CN102923767A - 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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Publication number
CN102923767A
CN102923767A CN2011102311463A CN201110231146A CN102923767A CN 102923767 A CN102923767 A CN 102923767A CN 2011102311463 A CN2011102311463 A CN 2011102311463A CN 201110231146 A CN201110231146 A CN 201110231146A CN 102923767 A CN102923767 A CN 102923767A
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sodium hydroxide
titanium dioxide
titanium material
intermediate product
molten
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CN102923767B (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

The method that a kind of 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 the chemical industry, nontoxic, be harmless to the health, it is most important white pigment, accounts for 80% of whole white pigment usage quantitys, it also is the main product of titanium system, 90% of titanium resource all be used for making titanium dioxide in the world, titanium dioxide is widely used in modern industry, agricultural, national defence, scientific and technical numerous areas, with people's lives and national economy close contacting is arranged.
At present, the industrial process of titanium dioxide has sulfuric acid process and chlorination process, and these methods exist all that the refuse amount is large, strong toxicity and environmental pollution heavily wait problem.Chinese Academy Of Sciences Process Engineering Research Institute is on the basis of the inferior fused salt chemical industry metallurgical technology of research and development, the method of low-temperature molten salt cleaner production titanium white has been proposed, the method is take titanium slag (containing titanium dioxide greater than 90wt%) as raw material, take the sodium hydroxide fused salt as reaction medium, eliminate environmental pollution from beginning of production, realize the comprehensive utilization of the efficient and cleaning of titanium resource and valuable component; In this method, at first titanium slag and sodium hydroxide are mixed according to weight part ratio at 1.2: 1, then with mixture direct heating to 550 ℃ and under this temperature reaction obtained the fused salt intermediate product in 1 hour; Then be washing in the technical scheme of CN200610114130.3 according to number of patent application, acid is molten, reduction, and the steps such as hydrolysis and calcining obtain the titanium dioxide of anatase titanium dioxide or rutile-type.
The researchist attempted once that (containing content of titanium dioxide 70wt%~85wt%) substitutes titanium slag and prepare titanium dioxide by molten salt react ion with rich titanium material, but because calcium in the rich titanium material, magnesium, the foreign matter contents such as silicon are more, in the molten salt react ion process, corresponding impurity can generate the water glass salt, the impurity such as calcium hydroxide and magnesium hydroxide, these impurity can stick together the meta-titanium perborate intermediate product that generates, the molten salt react ion intermediate product caking that exists generation is more serious, and cover the reactor wall, hinder the mass transfer of reaction process, conduct heat the reaction conversion ratio decrease of principal element titanium.
Summary of the invention:
The objective of the invention is to overcome a difficult problem that substitutes the reaction intermediate caking in titanium slag prepares titanium dioxide by molten salt react ion the production technique with rich titanium material, and the method that provides a kind of 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) be that 15%~40% sodium hydroxide solution is heated to 100 ℃~150 ℃ with concentration; Rich titanium material joined in the sodium hydroxide solution after the above-mentioned heating carry 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 the desiliconization that step (1) is obtained and sodium peroxide powder evenly are 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 temperature is to react 1~5 hour in 350~400 ℃ the molten state sodium hydroxide; Continue again to be 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;
Wash successively, acid is molten by process for the loose molten salt react ion intermediate product that (4) will obtain, reduce, be hydrolyzed and calcine the titanium dioxide that obtains anatase titanium dioxide or rutile-type.
Content of titanium dioxide is 70wt%~85wt% in the described rich titanium material.
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 at first uses alkali lye that rich titanium material is carried out desiliconization, has reduced the growing amount of molten salt react ion mesosilicic acid sodium; Next has changed type of heating, carries out molten salt react ion at 350 ℃ to 550 ℃, and different like this elements molten salt react ion can not occur simultaneously, has therefore reduced sticking amount; At last, add a certain amount of sodium peroxide in molten salt react ion, sodium peroxide can generate oxygen bubbles in the molten salt react ion process, so that the molten salt react ion product presents the structure of a porous; The phenomenon of reaction intermediate caking when therefore the present invention can effectively reduce rich titanium material and sodium hydroxide generation molten salt react ion so that the molten salt react ion product presents with the powdery form more, and has increased the transformation efficiency of reaction;
The method that the alkaline process fused salt of anti-intermediate product caking of the present invention is produced titanium dioxide has following advantage: 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:
The 48g solid sodium hydroxide put into be heated to 350 ℃ in the nickel plating reactor, the sodium hydroxide that 40g titanium slag (its composition is as shown in table 1) is joined in the reactor with liquid state reacts.Temperature was elevated to 500 ℃ gradually in 2 hours, 500 ℃ of lower maintenances 1 hour, taking-up reaction intermediate (sample one in the table 2) is to be measured.
The 48g solid sodium hydroxide put into be heated to 350 ℃ in the nickel plating reactor, the sodium hydroxide that the rich titanium material of 40g 1 (its composition is as shown in table 1) joined in the reactor with liquid state reacts.Temperature was elevated to 500 ℃ gradually in 2 hours, 500 ℃ of lower maintenances 1 hour.Take out reaction intermediate (sample two in the table 2) to be measured.
The 48g solid sodium hydroxide put into be heated to 350 ℃ in the nickel plating reactor, the sodium hydroxide that the rich titanium material of 40g 2 (its composition is as shown in table 1) are joined in the reactor with liquid state reacts.Temperature was elevated to 500 ℃ gradually in 2 hours, 500 ℃ of lower maintenances 1 hour.Take out reaction intermediate (sample three in the table 2) to be measured.
The 48g solid sodium hydroxide put into be heated to 350 ℃ in the nickel plating reactor, the sodium hydroxide that the rich titanium material of 40g 3 (its composition is as shown in table 1) are joined in the reactor with liquid state reacts.Temperature was elevated to 500 ℃ gradually in 2 hours, 500 ℃ of lower maintenances 1 hour.Take out reaction intermediate (sample four in the 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, the intermediate product caking phenomenon can occur; 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 into be heated in the nickel plating reactor 350 ℃ molten state sodium hydroxide;
2, the rich titanium material 1 of 40g desiliconization and 8g sodium peroxide powder evenly are mixed to get compound, again compound are added in the nickel plating reactor of step 1 with molten state sodium hydroxide 350 ℃ of reactions 5 hours; In 1 hour, the nickel plating temperature of reaction kettle is elevated to 450 ℃ gradually afterwards, 450 ℃ of lower maintenances 1 hour, obtains loose molten salt react ion intermediate product (sample five in the 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 be heated to 100 ℃, rich titanium material 1 (rich titanium material 1 forms as shown in table 1) is joined in the reactor, with alkali lye (sodium hydroxide solution) desilication reaction 2 hours occur; Filter afterwards and to get the rich titanium material 1 of desiliconization, the richer titanium material 1 of desiliconization is washed and drying, 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 into be heated in the nickel plating reactor 380 ℃ molten state sodium hydroxide;
2, the rich titanium material 1 of 40g desiliconization and 0.8g sodium peroxide powder evenly are mixed to get compound, again compound are added in the nickel plating reactor of step 1 with molten state sodium hydroxide 350 ℃ of reactions 1 hour; In 1.5 hours, the nickel plating temperature of reaction kettle is elevated to 500 ℃ gradually afterwards, 500 ℃ of lower maintenances 1 hour, obtains loose molten salt react ion intermediate product (sample six in the 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 be heated to 150 ℃, rich titanium material 1 (rich titanium material 1 forms as shown in table 1) is joined in the reactor, with alkali lye (sodium hydroxide solution) desilication reaction 2 hours occur; Filter afterwards and to get the rich titanium material 1 of desiliconization, the richer titanium material 1 of desiliconization is washed and drying, 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 into be heated in the nickel plating reactor 400 ℃ molten state sodium hydroxide;
2, the rich titanium material 1 of 40g desiliconization and 4g sodium peroxide powder evenly are mixed to get compound, again compound are added in the nickel plating reactor of step 1 with molten state sodium hydroxide 400 ℃ of reactions 2 hours; In 1.5 hours, the nickel plating temperature of reaction kettle is elevated to 550 ℃ gradually afterwards, 550 ℃ of lower maintenances 1 hour, obtains loose molten salt react ion intermediate product (sample seven in the table 2) to be measured;
Embodiment 5:
1,40g sodium hydroxide is put into be heated in the nickel plating reactor 400 ℃ molten state sodium hydroxide;
2, the rich titanium material 2 of 40g and 4g sodium peroxide powder evenly are mixed to get compound, again compound are added in the nickel plating reactor of step 1 with molten state sodium hydroxide 400 ℃ of reactions 2 hours; In 1.5 hours, the nickel plating temperature of reaction kettle is elevated to 550 ℃ gradually afterwards, 550 ℃ of lower maintenances 1 hour, obtains loose molten salt react ion intermediate product (sample eight in the table 2) to be measured;
Embodiment 6:
1,40g sodium hydroxide is put into be heated in the nickel plating reactor 400 ℃ molten state sodium hydroxide;
2, the rich titanium material 3 of 40g and 4g sodium peroxide powder evenly are mixed to get compound, again compound are added in the nickel plating reactor of step 1 with molten state sodium hydroxide 400 ℃ of reactions 2 hours; In 1.5 hours, the nickel plating temperature of reaction kettle is elevated to 550 ℃ gradually afterwards, 550 ℃ of lower maintenances 1 hour, obtains loose molten salt react ion intermediate product (sample nine in the 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 be heated to 120 ℃, rich titanium material 1 (rich titanium material 1 forms as shown in table 1) is joined in the reactor, with alkali lye (sodium hydroxide solution) desilication reaction 2 hours occur; Filter afterwards and to get the rich titanium material 1 of desiliconization, the richer titanium material 1 of desiliconization is washed and drying, 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 and rich titanium material 1 contained component:
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 obtains take rich titanium material 1 as raw material is suitable with the small-particle massfraction of the molten salt react ion intermediate product that obtains take titanium slag as raw material, has effectively prevented the phenomenon of reaction caking.

Claims (3)

1. the alkaline process fused salt of the anti-intermediate product caking method of producing titanium dioxide, its step is as follows:
(1) be that 15%~40% sodium hydroxide solution is heated to 100 ℃~150 ℃ with concentration; Rich titanium material joined in the sodium hydroxide solution after the above-mentioned heating carry 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 the desiliconization that step (1) is obtained and sodium peroxide powder evenly are 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 temperature is to react 1~5 hour in 350~400 ℃ the molten state sodium hydroxide; Continue again to be 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;
Wash successively, acid is molten by process for the loose molten salt react ion intermediate product that (4) will obtain, reduce, be hydrolyzed and calcine the titanium dioxide that obtains 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 content of titanium dioxide is 70wt%~85wt% in the described rich titanium material.
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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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101172648A (en) * 2006-10-30 2008-05-07 中国科学院过程工程研究所 Method for clean production of titanium dioxide by using sodium hydroxide
CN100460331C (en) * 2006-02-17 2009-02-11 中国科学院过程工程研究所 Process for clean producing titanium dioxide and potassium hexatitanate wiskers by titanium iron ore or high-titanium dreg sub-molten salt

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100460331C (en) * 2006-02-17 2009-02-11 中国科学院过程工程研究所 Process for clean producing titanium dioxide and potassium hexatitanate wiskers by titanium iron ore or high-titanium dreg sub-molten salt
CN101172648A (en) * 2006-10-30 2008-05-07 中国科学院过程工程研究所 Method for clean production of titanium dioxide by using sodium hydroxide

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
LIU Y M ET AL.: "Decomposition of ilmenite by concentrated KOH solution under atmospheric pressure", 《INTERNATIONAL JOURNAL OF MINERAL PROCESSING》, vol. 81, 31 December 2006 (2006-12-31), pages 79 - 84, XP027881561 *
张晓等: "NaOH熔盐法处理富钛料制备TiO2基础研究", 《冶金研究》, 31 December 2009 (2009-12-31), pages 233 - 238 *
王强等: "熔盐法处理富钛渣制备金红石型TiO2", 《应用化工》, vol. 37, 29 February 2008 (2008-02-29), pages 140 - 143 *
薛天艳: "氢氧化钠熔盐分解高钛渣制备二氧化钛清洁新工艺的研究", 《大连理工大学博士学位论文》, 31 December 2009 (2009-12-31) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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