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Author: Subject: Novel production of titanium from rutile?
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[*] posted on 14-8-2015 at 13:21
Novel production of titanium from rutile?


I was interested in whether it might be possible to react rutile which is is a mixture of SiO2 an TiO2 with hydrogen fluoride to produce TiF4 which is a solid and SiO2 which is a gas, effecting separation.
Then vaporizing the TiF4 at about 400 degrees Centigrade and reacting with H2 to form titanium metal and HF. I have seen a paper for this somewhere, but I can't find it now.
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[*] posted on 14-8-2015 at 14:44


Silicon dioxide is not a gas, at least not at any sane temperatures. Titanium(iv) fluoride will sublime long before quartz even melts.

Silicon tetrafluoride, which is a gas, would form. Did you mean that instead?




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[*] posted on 14-8-2015 at 14:50


Quote: Originally posted by xxxxx  
I was interested in whether it might be possible to react rutile which is is a mixture of SiO2 an TiO2 with hydrogen fluoride to produce TiF4 which is a solid and SiO2 which is a gas, effecting separation.
Then vaporizing the TiF4 at about 400 degrees Centigrade and reacting with H2 to form titanium metal and HF. I have seen a paper for this somewhere, but I can't find it now.


Rutile is the term for one crystalline form of TiO2. Pure Rutile contains no SiO2. The other crystalline form of TiO2 is called Anatase.

It's very unlikely that TiF4 could be reduced with hydrogen. Please provide a reference for that bold assertion.

[Edited on 14-8-2015 by blogfast25]




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[*] posted on 18-8-2015 at 10:33


Yes, I did mean SiF4 is a gas, not SiO2.
I did find this paper on the reduction of TiO2 with H2 at 300 - 500 degrees Centigrade, which would be an even simpler process, if it works, and would support the premise that H2 could reduce TiF4 at a comparable temperature.

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[*] posted on 18-8-2015 at 10:47


Quote: Originally posted by xxxxx  
Yes, I did mean SiF4 is a gas, not SiO2.
I did find this paper on the reduction of TiO2 with H2 at 300 - 500 degrees Centigrade, which would be an even simpler process, if it works, and would support the premise that H2 could reduce TiF4 at a comparable temperature.



The article you cite is about very partial reduction of TiO<sub>2</sub> to TiO<sub>2-x</sub> with x < 1, not to elemental Ti.

The reduction with hydrogen is thermodynamically unfavourable.

Do you really think if reduction with hydrogen was possible it would have been necessary to develop the Kroll process? If so I've got a bridge in Brooklyn you might be interested in! :D


[Edited on 18-8-2015 by blogfast25]




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[*] posted on 19-8-2015 at 15:44


From the Kroll process on Wikipedia I got this:

"Titanium tetrachloride was found to reduce with hydrogen at high temperatures to give hydrides that can be thermally processed to the pure metal."

So I am guessing that it would be general for TiF4.

Even if it is not thermodynamically favorable the reaction could be driven to the right by the solid metal or hydrides precipitating out of the gaseous reaction zone.
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[*] posted on 19-8-2015 at 15:57


Quote: Originally posted by xxxxx  

So I am guessing that it would be general for TiF4.



Good luck processing hot, gaseous TiF<sub>4</sub>! :)

This thread is one of the many wild goose chases that never lead to anything.

[Edited on 20-8-2015 by blogfast25]




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[*] posted on 19-8-2015 at 16:25


Subtle as always blogfast, :)
The problem with Ti as I understand it is that
(1) It has a fairly high reduction potential similar to Al. Just as Al is difficult to reduce by chemical means, so it is with Ti. Any wet chemistry is out.
(2) It has a high melting point which means that any reduction in the liquid phase is problematic.
(3) It has a very stable oxide that passivates the surface effectively. In use this is a good thing since it protects the surface. In any reduction you might propose it makes life a headache.
(4) That oxide also has a high electrical resistance. Meaning that any electrochemical process is difficult.

Ti would be the ideal construction material if only it was easier to produce. There is a significant history of attempts to make it cheaply and easily. It is not like the raw material is difficult to obtain. But all proposed routes have had to face significant engineering hurdles. Not to say that there is no competition for the Kroll process or that all possible routes have been explored fully, but be aware that anything novel faces a difficult uphill battle. Gaseous TiF4 might be only the first of many difficulties. I highly recommend some reading on the subject.

By way of comparison, take a read of the thread on "the trials and tribulations of thorium production". It has been a several year battle to obtain thorium and it is not over yet. The solution is elegant but has required significant engineering to accomplish and really has put itself beyond backyard chemistry. Ti will be much the same via the route you suggest.

That said, it is possible to produce Ti by means of a thermite-type reaction using CaSO4, TiO2 and CaF2 as a flux. (I think there is a fourth ingredient but I forget.) I intend to do this some time. MrHomeScientist has a video of his semi-successful attempts at this and his blog is worth reading.
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[*] posted on 19-8-2015 at 17:00


Quote: Originally posted by j_sum1  


That said, it is possible to produce Ti by means of a thermite-type reaction using CaSO4, TiO2 and CaF2 as a flux. (I think there is a fourth ingredient but I forget.) I intend to do this some time. MrHomeScientist has a video of his semi-successful attempts at this and his blog is worth reading.


It was actually me who developed that method. You can find the full account of my exploits here. But 'thermite titanium' has one major drawback: it's not ductile, so it has no serious commercial applications. Ductile titanium requires strictly anaerobic reduction conditions.

J_sum1: it might not be 'subtle' but preparing and handling purely anhydrous TiF<sub>4</sub> at hobby level is not realistic, to put it mildly. Hell, the less dangerous TiCl<sub>4</sub> is bad enough!

[Edited on 20-8-2015 by blogfast25]




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[*] posted on 19-8-2015 at 17:12


Wow! You came up with that method? Honoured to meet you sir!
All I know is that it is essential to use anhydrous CaSO4 lest you encounter porosity in your product or worse, the steam explosion spreads your efforts over a wide area.

My goal is to get a sizable nugget to add to the element collection. I already have some nice Ti samples but there is something satisfying about a sample you have synthesised yourself. Summer project perhaps.

Thanks for the link. I will have to spend some time browsing your blog at some stage.
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[*] posted on 19-8-2015 at 17:17


Quote: Originally posted by j_sum1  
Wow! You came up with that method? Honoured to meet you sir!
All I know is that it is essential to use anhydrous CaSO4 lest you encounter porosity in your product or worse, the steam explosion spreads your efforts over a wide area.



I've also prepared Ti by the same method but using KClO3 and KNO3 (in fact my first tests used these, the idea for using CaSO4 only came later, as an OTC substitute for chlorate or nitrate).

Yes, the CaSO4 has to be anhydrous, although a bit of moisture is unlikely to cause steam 'explosions'. Using KClO3 generates LOTS of KCl vapour but the reaction runs very well and nicely contained.

[Edited on 20-8-2015 by blogfast25]




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[*] posted on 19-8-2015 at 18:26


Our company is fabricating a pilot titanium plant that is a continuous process, tiny pellets go in one end of the m/c travel on a convayer belt through 900c temperature in vacume and come out as titanium powder, they can make 1 ton a day for a investment of 1.5 million dollars.





[Edited on 20-8-2015 by nux vomica]

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[*] posted on 19-8-2015 at 18:39


What are the tiny pellets? What process is being employed?
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[*] posted on 19-8-2015 at 19:10


I dont know the exact composition of the pellets but there is MgCl2 involved its a continuous kroll process I think, they call them poppy seed cause of there size , they are made in a fluid bed reactor , the titanium powder is useable straight from the m/c because its over 99.8 pure , its going to be used in 3d metal printing m/c I heard.

[Edited on 20-8-2015 by nux vomica]
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[*] posted on 19-8-2015 at 19:30


Very cool. And if the 3-d titanium printing is successful then Ti might just achieve its rightful status as a versatile and widely used engineering material.
But you have three technologies or three processes at least: making the poppy seeds, the reduction process that you are working on and the Ti capable 3-d printers. It will remain low volume until all three of these become mainstream.
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[*] posted on 19-8-2015 at 19:51


I think the kroll process takes 5 stages to get to the powder stage , there is talk of a hybrid powded metal fab prosses where they mold the poppy seed in a shape that will be siniterd into a rough blank for machining , no more wasting time and material making parts from large stock.
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[*] posted on 19-8-2015 at 19:58


Wouldn't that end up being porous? I mean, that is fine if you want a defacto honeycomb structure, but might not be useful in all applications.
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[*] posted on 19-8-2015 at 20:06


They will use heat and pressure to bond it all together like siniterd metal parts.
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[*] posted on 19-8-2015 at 20:26


Japanese Patent JP2005298295

PROBLEM TO BE SOLVED: To provide an easy, industrially efficient method for obtaining titanium oxide comprising a single crystal form from a mixture of titanium oxides with different crystal forms.

SOLUTION: In the method for refining the titanium oxide, the titanium oxide comprising the single crystal form is obtained by subjecting the mixture of titanium oxides with different crystal forms to a treatment with an alkaline hydrogen peroxide solution or sulfuric acid. The refining method includes methods for obtaining anatase type titanium oxide and rutile type titanium oxide by subjecting a mixture of anatase type titanium oxide and rutile type titanium oxide to treatment with the alkaline hydrogen peroxide solution and sulfuric acid, respectively


METAL HALIDE REDUCTION WITH MOLTEN SODIUM/POTASSIUM ALLOY WO1986007097A1.pdf

SYSTEM AND METHOD FOR EXTRACTION AND REFINING OF TITANIUM 20130164167.pdf

A SYSTEM AND METHOD FOR EXTRACTION AND REFINING OF TITANIUM WO2013096893A1.pdf

TREATMENT OF TITANIUM ORES US20120152756A1.pdf

Titanium purification process US3929962.pdf

Process for making titanium metal from titanium ore US4390365.pdf

TREATMENT OF TITANIUM ORES WO2011015845A2.pdf

LOW COST HIGH SPEED TITANIUM AND ITS ALLOY PRODUCTION WO2000023628A2.pdf

Electrolytic recovery system for obtaining titanium metal from its ore US4487677.pdf

Method of producing titanium US7670407B2.pdf



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[*] posted on 19-8-2015 at 20:39


Method of producing titanium US7846232

Method of Producing Titanium US20100173170

Electrochemical process for titanium production EP2322693A1

LOW COST HIGH SPEED TITANIUM AND ITS ALLOY PRODUCTION WO/2004/050928A1

Titanium metal powder produced from titanium tetrachloride using an ionic liquid and high-shear mixing

Low cost high speed titanium and its alloy production US6824585

Method of Producing Titanium US20080145687

Method for electrowinning of titanium metal or alloy from titanium oxide containing compound in the liquid state US7504017



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A few more you can look up at http://www.freepatentsonline.com/

2951021 Electrolytic production of titanium 1960-08-30
2943032 Electrolytic production of titanium 1960-06-28
2880156 Production of metals 1959-03-31
2858189 Production of titanium tetrachloride 1958-10-28
2830940 Production of metals 1958-04-15
2789943 Production of titanium 1957-04-23
2486912 Process for producing titanium tetrachloride 1949-11-01




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[*] posted on 25-8-2015 at 07:14


I would argue that you are over thinking it. Heat TiO2 with C and Cl gas (produced from brine electrolysis). That will give you TiCl4. React that with Mg metal via thermite reaction.

Source: http://www.titaniumexposed.com/titanium-industries.html.




Elements Collected: 19/81 (Excluding all radioactive, using placecard for those)

Any tips or good sources are welcome.
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[*] posted on 25-8-2015 at 09:42


Quote: Originally posted by DalisAndy  
I would argue that you are over thinking it. Heat TiO2 with C and Cl gas (produced from brine electrolysis). That will give you TiCl4. React that with Mg metal via thermite reaction.

Source: http://www.titaniumexposed.com/titanium-industries.html.


I'm not sure who you are addressing here but whoever it is is, I can assure you he/she isn't over thinking anything. Both the production of TiCl<sub>4</sub> from TiO<sub>2</sub>, C and Cl<sub>2</sub> and the subsequent reduction of TiCl<sub>4</sub> by Mg metal are complicated processes, fraught with danger and almost completely outside the capability of nearly 100 % of amateur scientists.

And the reduction of TiCl<sub>4</sub> by Mg metal isn't a 'thermite reaction', not even remotely.

Here's quite a good video of the Kroll process:

https://www.youtube.com/watch?v=oWyrzZh3We0

[Edited on 25-8-2015 by blogfast25]




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