Information
-
Patent Grant
-
6824585
-
Patent Number
6,824,585
-
Date Filed
Tuesday, December 3, 200221 years ago
-
Date Issued
Tuesday, November 30, 200419 years ago
-
Inventors
-
Original Assignees
-
Examiners
Agents
- Liner, Yankelevitz, Sunshine & Regenstreif, LLP
-
CPC
-
US Classifications
Field of Search
US
- 075 1019
- 075 1021
- 420 590
-
International Classifications
-
Abstract
A method for refining a titanium metal containing ore such as rutile or ilmenite or mixtures to produce titanium ingots or titanium alloys and compounds of titanium involves production of titanium tetrachloride by processing the ore with a chlorinating procedure and removing various impurities by a distillation or similar procedures to form a relatively pure titanium tetrachloride. Thereafter, the titanium tetrachloride is introduced continuously into a reactor at the focal point of a plasma under atmospheric pressures of inert gas along with molten metallic reductant for the initial reduction of gas phase titanium tetrachloride into molten titanium drops which are collected in a set of skulled crucibles. Thereafter, further processing is carried out at atmospheric pressures in under inert gas where the titanium is heated by plasma guns to maximize titanium purity and, in a final optional stage, alloying compounds are added under the same controlled environment and high temperature conditions.
Description
BACKGROUND OF THE INVENTION
The present invention relates to processing of titanium bearing ores and more specifically to an improved process for low cost and high speed extraction, production and refining of titanium and titanium alloys.
The present invention is a further improvement of Dr. Joseph's prior patents, U.S. Pat. No. 5,503,655 issued Apr. 2, 1995 and U.S. Pat. No. 6,136,060 issued Oct. 24, 2000, the disclosures of which are incorporated herein by reference. The first patent describes a process in which a liquid slag containing titanium dioxide is reduced to a mixture of titanium dioxide and iron; the iron is then separated out to produce about 95% pure titanium dioxide. In subsequent processing, the partially pure titanium dioxide is melted and processed to remove any residual iron and other impurities to form titanium dioxide powder.
The second patent discloses a process for production of titanium and titanium alloys using a reductive process under vacuum. The reduction step is carried out by molten metallic sodium, whereas in the present disclosure, the reductant could be any of magnesium, sodium, hydrogen, lithium, potassium, rubidium, cesium, francium, beryllium, calcium, strontium, barium or radium.
Canadian Patent No. 549299 to Gross et al. discloses the production of titanium metal by decomposing titanium halides under controlled temperatures. U.S. Pat. No. 4,793,854 to Shimotori et al. produces titanium by electrolysis of molten titanium slat followed by purification under high vacuum conditions.
A large number of prior art references describe various aspects of refining metals and particularly refining titanium. Great Britain Patent No 809,444 , U.S. Pat. No. 3,546,348 to DeCorso and U.S. Pat. No. 3,764,297 to Coad et al. describe the use of electric arcs under vacuum to melt metals. U.S. Pat. No. 2,997,760 to Hanks et al. describes melting metals under vacuum to remove volatile impurities. U.S. Pat. No. 3,237,254 (Hanks et al.), U.S. Pat. No. 3,342,250 (Treppschuh et al.) and U.S. Pat. No. 3,343,828 (Hunt) describe melting metals under vacuum with electron beam guns. U.S. Pat. No. 3,494,804 to Hanks et al. also describes vacuum heating with an electron beam gun and discloses the idea of using a “skull” to prevent contamination of a melt by the walls of a crucible. U.S. Pat. No. 4,027,722 to Hunt and U.S. Pat. No. 4,488,902, also to Hunt, describe additional details of electron beam based processes U.S. Pat. No. 3,210,454 to Morley and U.S. Pat. No. 4,838,340 to Entrekin et al. disclose the use of plasma torches to maintain metals in a molten state.
Titanium, especially some of its alloys such as titanium-aluminum-vanadium (Ti-6Al-4V) are important because they are ideally suited for a wide variety of applications in the aerospace, aircraft, military, and automotive fields. Titanium and its alloys, including that mentioned, combine the attractive properties of high strength and light weight with resistance to corrosion and stability under high temperatures. For example, titanium is very strong but only about 60% as dense as iron and parts made of titanium will weigh only 60% as much as the same part made of steel. While titanium is relatively easy to fabricate, there are numerous impediments to its widespread use. As demonstrated by the above cited references, refining titanium is energy intensive and involves significant costs in handling due to the need for toxic chemicals for its refining. Furthermore, in refining titanium, there may also be a high cost involved in disposing of the toxic byproducts produced in the refinery process.
Thus, it is a primary object of this invention to provide an improved and cost effective process for the production of high purity titanium and its alloys from a starting ore containing titanium, preferably in an oxide form.
Another object of the present invention is the conversion of a titanium bearing ore such as rutile or ilmenite to an essentially pure titanium tetrachloride followed by reduction to titanium which is then followed by refining of the titanium to a pure state and optionally alloying the same.
These objects and features of the present invention will become more apparent from the following detailed description which provides detailed information regarding both the process and apparatus and which is for purposes of illustration and should not be construed as a limitation on the present invention.
SUMMARY OF THE INVENTION
The present invention is a process for refining titanium containing ore and more particularly a sequence which involves converting the titanium ore to titanium tetrachloride, the latter continuously reduced to titanium metal in a plasma reactor in the presence of a metallic reductant under inert gas at atmospheric pressures. The resulting titanium is continuously fed and further processed to a relatively high purity while molten and under inert gas at atmospheric pressures followed optionally by alloying with other metals such as aluminum and vanadium.
First, titanium tetrachloride is produced from the ore and many of the impurities such as iron chloride and vanadium are removed in this step resulting in an intermediate with less than four parts per billion.
Then the titanium tetrachloride is reduced with molten magnesium or sodium, or alternatively with lithium, potassium, rubidium, cesium, francium, beryllium, calcium, strontium, barium or radium under inert gas at atmospheric pressures in a plasma reactor preferably using a hydrogen plasma. Thereafter, the molten titanium is processed in the presence of inert gas under atmospheric pressures (approximately 760 Torr ) and elevated temperatures. During this processing alloying optionally may take place.
An appreciation of the other aims and objectives of the present invention and an understanding of it may be achieved by referring to the accompanying drawings and description of a preferred embodiment.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1
is a diagrammatic illustration of the general steps for production of titanium alloy from titanium ore in accordance with the present invention;
FIG. 2
is a process flow sheet for the production of titanium tetrachloride in accordance with this invention;
FIG. 3
is a sketch of the plasma reactor for the reduction of titanium tetrachloride in accordance with this invention;
FIG. 4
is an illustration of the titanium tetrachloride supply system used with the plasma reactor of
FIG. 3
in accordance with this invention; and
FIG. 5
is an illustration of the apparatus for the steps of titanium alloying and purification following reduction.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
While the present invention is described herein with reference to illustrative embodiments for particular applications, it should be understood that the invention is not limited thereto. Those having ordinary skill in the art and access to the teachings provided herein will recognize additional modifications, applications, and embodiments within the scope thereof and additional fields in which the present invention would be of significant utility.
The process previously patented by Dr. Joseph utilizes sodium as a reductant, and produces high-grade titanium metal from titanium tetrachloride under vacuum conditions. In the improved process, magnesium, lithium, potassium, rubidium, cesium, francium, beryllium, calcium, strontium, barium or radium can also be used as the reductant instead of sodium. Because of cost and toxicity sodium or magnesium are preferred.
The choice of reductant between sodium and magnesium can be based on:
Suitability for reaction—thermodynamics and kinetics;
Cost of the reductant;
Ease of delivery or handling;
Disengagement of the products; and
Safety.
The following table of physical characteristics is useful for making this selection:
|
Component
Melting Point ° C.
Boiling Point ° C.
|
|
|
Na
98
882
|
Mg
650
1105
|
Ti
1667
3285
|
TiCl
4
−25
137
|
NaCl
801
1465
|
MgCl
2
714
1418
|
TiCl
3
730
750
|
|
Thermodynamic analysis shows no real benefit of sodium over magnesium as reductant as far as can be discerned from equilibrium considerations. From the Kroll and Hunter processes (see
Hawley's Condensed Chemical Dictionary
(11th ed. 1987)) it appears that any of the reduction reactions is possible and no data have been found to support a preference for one reductant over the others.
Kinetic data in a publication by Tisdale et al. give some useful indicators that the reaction of titanium tetrachloride with magnesium metal is sufficiently fast in the vapor phase at 1150-1250° C. to preclude concerns over excessively long reaction times for a continuous process. “Vapor phase titanium production”, D. G. Tisdale, J. M. Toguri, and W. Curlook, CIM Bulletin, March 1997:159-163.
The cost of the reductant metal is a major consideration. Sodium and magnesium have similar atomic weights, but on a molar basis only one half as much magnesium is required. Therefore, there is less reductant to heat up to reaction temperatures with magnesium, thus lowering energy input. The fact that magnesium is currently in abundance and roughly half the cost of the sodium per pound or kilogram is an additional point in its favor.
Both magnesium and sodium are flammable and great care should be exercised in their handling. Sodium melts at a much lower temperature: so maintaining feed systems in the molten state is simpler. It is however more reactive with water and has to be stored under paraffin, as it will oxidize rapidly in air. Magnesium on the other hand can be delivered as ingots or “bricks” and is stable at room temperature. The products of the reactions have their respective advantages and disadvantages. The reactor has to be held above the condensation point of the reactants and products to enable good separation of the products. Reference to the database of physical properties allows one to estimate optimal reaction temperatures for any set of reactants.
To evacuate the process stream of product chloride and metal requires an operating temperature of at least 1465° C. Alternatively, sufficient flushing gas such as argon must be provided to assure that the walls of the vessel are above the dew point determined by the vapor pressure of any residual chloride or metal in this gas stream. While sodium metal is clearly more volatile than magnesium and therefore should be easily stripped from the melt at high temperatures, it actually has a marginally higher boiling point than magnesium chloride.
Development of a low cost, high speed, continuous or near-continuous process for producing high-grade titanium metal which is essentially pure, represents a great improvement in the field of metallurgy, and satisfies a long felt need for a commercial process with a high potential capacity, but which is less labor intensive. Further, any component which will make the process even more cost effective and efficient is beneficial.
Referring to the drawings which illustrate a preferred embodiment of this invention, the general flow diagram of
FIG. 1
shows the general sequence of steps. The first step
10
includes the formation of essentially pure titanium tetrachloride (TiCl
4
) from a starting titanium bearing ore such as rutile or ilmenite or mixtures of ores. Rutile is an ore containing titanium and oxygen (TiO
2
) while ilmenite is an ore containing iron, titanium and oxygen (TiO
2
Fe
2
O
3
). For the purposes of this invention, any titanium containing ore or mixtures of ores preferably with oxygen, with or without other metals, may be used as the starting ore. The titanium ore is dressed in a conventional manner to produce an ore concentrate. In effect, the first general step
10
includes conversion of the starting ore to titanium tetrachloride preferably having less than 4 parts per billion of metallic impurities since the latter are difficult to remove in later processing. Generally, this step includes reacting chlorine with the ore to form titanium tetrachloride.
The next general step
12
involves conversion of the essentially pure titanium tetrachloride to titanium metal by plasma arc treatment in a chemical reduction process resulting in the reduction of the TiCl
4
to titanium and 2(XCl
2
), where X is a divalent reductant such as beryllium, magnesium, calcium, strontium, barium or, radium, or 4(YCl), where Y is a monovalent reductant such as lithium, sodium, potassium, rubidium, cesium or francium. In this second general step
12
, a plasma reactor
40
(
FIG. 3
, to be described below) is used in which magnesium, sodium, lithium, potassium, rubidium, cesium, francium, beryllium, calcium, strontium, barium or radium is melted if necessary, and is injected continuously into a reaction chamber with heated titanium tetrachloride resulting in the formation of titanium metal and 2(XCl
2
), or 4(YC1), depending on the choice of reductant.
The third general step
15
involves processing the titanium from the second step under a controlled environment in which the titanium is heated and kept molten by plasma guns
130
(
FIG. 5
) and at controlled environment conditions resulting in a very pure titanium metal which can be cast into ingots
125
or converted to an aluminum-vanadium alloy while the titanium metal is in liquid form. In this third general step
15
, dissolved gases such as hydrogen and chlorine are removed by out gassing. Since out gassing generally cannot remove oxygen, nitrogen and carbon, the entire process takes place at atmospheric pressures in an inert gas environment to flush out these impurities.
FIG. 2
illustrates the details of the process involved in the first general step
10
shown in
FIG. 1
for the production of titanium tetrachloride from a suitable ore. As shown, a titanium and oxygen bearing ore
17
such as rutile or ilmenite or mixtures, is dressed
16
with petroleum coke
18
and chlorine gas
19
and processed in a chlorination step
20
at an elevated temperature. After chlorination
20
, the mixture contains titanium tetrachloride and iron chloride and other impurities which are separated out in a separation and condensation step
22
. The impurities are separated at
24
resulting in the formation of a crude titanium tetrachloride as shown at
25
.
The crude titanium tetrachloride
25
is then processed at
28
to remove vanadium, as shown at
29
, followed by distillation at
30
, again at an elevated temperature, to remove silicon chloride as shown at
32
. After removal of vanadium
29
and silicon chloride
32
, the concentration of impurities is preferably below about 4 parts per billion. The result is essentially pure titanium tetrachloride (TiCl
4
).
Thus, the first detail step within the first general step
10
involves ore dressing
16
to produce an ore concentrate. The second detail step involves chlorination
20
of the ore concentrate to form crude metal
25
. This second detail step involves two separate sub-steps:
(a) Conversion of the ore concentrate to crude TiCl
4
25
. This is done in the chlorination process
20
and is represented by the reaction (where “s” indicates solid and “g” indicates gas):
TiO
2
(
s
)+2Cl
2
(
g
)+2C(
s
)→TiCl
4
(
g
)+2CO(
g
)
The chlorination process
20
is carried out in a chlorinator. With rutile ores, in the case of ilmenite, iron chloride is also formed and has to be removed as a separate step
22
.
(b) The crude TiCl
4
25
is further purified
28
,
30
to remove vanadium
29
and silicon
32
impurities. The final product is pure TiCl
4
. All the metallic impurities have to be removed, in this step since they cannot be removed subsequently.
The next general step
12
is the plasma arc reduction of titanium tetrachloride in the presence of gaseous hydrogen for the plasma and molten metallic magnesium, sodium, lithium, potassium, rubidium, cesium, francium, beryllium, calcium, strontium, barium or radium reductant to produce titanium and 2(XCl
2
), where X is divalent reductant such as beryllium, magnesium, calcium, strontium, barium or, radium, or 4(YCl), where Y is a monovalent reductant such as lithium, sodium, potassium, rubidium, cesium or francium according to the equation:
TiCl
4
+2X→Ti+2(XCl
2
)
where X is beryllium, magnesium, calcium, strontium, barium or, radium, or
TiCl
4
+4Y→Ti+4(YCl)
where Y is lithium, sodium, potassium, rubidium, cesium or francium.
The plasma reduction step
12
may be carried out in an apparatus
40
illustrated in FIG.
3
and referred to as a plasma reactor utilizing an inert atmosphere of argon or helium. The reactor
40
includes basically two zones both of which contain inert gas at atmospheric pressures. The upper zone
41
contains the plasma arc in which the reduction occurs, and the lower zone
43
is the input side of the refining and alloying apparatus (step
15
of
FIG. 1
; illustrated in
FIG. 5
) also at a controlled pressure of about 760 Torr, as are later stages. The two zones
41
,
43
are separated by a flange
45
, from which is suspended a collar
107
holding collector crucible
110
(to be described).
The top portion
50
of the reactor
40
includes an injection port
51
through which the reductant metallic magnesium, sodium, lithium, potassium, rubidium, cesium, francium, beryllium, calcium, strontium, barium or radium (herein after, metallic reductant) is introduced into the reactor
40
. Surrounding the top portion
50
is a graphite block
54
for high temperature resistance.
The metallic reductant is heated and melted (if necessary) by a plurality of plasma torches
52
arranged at a tilted down 60 degree angle and disposed circumferentially at 120 degrees from each other, two being shown at
52
, and located vertically below the metallic reductant injection port
51
. The metallic reductant is introduced at the focal point of the torches
52
, as illustrated diagrammatically as “*”. Located vertically below the torches
52
is a titanium tetrachloride injection port
55
such that the molten metallic reductant comes into intimate contact with the injected titanium tetrachloride and is intermixed therewith for reaction. A constant stream of inert gas (such as argon or helium) and hydrogen for the plasma is introduced into zone
41
through ports such as ports
53
that can be coaxial with the torches
52
. Located vertically below the titanium tetrachloride injection port
55
is a dual reactor section
57
,
58
, including a graphite liner
54
a
, for reaction between the molten metallic reductant and the heated titanium tetrachloride. Graphite rings
56
are used for temperature resistance, and within the reactor sections
57
,
58
are temperature resistant graphite columns
56
a
. Vertically below the reactor sections
57
,
58
is a separator section
59
through which the 2(XCl
2
) or 4(YCl) is withdrawn through an exhaust system (not shown). Titanium metal in the form of molten titanium droplets passes from the separator
59
into region
43
and the crucible
110
which links the reactor
40
to the refining apparatus
100
.
A titanium tetrachloride supply system
60
for titanium tetrachloride injection into the plasma reactor
40
is illustrated diagrammatically in FIG.
4
. The supply system
60
includes a sealed titanium tetrachloride reservoir tank
62
which receives relatively pure titanium tetrachloride from the distillation step
30
of FIG.
2
. The tank
62
includes an inert gas supply system
63
for argon or helium gas, for example, supplied from a pressurized gas source such as an argon or helium gas tanks (not shown) through a two-stage pressure regulator. The tank
62
also includes an in-line pressure relief valve
66
which may vent to a hood and a pressure gage
64
to monitor the internal pressure of the tank
62
. The tank
62
also includes an outlet system
65
whose output is connected to a titanium tetrachloride-boiler vessel
70
.
The outlet system
65
includes a series of manually operated valves
71
,
72
and Swagelok® unions
74
for disconnecting the reservoir tank
62
from the remainder of the system
60
. Down stream of the valves
71
,
72
is a flowmeter
75
controlled by a manually operated valve
77
. The outlet
78
of the flowmeter is connected as the inlet at the bottom of the boiler vessel
70
. The boiler vessel
70
itself includes an inner heater section
80
and an outer titanium tetrachloride heater chamber
82
. The heater chamber
82
surrounds the heater section
80
and is sealed relative thereto. The titanium tetrachloride is fed into the heater chamber
82
under a blanket of argon or helium gas.
The heater section
80
includes an immersion heater assembly
85
which includes an immersion heater device
86
which extends into the heater section
80
and which is supported at the top of the tank
70
by means well known in the art. The immersion heater
86
may be any one of the immersion heaters well known in the art. As shown, the immersion heater
86
is spaced from the wall forming the heater chamber
82
and is preferably filled with a heat transfer fluid for effective transmission of heat from the immersion heater
86
to the wall of the chamber
82
.
Surrounding the outer wall of the tank
70
is a heater tape unit
90
connected to a source of electrical power through a junction
91
. Mounted at the top of the tank
70
and communicating with the heater chamber
82
is an in-line pressure relief valve
92
which vents to a hood. The tank
70
and the heater chamber
82
include an outlet
93
. The exit side
95
of the outlet forms the inlet injection nozzle for the injector
55
of the plasma reactor
40
of FIG.
3
. The outlet system
93
from tank
70
includes heating tapes
96
supplied with power from a junction
97
. Downstream of the tapes
96
is an argon or helium purge valve
98
controlled by a three way electrically operated solenoid valve
99
.
The apparatus
100
for refining and/or alloying the titanium metal output from the device of
FIG.3
is shown in FIG.
5
. The apparatus
100
includes multiple chambers
102
,
104
separated into two general zones by a gate valve
105
(as shown). The zone
102
on the left contains an input through the collar
107
from the titanium reduction plasma apparatus
43
(FIG.
3
), and additional plasma gun
108
for heating the titanium carrying ceramic vessel or crucible
110
and the molten titanium as it is produced. Zone
102
is at atmospheric pressure, e.g. 760 Torr, and receives molten titanium, in the form of titanium droplets, from the section
43
of the reactor
40
. The liquid titanium droplets entering section
102
through the collar
107
are heated by the plasma gun
108
and the gun output impinges on a molten titanium pool in the ceramic vessel or crucible
110
provided with a water cooled copper insert (
FIG. 3
) on which titanium has previously solidified on the crucible walls to form a skull or solidified titanium coating
114
of essentially pure titanium metal. The titanium skull
114
prevents the molten titanium from contacting the bare walls of the crucible
110
which would result in reaction with resultant contamination of the titanium. Thus, incoming molten titanium contacts the solid titanium coating
114
of the crucible
110
, the coating
114
being maintained solid by the water cooled insert in the ceramic crucible
110
.
The zone
104
on the right of zone
102
is also at 760 Torr (atmospheric pressure) and contains a hearth
116
on which a titanium skull
118
has been previously formed. The copper hearth
1
16
may be cooled by interior water cooling pipes, not shown. There are multiple sections in this zone: the first section
120
at atmospheric pressure; the next and successive section
122
is at the same pressure as the first section, e.g., 760 Torr, the final section
122
including the cold hearth
116
having a lip
123
over which the molten metal flows to be cast into a retractable ingot mold
125
. Plasma guns
130
keep the titanium molten in each of these sections. Alloying elements can be introduced into the second section
122
operating at 760 Torr so that an alloy, as previously described, may be formed. To form the alloy mentioned, powdered aluminum in an amount of 6% by weight and powdered vanadium in an amount of 4% by weight are introduced into the chamber
122
. The flow rate through the sections
120
,
122
has to be a constant if the proper amount of alloys are to be introduced to meet alloy specifications.
There may be one to three ceramic vessels or crucibles
110
,
110
a
with titanium skulls
114
,
114
a
, formed as described. The ceramic crucibles
110
,
110
a
are positioned and supported on a table
135
which can be rotated 180 degrees so that the crucible
110
,
110
a
full of molten titanium can be swung from zone
102
into the left part of zone
104
(of section
120
). There is also a tilt mechanism
138
in the left position of zone
104
(of section
120
) which permits the molten titanium to be gradually poured over the sloping hearth
116
and flow from left to right and be cast into an ingot in mold
125
. As shown, each of sections
120
and
122
includes exit ports
140
for degassing control. These zones are constantly purged by inert gas (such as argon or helium ) entering through input ports
142
.
With this design, the reduced titanium metal collection rate in zone
102
is independent of the flow rate on the hearth
116
in zone
104
. Since two vastly different technologies are operating in the zones
102
and
104
, it is almost impossible to match the reduction rate in the right zone
102
to the flow rate on the hearth
116
in the left zone
104
.
In operation, the first step is to turn on the plasma guns
108
and melt the surface of the skull
114
in zone
102
. In the next step, the plasma reduction reactor is brought into operation, and the newly reduced titanium falls onto the molten surface of the skull
114
to fill it up.
Once the skull
1
14
is filled, the succeeding step is to open the gate valve
105
between zones
102
and
104
and swing the crucible
110
full of molten titanium to zone
104
while an empty skull
114
swings to position in zone
102
. Alternate arrangements as may be apparent to those skilled in the art may also be used for this operation. The next step is to close the gate valve
105
isolating the two zones
102
and
104
.
Following the closure of the gate valve
105
, the plasma guns
130
in zone
104
are turned on to melt the surface of the skull
118
in the sloping hearth
116
. The crucible
110
a
full of molten titanium is tilted and poured at a steady rate onto the hearth
116
so that the gaseous contaminants, chlorine and hydrogen, are removed by outgassing and the titanium is cast into the ingot mold
125
. The rate at which the metal is poured over the hearth
116
depends on the quantity of gases present in the titanium from the reduction step. The larger this quantity, the slower the rate so as to give enough time for degassing to occur. A constant flow of inert gas entering ports
142
carries the contaminants away through exit ports
140
.
While the preceding step is occurring in zone
104
, the first step is operational in zone
102
. The virtue of this arrangement is that the processing rates in the left
102
and right
104
zones can be controlled independently of each other to achieve an overall steady production rate.
This process produces reduced titanium free from dissolved impurities, i.e., chlorine, oxygen, nitrogen, carbon, and hydrogen. Chlorine and hydrogen can be readily removed by exposing the molten titanium surface to high velocity argon or helium plasma, while keeping the titanium sufficiently hot so that it can be cast as an ingot after the degassing operation. As noted, oxygen, nitrogen and carbon cannot be removed in this late stage and hence must be kept out of the titanium by carrying out all processing in an environment where the partial pressures of these gases is very low, i.e., in an inert atmosphere, taking great care that there are no leaks to or from the atmosphere in any of the processing vessels by overflow of argon or helium gas.
Thus, one of the advantages of this invention is that the plasma reactor
40
and the refining station
104
are basically one integrated apparatus
100
. In this way the reduced titanium tetrachloride in the form of molten titanium droplets exits the reactor
40
directly to the second processing stage. The transition zone
43
from the reactor
40
is between the reactor
40
and the reducing refining zones
102
,
104
and thus the molten drops of titanium are not exposed to fresh ambient environment or at least the exposure to fresh ambient environment is minimized. The purity of the plasma gas, argon or helium, were chosen to maximize the purity of the titanium.
In effect, from the time of the formation of the molten titanium, the metal is under controlled conditions and inert gas so that the partial pressures of the gases which are difficult to remove by outgassing are kept at. a minimum. This is achieved by a single integrated apparatus
100
so that the molten titanium metal can be handled and transferred within a controlled environment provided by a single contained apparatus
100
which is effective not only to maintain environmental conditions surrounding the molten titanium under control, but also to exclude contaminant gases.
An additional and valuable option is the ability to alloy the titanium while it is still molten and make a much more valuable titanium alloy, e.g., 4Ti-6Al-4V. This may be accomplished in the right hand section
104
of the device.
Another advantage of this invention is the formation of essentially pure titanium tetrachloride which is then processed to provide essentially pure titanium metal which can be alloyed, as desired. Moreover, while the starting material is a titanium containing ore
17
, this is preferred as opposed to the use of titanium dioxide powders since the latter are relatively expensive and may contain impurities which may be difficult to remove and which may adversely impact the overall purity of the final titanium product. Another advantage of the present invention is that the final refining and alloying operation is carried out in a single device
100
, under controlled atmosphere pressure conditions, i.e., inert gas environment. These atmospheric conditions are relatively benign in the sense that the atmosphere with which the molten titanium is in contact does not include contaminating gas or gases. Because there is a constant out flow of inert gas the purity of the final product is not compromised by exposure to ambient air and the contaminants in air.
The present invention has been described herein with reference to a particular embodiment for a particular application. Those having ordinary skill in the art and access to the present teachings will recognize additional modifications, applications and embodiments within the scope thereof.
It is therefore intended by the appended claims to cover any and all such applications, modifications and embodiments within the scope of the present invention.
Claims
- 1. A process for the production of titanium metal comprising the steps of chlorinating titanium bearing ore to form titanium tetrachloride, purifying the titanium tetrachloride, and heating and continuously reacting the titanium tetrachloride at atmospheric pressures under inert gas with a metallic reductant in a plasma to yield molten titanium metal which is further processed in a connected apparatus at atmospheric pressures in an environment of inert gas.
- 2. The process according to claim 1, wherein the metallic reductant is magnesium.
- 3. The process according to claim 1, wherein the metallic reductant is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, calcium, strontium, barium and radium.
- 4. The process according to claim 1, wherein the step of reacting the titanium tetrachloride includes the step of introducing the titanium tetrachloride and the metallic reductant continuously into the focal point of plasma torches.
- 5. The process according to claim 1, wherein impurities outgas during the further processing under inert gas.
- 6. The process according to claim 1, wherein the inert gas is selected from the group consisting of argon and helium.
- 7. The process according to claim 5, wherein the inert gas is selected from the group consisting of argon and helium.
- 8. The process according to claim 5, further comprising the step of alloying the molten titanium metal with an additional metal.
- 9. The process according to claim 8, wherein the additional metal is selected from the group consisting of aluminum and vanadium.
- 10. The process according to claim 8, wherein aluminum and vanadium are introduced into the molten titanium to produce a titanium-aluminum-vanadium alloy.
US Referenced Citations (21)
Foreign Referenced Citations (2)
Number |
Date |
Country |
549299 |
Nov 1957 |
CA |
809444 |
Feb 1959 |
GB |