# Patent

## Title
Method for preparing sponge titanium from sodium fluotitanate by aluminothermic reduction

## Abstract

The invention provides a method for preparing sponge titanium from sodium fluotitanate by aluminothermic reduction, comprising the following steps: a reaction step: aluminum and zinc are mixed under a vacuum state, and sodium fluotitanate is then added into the mixture for reaction; a separation step: the product resulting from the complete reaction stands still and is then introduced with inert gas, and NaF and AlF3 in upper-layer liquid phase are extracted; and a distillation step: Zn in the remaining product Zn—Ti is distilled out under a vacuum state, wherein the mass ratio of the aluminum to the zinc is 1:2 to 1:10.

## Background
TECHNICAL FIELD OF THE INVENTION
The invention relates to a method for preparing sponge titanium from sodium fluotitanate by aluminothermic reduction, more particularly to a method for preparing sponge titanium from sodium fluotitanate by aluminothermic reduction, which has the advantages of low cost, high efficiency and continuous operation.
BACKGROUND OF THE INVENTION
The sponge titanium production processes that have been well-known domestically and overseas mainly include: metallothermic reduction process, electrolysis process, direct thermolysis process and electronically mediated reaction process, etc., and the typical raw materials include titanium chloride (TiCl4, TiI4), titanium oxide (TiO2) and titanium compounds (K2TiF6, Na2TiF6). Among various sponge titanium production processes, the traditional titanium tetrachloride aluminum-magnesium thermal reduction process (Kroll process), though mature and industrialized, has complex process and high cost and is pollutant to environment, thus limiting its further application and popularization. The method for preparing sponge titanium from sodium fluotitanate by metallothermic reduction process is a production method which is continuous, low in cost and high in efficiency and can settle plenty of problems in the traditional process efficiently, however, there are only a few domestic and overseas reports, and so far, a successful industrialization case has not been found yet.
SUMMARY OF THE INVENTION
The invention provides a method for preparing sponge titanium from sodium fluotitanate by aluminothermic reduction,
Proposal 1: method for preparing titanium from sodium fluotitanate by aluminothermic reduction process:
The equation related is as follows: 3Na2TiF6+4Al=3Ti+6NaF+4AlF3 
Proposal 2: method for preparing sponge titanium from sodium fluotitanate by magnesiothermic reduction process:
The equations related are as follows:

3Na2TiF6+4Al=3Ti+6NaF+4AlF3 

Na2TiF6+2Mg=Ti+2MgF2+2NaF

The method comprises the following steps:
a reaction step: aluminum and zinc are mixed under a vacuum state, and the mixture is then reacted with sodium fluotitanate;
a separation step: inert gas is introduced after complete reaction, and NaF and AlF3 in upper-layer liquid phase are extracted;
and a distillation step: Zn in the remaining product is distilled out under a vacuum state;
wherein the mass ratio of the aluminum to the zinc is 1:2 to 1:10.
Preferably, the reaction temperature in the reaction step is 1000° C.
Preferably, the liquid phase extraction temperature in the separation step is 1050° C.
Preferably, the distillation temperature in the distillation step is 1000° C.
The invention further provides another method for preparing sponge titanium from sodium fluotitanate by aluminothermic reduction, comprising the following steps:
a reaction step: aluminum, zinc and magnesium are mixed under a vacuum inert gas introduction condition, and sodium fluotitanate is then added into the mixture for reaction;
a separation step: inert gas is introduced after complete reaction, and NaF, AlF3 and MgF2 in upper-layer liquid phase are extracted;
and a distillation step: Mg and Zn in the remaining product are distilled out under a vacuum state;
wherein the mass ratio of the aluminum to the zinc to the magnesium is 18:108:1 to 1:6:1.
Preferably, the reaction temperature in the reaction step is 950° C.
Preferably, the liquid phase extraction temperature in the separation step is 1050° C.
Preferably, the distillation temperature in the distillation step is 1100° C.
Preferably, the vacuum degree in the distillation step is at least 1 MPa.
The invention has the advantages that: by adopting the technical proposal discussed above, the method is short in technological flow, low in cost, harmless and environment-friendly compared with traditional processes, and rivals the prior art for the reduction rate and yield of sponge titanium, furthermore, the final resultant sponge titanium can be directly applied to technological production, further saving resources and cost.


DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The preferred embodiments of the invention will be described below in further details:
Proposal 1: method for preparing sponge titanium from sodium fluotitanate by aluminothermic reduction process based on zinc matrix:
The equation related is as follows: 3Na2TiF6+4Al=3Ti+6NaF+4AlF3 
Embodiment 1: 36 g aluminum and 72 g zinc are mixed under a vacuum state, and the mixture is then reacted with 240 g sodium fluotitanate at 1000° C.;
the product stands still after complete reaction and is then introduced with inert gas, and NaF and AlF3 liquid phases in upper layer are extracted at 1050° C.;
under the state of high vacuum and 1000° C., Zn in the remaining product is distilled out to obtain 45.01 g sponge titanium; the titanium content in the product is 87.76% and the reduction rate is 82.3%.
Embodiment 2: 36 g aluminum and 144 g zinc are mixed under a vacuum state, and the mixture is then reacted with 240 g sodium fluotitanate at 1000° C.;
the product stands still after complete reaction and is then introduced with inert gas, and NaF and AlF3 liquid phases in upper layer are extracted at 1050° C.;
under the state of high vacuum and 1000° C., Zn in the remaining product is distilled out to obtain 48.22 g sponge titanium; the titanium content in the product is 92.07% and the reduction rate is 92.5%.
Embodiment 3: 36 g aluminum and 216 g zinc are mixed under a vacuum state, and the mixture is then reacted with 240 g sodium fluotitanate at 1000° C.;
the product stands still after complete reaction and is then introduced with inert gas, and NaF and AlF3 liquid phases in upper layer are extracted at 1050° C.;
under the state of high vacuum and 1000° C., Zn in the remaining product is distilled out to obtain 49.04 g sponge titanium; the titanium content in the product is 92.29% and the reduction rate is 95%.
Embodiment 4: 36 g aluminum and 288 g zinc are mixed under a vacuum state, and the mixture is then reacted with 240 g sodium fluotitanate at 1000° C.;
the product stands still after complete reaction and is then introduced with inert gas, and NaF and AlF3 liquid phases in upper layer are extracted at 1050° C.;
under the state of high vacuum and 1000° C., Zn in the remaining product is distilled out to obtain 50.26 g sponge titanium; the titanium content in the product is 90.92% and the reduction rate is 95.2%.
Embodiment 5: 36 g aluminum and 360 g zinc are mixed under a vacuum state, and the mixture is then reacted with 240 g sodium fluotitanate at 1000° C.;
the product stands still after complete reaction and is then introduced with inert gas, and NaF and AlF3 liquid phases in upper layer are extracted at 1050° C.;
under the state of high vacuum and 1000° C., Zn in the remaining product is distilled out to obtain 49.7 g sponge titanium; the titanium content in the product is 92.14% and the reduction rate is 95.4%.







TABLE 1







Test Data















Actual





Addition Amount of
Theoretical
Rough
Ti Content



Raw Materials, g
Amount of
Titanium
In Product,
Reduction














Embodiment
Na2TiF6
Al
Zn
Ti, g
Product, g
%
Rate, %

















1
240
36
72
48
45.01
87.76
82.3


2
240
36
144
48
48.22
92.07
92.5


3
240
36
216
48
49.4
92.29
95.0


4
240
36
288
48
50.26
90.92
95.2


5
240
36
360
48
49.7
92.14
95.4





Reduction Rate (%) = (Actual Sponge Titanium Product × Ti Content In Product)/Theoretical Amount of Ti






Proposal 2: method for preparing sponge titanium from sodium fluotitanate by aluminothermic reduction process based on zinc-magnesium matrix:
The equations related are as follows:

3Na2TiF6+4Al=3Ti+6NaF+4AlF3 

Na2TiF6+2Mg=Ti+2MgF2+2NaF

Embodiment 6: 36 g aluminum, 216 g zinc and 36 g magnesium are mixed under a vacuum inert gas introduction condition, and the mixture is then reacted with 240 g sodium fluotitanate at 950° C.;
the product stands still after complete reaction and is then introduced with inert gas, and NaF, MgF2 and AlF3 liquid phases in upper-layer liquid phase are extracted at 1050° C.;
under the state of high vacuum and 1100° C., Mg and Zn in the remaining product are distilled out to obtain 48.36 g sponge titanium; the titanium content in the product is 92.7% and the reduction rate is 93.4%.
Embodiment 7: 36 g aluminum, 216 g zinc and 18 g magnesium are mixed under a vacuum inert gas introduction condition, and the mixture is then reacted with 240 g sodium fluotitanate at 950° C.;
the product stands still after complete reaction and is then introduced with inert gas, and NaF, MgF2 and AlF3 liquid phases in upper-layer liquid phase are extracted at 1050° C.;
under the state of high vacuum and 1100° C., Mg and Zn in the remaining product are distilled out to obtain 47.8 g sponge titanium; the titanium content in the product is 92.78% and the reduction rate is 92.4%.
Embodiment 8: 36 g aluminum, 216 g zinc and 9 g magnesium are mixed under a vacuum inert gas introduction condition, and the mixture is then reacted with 240 g sodium fluotitanate at 950° C.;
the product stands still after complete reaction and is then introduced with inert gas, and NaF, MgF2 and AlF3 liquid phases in upper-layer liquid phase are extracted at 1050° C.;
under the state of high vacuum and 1100° C., Mg and Zn in the remaining product are distilled out to obtain 47.91 g sponge titanium; the titanium content in the product is 94.88% and the reduction rate is 94.7%.
Embodiment 9: 36 g aluminum, 216 g zinc and 2 g magnesium are mixed under a vacuum inert gas introduction condition, and the mixture is then reacted with 240 g sodium fluotitanate at 950° C.;
the product stands still after complete reaction and is then introduced with inert gas, and NaF, MgF2 and AlF3 liquid phases in upper-layer liquid phase are extracted at 1050° C.;
under the state of high vacuum and 1100° C., Mg and Zn in the remaining product are distilled out to obtain 46.3 g sponge titanium; the titanium content in the product is 98.79% and the reduction rate is 95.3%.







TABLE 2







Test Data















Actual





Addition Amount of
Theoretical
Rough
Ti Content



Raw Materials, g
Amount of
Titanium
In Product,
Reduction















Embodiment
Na2TiF6
Al
Zn
Mg
Ti, g
Product, g
%
Rate, %


















6
240
36
216
36
48
48.36
92.7
93.4


7
240
36
216
18
48
47.8
92.78
92.4


8
240
36
216
9
48
47.91
94.88
94.7


9
240
36
216
2
48
46.3
98.79
95.3









Further detailed descriptions are made to the invention with reference to the preferred embodiments in the above discussions and it could not be considered that the embodiments of the invention are limited to these descriptions only. Many simple derivations or alternations could be made without departing from the concept of the invention by ordinary skilled in this art to which the invention pertains, and shall be contemplated as being within the scope of the invention.

## Claims

1. A method for preparing sponge titanium from sodium fluotitanate by aluminothermic reduction, characterized in that, the method comprises the following steps:
a reaction step: aluminum and zinc are mixed under a vacuum state, and sodium fluotitanate is then added into a mixture for reaction;
a separation step: inert gas is introduced after complete reaction, and NaF and AlF3 in upper-layer liquid phase are extracted; and
a distillation step: Zn in a remaining product is distilled out under a vacuum state;
wherein a mass ratio of the aluminum to the zinc is 1:2 to 1:10.

2. The method for preparing sponge titanium according to claim 1, wherein a reaction temperature in the reaction step is 800° C.

3. The method for preparing sponge titanium according to claim 1, wherein a liquid phase separation temperature in the distillation step is 1050° C.

4. The method for preparing sponge titanium according to claim 1, wherein a distillation temperature in the distillation step is 1000° C.

5. The method for preparing sponge titanium according to claim 1, wherein a vacuum degree in the distillation step is 1 MPa.

6. A method for preparing sponge titanium from sodium fluotitanate by aluminothermic reduction, characterized in that, the method comprises the following steps:
a reaction step: aluminum, zinc and magnesium are mixed under a vacuum inert gas introduction condition to form a mixture, and sodium fluotitanate is then added into the mixture for reaction;
a separation step: inert gas is introduced after complete reaction, and NaF, AlF3 and MgF2 in upper-layer liquid phase are extracted; and
a distillation step: Mg and Zn in a remaining product are distilled out under a vacuum state;
wherein a mass ratio of the aluminum to the zinc to the magnesium is 18:108:1 to 1:6:1.

7. The method for preparing sponge titanium according to claim 6, wherein a reaction temperature in the reaction step is 950° C.

8. The method for preparing sponge titanium according to claim 6, wherein a liquid phase separation temperature in the distillation step is 1050° C.

9. The method for preparing sponge titanium according to claim 6, wherein a distillation temperature in the distillation step is 1100° C.

10. The method for preparing sponge titanium according to claim 6, wherein a vacuum degree in the distillation step is 1 MPa.