitys, it is also the main product of titanium system, 90% of titanium resource be all used for manufacturing titanium dioxide in the world, titanium dioxide is widely used in modern industry, agricultural, national defence, scientific and technical numerous areas, has close contacting with people's lives and national economy.
At present, the industrial process of titanium dioxide has sulfuric acid process and chlorination process, and these methods all exist that refuse amount is large, strong toxicity and the environmental pollution problem such as heavily.Chinese Academy Of Sciences Process Engineering Research Institute is on the basis of the sub-fused salt chemical industry metallurgical technology of research and development, the method of low-temperature molten salt cleaner production titanium white has been proposed, it is raw material that the method be take titanium slag (being greater than 90wt% containing titanium dioxide), take sodium hydroxide fused salt as reaction medium, from beginning of production, eliminate environmental pollution, realize the efficient and clean comprehensive utilization of titanium resource and valuable component; In this method, first titanium slag and sodium hydroxide are mixed according to weight part ratio 1.2:1, then by mixture direct heating to 550 ℃ and react at this temperature and within 1 hour, obtain fused salt intermediate product; Then the washing in the technical scheme that is CN200610114130.3 according to number of patent application, acid is molten, reduction, hydrolysis and the step such as calcining, obtain the titanium dioxide of anatase titanium dioxide or rutile-type.
Researchist once attempted substituting titanium slag with rich titanium material (containing content of titanium dioxide 70wt%~85wt%) and prepared titanium dioxide by molten salt react ion, but due to calcium in rich titanium material, magnesium, the foreign matter contents such as silicon are more, in molten salt react ion process, corresponding impurity can generate water glass salt, the impurity such as calcium hydroxide and magnesium hydroxide, these impurity can stick together the meta-titanium perborate intermediate product of generation, the molten salt react ion intermediate product caking that exists generation is more serious, and cover reactor wall, hinder the mass transfer of reaction process, conduct heat, the reaction conversion ratio of principal element titanium significantly reduces.
Summary of the invention:
The object of the invention is to overcome with rich titanium material and substitute titanium slag is prepared the reaction intermediate caking in the production technique of a titanium dioxide difficult problem by molten salt react ion, and a kind of method that provides alkaline process fused salt of anti-intermediate product caking to produce titanium dioxide.
The present invention is realized by the following technical programs:
The method that the alkaline process fused salt of anti-intermediate product caking provided by the invention is produced titanium dioxide, its step is as follows:
(1) sodium hydroxide solution that is 15%~40% by concentration is heated to 100 ℃~150 ℃; Rich titanium material is joined in the sodium hydroxide solution after above-mentioned heating and carries out desilication reaction, obtain the rich titanium material of desiliconization;
Described concentration is that 15%~40% sodium hydroxide solution and the weight part ratio of rich titanium material are 2~4:1;
(2) the rich titanium material of desiliconization and the sodium peroxide powder that step (1) are obtained are evenly mixed to get compound;
The weight part ratio of described sodium peroxide powder and rich titanium material is 1:5~50;
(3) compound being joined to temperature is to react 1~5 hour in the molten state sodium hydroxide of 350~400 ℃; Continue to be again warmed up to 450~550 ℃ of reactions 1~3 hour, obtain loose molten salt react ion intermediate product;
The weight part ratio of described compound and sodium hydroxide is 1:0.8~1.2;
(4) the loose molten salt react ion intermediate product obtaining successively, reduction molten through washing, acid, hydrolysis and calcining are obtained to the titanium dioxide of anatase titanium dioxide or rutile-type.
In described rich titanium material, content of titanium dioxide is 70wt%~85wt%.
Described molten state sodium hydroxide is heated to 350~400 ℃ by solid sodium hydroxide and obtains.
The method that the alkaline process fused salt of anti-intermediate product caking of the present invention is produced titanium dioxide, is first used alkali lye to carry out desiliconization to rich titanium material, has reduced the growing amount of molten salt react ion mesosilicic acid sodium; Next has changed type of heating, at 350 ℃ to 550 ℃, carries out molten salt react ion, and different like this elements molten salt react ion can not occur simultaneously, has therefore reduced sticky amount; Finally, add a certain amount of sodium peroxide in molten salt react ion, sodium peroxide can generate oxygen bubbles in molten salt react ion process, makes molten salt react ion product present the structure of a porous; When therefore the present invention can effectively reduce rich titanium material and sodium hydroxide generation molten salt react ion, the phenomenon of reaction intermediate caking, presents molten salt react ion product more with powdery form, and has increased the transformation efficiency of reaction;
The method tool that the alkaline process fused salt of anti-intermediate product caking of the present invention is produced titanium dioxide has the following advantages: the method can effectively prevent rich titanium material and sodium hydroxide intermediate product generation sintering when molten salt react ion; Additive in its production technique is sodium peroxide, the impurity not having to introduce in former system; When guaranteeing reaction conversion ratio, prevent the successful that lumps, simple to operation.
Embodiment
Embodiment 1:
48g solid sodium hydroxide is put in nickel plating reactor and is heated to 350 ℃, 40g titanium slag (its composition is as shown in table 1) is joined in reactor and reacted with liquid sodium hydroxide.Temperature was elevated to gradually to 500 ℃ in 2 hours, keeps 1 hour at 500 ℃, taking-up reaction intermediate (sample one in table 2) is to be measured.
48g solid sodium hydroxide is put in nickel plating reactor and is heated to 350 ℃, its composition of the rich titanium material of 40g 1(is as shown in table 1) join in reactor and react with liquid sodium hydroxide.Temperature was elevated to gradually to 500 ℃ in 2 hours, at 500 ℃, keeps 1 hour.Take out reaction intermediate (sample two in table 2) to be measured.
48g solid sodium hydroxide is put in nickel plating reactor and is heated to 350 ℃, its composition of the rich titanium material of 40g 2(is as shown in table 1) join in reactor and react with liquid sodium hydroxide.Temperature was elevated to gradually to 500 ℃ in 2 hours, at 500 ℃, keeps 1 hour.Take out reaction intermediate (sample three in table 2) to be measured.
48g solid sodium hydroxide is put in nickel plating reactor and is heated to 350 ℃, its composition of the rich titanium material of 40g 3(is as shown in table 1) join in reactor and react with liquid sodium hydroxide.Temperature was elevated to gradually to 500 ℃ in 2 hours, at 500 ℃, keeps 1 hour.Take out reaction intermediate (sample four in table 2) to be measured.
As seen from the above: use rich titanium material to replace titanium slag alkaline process fused salt to produce in the technological process of titanium dioxide, there will be intermediate product caking phenomenon; This is having a strong impact on the feasibility of molten-salt growth method titanium white explained hereafter.
Embodiment 2:
1,32g sodium hydroxide is put in nickel plating reactor, be heated to 350 ℃ molten state sodium hydroxide;
2, the rich titanium material 1 of 40g desiliconization and 8g sodium peroxide powder are evenly mixed to get to compound, then compound are added in the nickel plating reactor of step 1 and react 5 hours at 350 ℃ with molten state sodium hydroxide; In 1 hour, nickel plating temperature of reaction kettle is elevated to 450 ℃ gradually afterwards, at 450 ℃, keeps 1 hour, obtain loose molten salt react ion intermediate product (sample five in table 2) to be measured;
Being prepared as follows of the rich titanium material 1 of desiliconization wherein:
The sodium hydroxide solution of concentration 15wt% is put into reactor and is heated to 100 ℃, the rich titanium material 1 of rich titanium material 1(is formed as shown in table 1) join in reactor, there are desilication reaction 2 hours with alkali lye (sodium hydroxide solution); Filter afterwards to obtain the rich titanium material 1 of desiliconization, the richer titanium material 1 of desiliconization is washed and is dried, obtain the rich titanium material 1 of desiliconization;
In the present embodiment, the weight part ratio of the sodium hydroxide solution of described concentration 15wt% and rich titanium material 1 is 2:1.
Embodiment 3:
1,48g sodium hydroxide is put in nickel plating reactor, be heated to 380 ℃ molten state sodium hydroxide;
2, the rich titanium material 1 of 40g desiliconization and 0.8g sodium peroxide powder are evenly mixed to get to compound, then compound are added in the nickel plating reactor of step 1 and react 1 hour at 350 ℃ with molten state sodium hydroxide; In 1.5 hours, nickel plating temperature of reaction kettle is elevated to 500 ℃ gradually afterwards, at 500 ℃, keeps 1 hour, obtain loose molten salt react ion intermediate product (sample six in table 2) to be measured;
Being prepared as follows of the rich titanium material 1 of desiliconization wherein:
The sodium hydroxide solution of concentration 40wt% is put into reactor and is heated to 150 ℃, the rich titanium material 1 of rich titanium material 1(is formed as shown in table 1) join in reactor, there are desilication reaction 2 hours with alkali lye (sodium hydroxide solution); Filter afterwards to obtain the rich titanium material 1 of desiliconization, the richer titanium material 1 of desiliconization is washed and is dried, obtain the rich titanium material 1 of desiliconization;
In the present embodiment, the weight part ratio of the sodium hydroxide solution of described concentration 40wt% and rich titanium material 1 is 4:1.
Embodiment 4:
1,40g sodium hydroxide is put in nickel plating reactor, be heated to 400 ℃ molten state sodium hydroxide;
2, the rich titanium material 1 of 40g desiliconization and 4g sodium peroxide powder are evenly mixed to get to compound, then compound are added in the nickel plating reactor of step 1 and react 2 hours at 400 ℃ with molten state sodium hydroxide; In 1.5 hours, nickel plating temperature of reaction kettle is elevated to 550 ℃ gradually afterwards, at 550 ℃, keeps 1 hour, obtain loose molten salt react ion intermediate product (sample seven in table 2) to be measured;
Embodiment 5:
1,40g sodium hydroxide is put in nickel plating reactor, be heated to 400 ℃ molten state sodium hydroxide;
2, the rich titanium material 2 of 40g and 4g sodium peroxide powder are evenly mixed to get to compound, then compound are added in the nickel plating reactor of step 1 and react 2 hours at 400 ℃ with molten state sodium hydroxide; In 1.5 hours, nickel plating temperature of reaction kettle is elevated to 550 ℃ gradually afterwards, at 550 ℃, keeps 1 hour, obtain loose molten salt react ion intermediate product (sample eight in table 2) to be measured;
Embodiment 6:
1,40g sodium hydroxide is put in nickel plating reactor, be heated to 400 ℃ molten state sodium hydroxide;
2, the rich titanium material 3 of 40g and 4g sodium peroxide powder are evenly mixed to get to compound, then compound are added in the nickel plating reactor of step 1 and react 2 hours at 400 ℃ with molten state sodium hydroxide; In 1.5 hours, nickel plating temperature of reaction kettle is elevated to 550 ℃ gradually afterwards, at 550 ℃, keeps 1 hour, obtain loose molten salt react ion intermediate product (sample nine in table 2) to be measured;
Being prepared as follows of the rich titanium material 1 of desiliconization wherein:
The sodium hydroxide solution of concentration 30wt% is put into reactor and is heated to 120 ℃, the rich titanium material 1 of rich titanium material 1(is formed as shown in table 1) join in reactor, there are desilication reaction 2 hours with alkali lye (sodium hydroxide solution); Filter afterwards to obtain the rich titanium material 1 of desiliconization, the richer titanium material 1 of desiliconization is washed and is dried, obtain the rich titanium material 1 of desiliconization;
In the present embodiment, the weight part ratio of the sodium hydroxide solution of described concentration 30wt% and rich titanium material 1 is 3:1.
Table 1 is the weight percentage of titanium slag, rich titanium material 1, rich titanium material 2 and rich titanium material 3 contained components:
Table 2
As can be seen from Table 2, embodiment 2-4 adopts method of the present invention, the molten salt react ion intermediate product that the rich titanium material 1 of take obtains as raw material, with to take the small-particle massfraction of the molten salt react ion intermediate product that titanium slag obtains as raw material suitable, has prevented the phenomenon of reaction caking effectively.

Claims (3)

1. the method that the alkaline process fused salt of anti-intermediate product caking is produced titanium dioxide, its step is as follows:
(1) sodium hydroxide solution that is 15%~40% by concentration is heated to 100 ℃~150 ℃; Rich titanium material is joined in the sodium hydroxide solution after above-mentioned heating and carries out desilication reaction, obtain the rich titanium material of desiliconization;
Described concentration is that 15%~40% sodium hydroxide solution and the weight part ratio of rich titanium material are 2~4: 1;
(2) the rich titanium material of desiliconization and the sodium peroxide powder that step (1) are obtained are evenly mixed to get compound;
The weight part ratio of described sodium peroxide powder and rich titanium material is 1: 5~50;
(3) compound being joined to temperature is to react 1~5 hour in the molten state sodium hydroxide of 350~400 ℃; Continue to be again warmed up to 450~550 ℃ of reactions 1~3 hour, obtain loose molten salt react ion intermediate product;
The weight part ratio of described compound and sodium hydroxide is 1: 0.8~1.2;
(4) the loose molten salt react ion intermediate product obtaining successively, reduction molten through washing, acid, hydrolysis and calcining are obtained to the titanium dioxide of anatase titanium dioxide or rutile-type.
2. the method for producing titanium dioxide by the alkaline process fused salt of anti-intermediate product caking claimed in claim 1, is characterized in that, in described rich titanium material, content of titanium dioxide is 70wt%~85wt%.
3. the method for producing titanium dioxide by the alkaline process fused salt of anti-intermediate product caking claimed in claim 1, is characterized in that, described molten state sodium hydroxide is heated to 350~400 ℃ by solid sodium hydroxide and obtains.
CN201110231146.3A 2011-08-12 2011-08-12 Method for producing titanium dioxide from alkali molten salt without intermediate caking Active CN102923767B (en)

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CN103950976A (en) * 2014-04-04 2014-07-30 中国科学院过程工程研究所 Method for preparing titanium dioxide by utilizing mixed alkali of sodium hydroxide and sodium nitrate

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