CA1145147A - Reduction of metals - Google Patents
Reduction of metalsInfo
- Publication number
- CA1145147A CA1145147A CA000360747A CA360747A CA1145147A CA 1145147 A CA1145147 A CA 1145147A CA 000360747 A CA000360747 A CA 000360747A CA 360747 A CA360747 A CA 360747A CA 1145147 A CA1145147 A CA 1145147A
- Authority
- CA
- Canada
- Prior art keywords
- boosters
- metal
- ore
- iron
- metals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- Manufacture And Refinement Of Metals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A method of reducing metals from the metal oxide or from the ore by aluminothermic reduction to produce relative-ly free iron-containing metal, using as heat boosters CaSO4, MnO2, S, SiO2, Ba(NO3)2, Sr(NO3)2 and Ca(NO3)2 free of iron.
The metals which may be reduced are Mn, V, Cr, Ta and Cb.
A method of reducing metals from the metal oxide or from the ore by aluminothermic reduction to produce relative-ly free iron-containing metal, using as heat boosters CaSO4, MnO2, S, SiO2, Ba(NO3)2, Sr(NO3)2 and Ca(NO3)2 free of iron.
The metals which may be reduced are Mn, V, Cr, Ta and Cb.
Description
il45147 REDt~CTION OF METALS
____ ____ _ The present inventlon relates to a method of aluminothermic reduction of metals from their oxides or from the ore. More specifically, the invention deals with reducing these metals using iron free thermic boosters.
Aluminothermic reduction of metals has been performed using iron oxides as heat boosters. This procedure always produces an iron-containing compound as the product. For example, in the aluminothermic reduction of columbium or tantalum from their ores, there is produced FeCb and FeTa.
The iron oxides are necessary to provide sufficient heat of reaction between the aluminum and oxygen to provide a molten product whereby the slag and dross may be separated from the liquid metal by differences in specific gravity, the slag or dross beinq less dense than the molten metal. The iron oxide heat boosters usually used are FeO, Fe203 and/or Fe304 and FeCb and FeTa are produced for alloying applications. This process, however, when used to produce columbium and tan-talum for alloying wherein no iron is desired, requires a further purification step to remove the iron from the FeCb and FeTa which is produced~
In the past when pure columbium is desired free from iron, a hydrogen fluoride dissolution or caustic fusion of the ore was used. These processes, however, are more expensive.
There is, therefore, a need for a process for pro-ducing metals from their ore or oxide by aluminothermic ; reduction free of iron except for the iron occurring naturally in the ore.
In accordance with the present invention it has been found that metals such as Cb, Ta, Mn, V, and Cr can be produced from their oxides or their ores by an alumino-thermic reduction process wherein the product formed is relatively free of iron. This is accomplished by using, as heat boosters, one or more of CaS04, MnO2, S, SiO2, Ba(NO3)2, Sr(NO3)2 and Ca(NO3)2.
While this invention is broadly concerned with a method for producing metals of the group Cb, Ta, Mn, V and Cr from their o~ides and ores by an aluminothermic reduction process whereby the product produced is relatively free from ., ~
.,~ ~
51~'7 iron, for purposes of illustration, the production of Cb from its ore will be described in detail herein, but it is to be understood that the other metals mentioned above can be produced by a similar method.
With regard to upgraded Cb and/or Ta ores, the alumino-thermic reduction thereof is performed in accordance with this invention using as heat boosters at least one of CaS04, MnO2, S, SiO2, Ba(N03)2, Sr(N03)2 and Ca(N03)2. By this pr~cess, Cb is recovered without increasing the iron content of the product. This process for producing relatively iron free Cb is less expensive than prior art methods wherein hydrogen fluoxide dissolution or caustic fusion of the ores are required.
A particular advantage in using calcium sulphate as an oxidizer in the reaction is its great stability, making it much safer to handle when mixed with atomized aluminum powder or other metal powders. Further, radioactive elements such as U and Th are found in ores containing Cb and Ta. This method of reduction separates the Cb and Ta from the radionuclides by not reducing the radionuclides to a metallic state but leaving them in the slag in a combined and diluted state.
When using CaLN03)2 it is necessary, because of its delinquenscent properties, to dry the material or to use it in a controlled atmosphere or vacuum. It should further be noted that SiO2 and MnO2 cause the slag to be more viscous while CaS04 and Ba(N03)2 cause the slag to be less viscous.
It is, therefore, necessary to combine various amounts of the above to achieve the slag viscosity desired.
~0 Using Ba(N03)2 as a booster it can react in various .
ways with aluminum powder always yielding BaO and A1203, following some examples of possible reactions:
3Ba(N03)2 + lOAl = 3BaO + 5A1203 + 3N2 3Ba(N03)2 + 2Al = 3BaO ~ A1203 + 6N02 or with Cb2o5 3Cb205 + 3BalN03)2 + 20Al = 3BaO + lOA1203 + 6CbN
In reality a combination of these reactions takes place along with reactions with the minor constituents of the ore.
: - -~' Sl4~
The ignition temperature used for the above booster ores mix is generally from about 200C to about 3000~C.
This temperature is controlled by the mi~ used and the ratio boosters to ore. The boosters generally do not exceed about 75 ~ by weight of the mix. The boosters are usually present in an amount to cause the reaction temperature to rise from about 10C to about 1000C above the melting point of the metal.
The following tests have been conducted using pyrochlore ores from Canada and Brazil. Atomized Al powder and the following oxides were also used: CaSO4, MnO2, Ba(NO3)2 and a mix of CaSO4 and Sr(NO3)2.
Example 1 Using CaSO4 as an oxidizer and heat booster for the reaction, the following mix was used:
5396 gms Pyrochlore Ore 2320 gms. Atomized Al ; 2320 gms. CaSO4 (Dry~
After blending 20 minutes, the mix was poured into an Al tube and ignited at a~ove 2000C. The mix burned rapidly, being completely burned in 50 seconds. The separation of the metal and slag was clean with no tendency for the metal and slag to adhere to each other. Recovery was in excess of ga wt.%.
Metal Analysis Cb 90.6%
S 2.08%
Al 4.4%
Fe 1.8%
Ti 0. 75%
Si 0. 1%
U 3.3 ppm 0 1.1%
Example 2 35 The following mix was used:
539~ gms. Pyrochlore Ore 2320 gms. Atomized Al ` 2226 gms. MnO2 The same mixing time and preparation as recited in ' ~
~1~5~
Example l was used. The mix burned very rapidly, in about 15 seconds, and there was an excellent separation of the slag and the metal, but the recovery was very low, approximately 61~. It is not clear why the recovery was so low because sufficient heat seemed to be generated.
As stated above, although the test was conducted with Cb ore for the production of Cb, the concept ol this invention is applicable to the extraction of any metal from the ore which can be reduced by atomized Aluminum powder;
i.e., Mn from MnO, MnO2 and Mn2O3; V, Cr, Ta from oxide or ore.
Exam~le 3 ~sing Ba(NO3)2 as an oxidizer and heat booster the following mix was blended 20 minutes in a V-cone blender:
5070 gms. Pyrochlore Ore 1465 gms. Atomized Aluminum Powder 6q6 gms. Ba(NO3~2 The blend was ignited and burned in 150 seconds pro-ducing a metal derby and slag which was well separated.
Metal Analysis ~
Cb 88 O 1.3 Al 3.2 N 0.92 Fe 2.9 Ti 1.6 Si 0.18 Example 4 Using CaSO4 + Sr(NO3)2 as oxidizers and heat boosters the following experiment was conducted:
- Blending for 20 minutes in a V-cone blender:
5070 gms. Pyrochlore Ore 1545 gms. Atomized Aluminum Powder q70 gms. CaSO4 (Dry~
243 gms. Sr~NO3)2 This blend was poured into an Al tube surrounded on all sides and the bottom by crushed slag. After igniting at above 2000C the mix burned in 120 seconds. Separation of the metal and slag was excellent with a Cb recovery of 11~51~7 approximate ly ~1% .
Metal Analysis 96 Cb 88.4 Al 0. 5 Fe 3.3 o 1.6 N 0.6 Si 0.5 Ti 0 . 2 3 S 4.5 ,1 , ,, ~
;: :
, ,.~ ``` ~ , , '. ~
____ ____ _ The present inventlon relates to a method of aluminothermic reduction of metals from their oxides or from the ore. More specifically, the invention deals with reducing these metals using iron free thermic boosters.
Aluminothermic reduction of metals has been performed using iron oxides as heat boosters. This procedure always produces an iron-containing compound as the product. For example, in the aluminothermic reduction of columbium or tantalum from their ores, there is produced FeCb and FeTa.
The iron oxides are necessary to provide sufficient heat of reaction between the aluminum and oxygen to provide a molten product whereby the slag and dross may be separated from the liquid metal by differences in specific gravity, the slag or dross beinq less dense than the molten metal. The iron oxide heat boosters usually used are FeO, Fe203 and/or Fe304 and FeCb and FeTa are produced for alloying applications. This process, however, when used to produce columbium and tan-talum for alloying wherein no iron is desired, requires a further purification step to remove the iron from the FeCb and FeTa which is produced~
In the past when pure columbium is desired free from iron, a hydrogen fluoride dissolution or caustic fusion of the ore was used. These processes, however, are more expensive.
There is, therefore, a need for a process for pro-ducing metals from their ore or oxide by aluminothermic ; reduction free of iron except for the iron occurring naturally in the ore.
In accordance with the present invention it has been found that metals such as Cb, Ta, Mn, V, and Cr can be produced from their oxides or their ores by an alumino-thermic reduction process wherein the product formed is relatively free of iron. This is accomplished by using, as heat boosters, one or more of CaS04, MnO2, S, SiO2, Ba(NO3)2, Sr(NO3)2 and Ca(NO3)2.
While this invention is broadly concerned with a method for producing metals of the group Cb, Ta, Mn, V and Cr from their o~ides and ores by an aluminothermic reduction process whereby the product produced is relatively free from ., ~
.,~ ~
51~'7 iron, for purposes of illustration, the production of Cb from its ore will be described in detail herein, but it is to be understood that the other metals mentioned above can be produced by a similar method.
With regard to upgraded Cb and/or Ta ores, the alumino-thermic reduction thereof is performed in accordance with this invention using as heat boosters at least one of CaS04, MnO2, S, SiO2, Ba(N03)2, Sr(N03)2 and Ca(N03)2. By this pr~cess, Cb is recovered without increasing the iron content of the product. This process for producing relatively iron free Cb is less expensive than prior art methods wherein hydrogen fluoxide dissolution or caustic fusion of the ores are required.
A particular advantage in using calcium sulphate as an oxidizer in the reaction is its great stability, making it much safer to handle when mixed with atomized aluminum powder or other metal powders. Further, radioactive elements such as U and Th are found in ores containing Cb and Ta. This method of reduction separates the Cb and Ta from the radionuclides by not reducing the radionuclides to a metallic state but leaving them in the slag in a combined and diluted state.
When using CaLN03)2 it is necessary, because of its delinquenscent properties, to dry the material or to use it in a controlled atmosphere or vacuum. It should further be noted that SiO2 and MnO2 cause the slag to be more viscous while CaS04 and Ba(N03)2 cause the slag to be less viscous.
It is, therefore, necessary to combine various amounts of the above to achieve the slag viscosity desired.
~0 Using Ba(N03)2 as a booster it can react in various .
ways with aluminum powder always yielding BaO and A1203, following some examples of possible reactions:
3Ba(N03)2 + lOAl = 3BaO + 5A1203 + 3N2 3Ba(N03)2 + 2Al = 3BaO ~ A1203 + 6N02 or with Cb2o5 3Cb205 + 3BalN03)2 + 20Al = 3BaO + lOA1203 + 6CbN
In reality a combination of these reactions takes place along with reactions with the minor constituents of the ore.
: - -~' Sl4~
The ignition temperature used for the above booster ores mix is generally from about 200C to about 3000~C.
This temperature is controlled by the mi~ used and the ratio boosters to ore. The boosters generally do not exceed about 75 ~ by weight of the mix. The boosters are usually present in an amount to cause the reaction temperature to rise from about 10C to about 1000C above the melting point of the metal.
The following tests have been conducted using pyrochlore ores from Canada and Brazil. Atomized Al powder and the following oxides were also used: CaSO4, MnO2, Ba(NO3)2 and a mix of CaSO4 and Sr(NO3)2.
Example 1 Using CaSO4 as an oxidizer and heat booster for the reaction, the following mix was used:
5396 gms Pyrochlore Ore 2320 gms. Atomized Al ; 2320 gms. CaSO4 (Dry~
After blending 20 minutes, the mix was poured into an Al tube and ignited at a~ove 2000C. The mix burned rapidly, being completely burned in 50 seconds. The separation of the metal and slag was clean with no tendency for the metal and slag to adhere to each other. Recovery was in excess of ga wt.%.
Metal Analysis Cb 90.6%
S 2.08%
Al 4.4%
Fe 1.8%
Ti 0. 75%
Si 0. 1%
U 3.3 ppm 0 1.1%
Example 2 35 The following mix was used:
539~ gms. Pyrochlore Ore 2320 gms. Atomized Al ` 2226 gms. MnO2 The same mixing time and preparation as recited in ' ~
~1~5~
Example l was used. The mix burned very rapidly, in about 15 seconds, and there was an excellent separation of the slag and the metal, but the recovery was very low, approximately 61~. It is not clear why the recovery was so low because sufficient heat seemed to be generated.
As stated above, although the test was conducted with Cb ore for the production of Cb, the concept ol this invention is applicable to the extraction of any metal from the ore which can be reduced by atomized Aluminum powder;
i.e., Mn from MnO, MnO2 and Mn2O3; V, Cr, Ta from oxide or ore.
Exam~le 3 ~sing Ba(NO3)2 as an oxidizer and heat booster the following mix was blended 20 minutes in a V-cone blender:
5070 gms. Pyrochlore Ore 1465 gms. Atomized Aluminum Powder 6q6 gms. Ba(NO3~2 The blend was ignited and burned in 150 seconds pro-ducing a metal derby and slag which was well separated.
Metal Analysis ~
Cb 88 O 1.3 Al 3.2 N 0.92 Fe 2.9 Ti 1.6 Si 0.18 Example 4 Using CaSO4 + Sr(NO3)2 as oxidizers and heat boosters the following experiment was conducted:
- Blending for 20 minutes in a V-cone blender:
5070 gms. Pyrochlore Ore 1545 gms. Atomized Aluminum Powder q70 gms. CaSO4 (Dry~
243 gms. Sr~NO3)2 This blend was poured into an Al tube surrounded on all sides and the bottom by crushed slag. After igniting at above 2000C the mix burned in 120 seconds. Separation of the metal and slag was excellent with a Cb recovery of 11~51~7 approximate ly ~1% .
Metal Analysis 96 Cb 88.4 Al 0. 5 Fe 3.3 o 1.6 N 0.6 Si 0.5 Ti 0 . 2 3 S 4.5 ,1 , ,, ~
;: :
, ,.~ ``` ~ , , '. ~
Claims (5)
1. In a method of producing a metal selected from the group consisting of Cb, Ta, Mn, V and Cr from its oxide or its ore by an aluminothermic reduction process using heat boosters, the improvement comprising, using as heat boosters at least one member selected from the group of CaSO4, MnO2, S, SiO2, Ba(NO3)2, Sr(NO3)2 and Ca(NO3)2.
2. The method according to claim 1 wherein the aluminothermic reduction process is ignited by heating to a temperature from about 200°C to about 3000°C.
3. The method according to claim 1 wherein the boosters cause the reaction temperature to rise to about 10°C
to about 1000°C above the melting point of the metal.
to about 1000°C above the melting point of the metal.
4. The method according to claim 1 wherein the booster is Ca(NO3)2 and the process is performed in a controlled atmosphere.
5. The method according to claim 1 wherein the boosters do not exceed 75% of the composition and are present in an amount sufficient to cause an increase in temperature from 10°C to 1000°C above the melting point of the metal.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US7867979A | 1979-09-25 | 1979-09-25 | |
| US078,679 | 1979-09-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1145147A true CA1145147A (en) | 1983-04-26 |
Family
ID=22145576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000360747A Expired CA1145147A (en) | 1979-09-25 | 1980-09-22 | Reduction of metals |
Country Status (2)
| Country | Link |
|---|---|
| BR (1) | BR8006119A (en) |
| CA (1) | CA1145147A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5002730A (en) * | 1989-07-24 | 1991-03-26 | Energy Conversion Devices | Preparation of vanadium rich hydrogen storage alloy materials |
-
1980
- 1980-09-22 CA CA000360747A patent/CA1145147A/en not_active Expired
- 1980-09-24 BR BR8006119A patent/BR8006119A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5002730A (en) * | 1989-07-24 | 1991-03-26 | Energy Conversion Devices | Preparation of vanadium rich hydrogen storage alloy materials |
Also Published As
| Publication number | Publication date |
|---|---|
| BR8006119A (en) | 1981-04-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |