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 PDFInfo
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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
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 150000003839 salts Chemical class 0.000 title claims abstract description 41
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000003513 alkali Substances 0.000 title abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 176
- 239000010936 titanium Substances 0.000 claims abstract description 71
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 71
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000007806 chemical reaction intermediate Substances 0.000 claims abstract description 19
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- 239000013067 intermediate product Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 8
- 239000000543 intermediate Substances 0.000 abstract 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 38
- 235000010215 titanium dioxide Nutrition 0.000 description 22
- 229910052759 nickel Inorganic materials 0.000 description 19
- 238000007747 plating Methods 0.000 description 19
- 230000036647 reaction Effects 0.000 description 8
- 239000002893 slag Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical class [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
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
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.
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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 |
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