CA2988445A1 - Direct production of aluminum and silicon from their ore - Google Patents
Direct production of aluminum and silicon from their ore Download PDFInfo
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- CA2988445A1 CA2988445A1 CA2988445A CA2988445A CA2988445A1 CA 2988445 A1 CA2988445 A1 CA 2988445A1 CA 2988445 A CA2988445 A CA 2988445A CA 2988445 A CA2988445 A CA 2988445A CA 2988445 A1 CA2988445 A1 CA 2988445A1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/023—Preparation by reduction of silica or free silica-containing material
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/02—Obtaining aluminium with reducing
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Abstract
Any aluminum source have silica present with it. Any aluminum production process separates silica and discards it incurring expenses and creating environmental hazard. Production of aluminum from enriched aluminum ore consumes high electric energy making economic survival of this industry difficult. The growing use of silicon in electronic field and engineering utilization of Si3N4 has created interest in the production of silicon. In the new process being presented here both Al and Si is being produced as pure materials but using the same equipment. Hydrogen and oxygen are energy source with electric energy as back up support. Both hydrogen and electricity are produced within the process. Every ingredient of the ore is changed into valuable product. No CO2 is emitted, no slag is produced,
Description
Patent Application Direct production of aluminum and Silicon from their Ore dec.2017 Canadian Intellectual Property Inventor Dr. Ghulam Nabi International classification. Chemistry, Chiavatti Dr. Chemical Engineering L3R 1E2 US Patents classification Telephone 905 513 7641 023, 044, 055, 060, 075, 095, 165, 266 Canada 350, 373, 520, 518, References:
Patents awarded to this inventor Canadian patent 2,019,050 Method and apparatus for steel making:
U.S. Patent5,286,273 Method for steel making in high temperature reactor U.S. Patent5,402õ990 Steel making Plant.
Publications references Transactions of the Metallurgical Society of AIME Vol.242 dec.1968.
Journal of Iron and Steel institute June Industrial and Engineering Chemistry (Fundamental) Nov.197Method and apparatus for Steel making March 1993 Abstract Abstract Any aluminum source have silica present with it. Any aluminum production process separates silica and discards it incurring expenses and creating environmental hazard.
Production of aluminum from enriched aluminum ore consumes high electric energy making economic survival of this industry difficult. The growing use of silicon in electronic field and engineering utilization of Si3N4 has created interest in the production of silicon. In the new process being presented here both Al and Si is being produced as pure materials but using the same equipment.
Hydrogen and oxygen are energy source with electric energy as back up support.
Both hydrogen and electricity are produced within the process. Every ingredient of the ore is changed into valuable product. No CO2 is emitted, no slag is produced, --------- -1. Low-pressure compress
Patents awarded to this inventor Canadian patent 2,019,050 Method and apparatus for steel making:
U.S. Patent5,286,273 Method for steel making in high temperature reactor U.S. Patent5,402õ990 Steel making Plant.
Publications references Transactions of the Metallurgical Society of AIME Vol.242 dec.1968.
Journal of Iron and Steel institute June Industrial and Engineering Chemistry (Fundamental) Nov.197Method and apparatus for Steel making March 1993 Abstract Abstract Any aluminum source have silica present with it. Any aluminum production process separates silica and discards it incurring expenses and creating environmental hazard.
Production of aluminum from enriched aluminum ore consumes high electric energy making economic survival of this industry difficult. The growing use of silicon in electronic field and engineering utilization of Si3N4 has created interest in the production of silicon. In the new process being presented here both Al and Si is being produced as pure materials but using the same equipment.
Hydrogen and oxygen are energy source with electric energy as back up support.
Both hydrogen and electricity are produced within the process. Every ingredient of the ore is changed into valuable product. No CO2 is emitted, no slag is produced, --------- -1. Low-pressure compress
2. Interco ler
3 Turbines
4 Drive compressors ¨
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, . =
¨ a. Geer box 9.111coraing hot gases TC
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Comptes Set 6 C) al, dew \ -.--',,L cathodes ,.
-¨, ----arto . , . õgi=.,=. .
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i 8 TC -..'f-,-- 'r, -'.= 1. _\-, I
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' i ts,y,kte, Ingtercgolet DIM.
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Stream _ _ ,.= = ., -9-4 - - ;-.:".'.4.- .... - - -- ,-4_ ag slagõ _ _ _ ..= Oa ----- -4.--......... _ ' -.,1-' ------sliding sea , . ,,,,,,f,,,, l = .i.!,,$,< 4:,( = ,,:-. ¨
ti,_¨ C0,112 i 4,,, PROD oar 4. igv.- O
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L, Sliding seal It , - -LA i , i-_ 14: Condenser . -õ_.;_., -' Figure 2. A two reactor to produce Aluminum from alumina Page 1 of 2 v Hydrogen for the process is produced by shift conversion of CO.H2 CO2 produced is processed in figure 6 The process explained in the flow sheet is applicable to the production of Si from SiO2 And Al and Si from mixed charge of A1203 +Si02 .
This process and equipment is applicable to the production of Cr from its oxides and other high melting oxides.
Direct production of aluminum and Silicon from their Ore There are two main types of aluminum ores which are processed for the production of aluminum at present:
Bauxites. These are high quality aluminum containg raw materials containing higher percentage alumina and about 10-15 silica. It may contain variable percentage of iron oxide calcium oxide magnesium oxide and others. High quality alumina is prepared by low temperature high pressure treatment which produces high environmental pollution.
High purity alumina is reduced to aluminum by electrolysis process (Hall ¨Heroult Process) using about 15 Mwh per ton of aluminum. Energy utilization is very high and process requires a second time purification process.
Nephlines. These aluminum raw materials have more silica than alumina and have similar type impurities as bauxites, generally have some sodium potassium Alkalies.
Enrichment process involves high temperature alkali heating where by Sodium aluminate and sodium silicate are obtained which are separated by Calcium treatment. Calcium silicate is separated. Generally 100,000 ton aluminum produces 750000 ton low quality cement.
A new process is introduced where all type of commercially exploited aluminum ore can be utilized. The purified material obtained is A1203 + Si02 which then used to produce Al and Si and their compound and alloys.
Nothing is discarded Fe, Mg, Ca are separated and product gases CO2 and H20 are changed to hydrocarbon gases and chemicals.
This process applies for aluminum production from purified alumina. The process can be extended to obtain aluminum and silicon from purified ore mixture of alumina and silica.
The following description is with reference to figure .
Small particles or powder alumina is charged through double locked hopper.
After the hopper calculated amount of oxygen is metered in ( 02) and then in a domed type reactor Hydrogen (H2) is introduced in down ward falling charge.
In this dome high temperature is achieved almost nearly 1800 C there being some excess H2. With the introduction of 02 and H2 with the charge in this reactor we are achieving exothermic conditions for the reaction:
A1203 +3 H+3 112 +3/2 02 ¨> 2A1 + 6H20 More 112 is introduced with electrodes discharge the heat energy is more than the heat of formation of A1203 (AH=-400 K.cal/ kg.mole). Refractory is graphite bricks which are cooled by conventional plate and stave coolers. Hydrogen in the reaction is in excess of any oxygen content. The system has the set up to go higher than 2100 C.
Product metal starts cooling down from the exit level.
The contribution from electric heating is small over- here, but can be increased if contribution from gases is desired to be decreased.
In place of hydrogen CO +H2 can be used as A14C3 is not formed above temperature of 1400C. Our product gases leave the system much above 1400C
Temperature of the exit gases is drastically cooled at the exit point (800-900C) and then it under-goes shift reaction by introduction of Co,H2 gases and heat recovery is done down to approximately 75C. Any blown out particles are retained and water is recycled and bleeds out.
Hydrogen is recovered and recycled with some additional H2 The system is approximately same when it is desired to process the combined oxides like A1203 + Si02 to Al and Si. This idea extends to direct alloys production of aluminum and some new materials and pure elements like Si, Mg. Ca Aluminum Production of A1203 9 Si02 and Na2CO3 Composition of Nephline ore is as following.
A1203 Si 02 Fe203 Ca0 Mg0 Na20 K20 H20 Kg per 26 39 5 7.9 - 11.8 2.7 92.5 7.6 100Kg Kg 2.6 6.5 0.31 1.4 1.9 0.4 4.2 moles per Kg -AH 298 AS 298 m.pt (C ) K.cal /mole cal/mole -degree A1203 400.9 12.2 2050 Na20 99.2 17.9 1132 Na Al 02 269.8 16.9 1560 Si02 217.6 9.91 1722 Na2 SiO3 371 27.2 1088 Na2CO3 279.3 33.1 850 Ca0 151.6 9.5 2615 Ca2SiO3 21.3 19.6 1544 Heat consumed by A1203 Cp approximate heat capacity K.cal/C mole -27 Si02 11 Fe203 35 Ca0 12 Na20 25 Total heats required to reach temperature 1550 C. = 283,092 K.cal Gases required 283092/60,000= 4.718 Kg, mole (CO,H2) Gases required to reduce.31 kg Fe203, =.1. kg.mole (CO,H2 ) Material and energy of chemical reactions 2.6(A1203 400.9 12.2) +
2.6(Na20 99.2 17.9) =5.2(Na Al 02 269.8 16.9) Heats evolved =- 105,000 K.cal
Comptes Set 6 C) al, dew \ -.--',,L cathodes ,.
-¨, ----arto . , . õgi=.,=. .
,,;-.. - = = ...' . = = . . .=
i 8 TC -..'f-,-- 'r, -'.= 1. _\-, I
2 a 3 , =
1 . .......=
, = water Ii ill ¨
4 0"
' i ts,y,kte, Ingtercgolet DIM.
sgot\1 1 .. = n=
¨
CtgIIPTt%sOf - - .
1444114 _ _ ..... ,.....A.:-.......,.,-water ---, _ . .
Stream _ _ ,.= = ., -9-4 - - ;-.:".'.4.- .... - - -- ,-4_ ag slagõ _ _ _ ..= Oa ----- -4.--......... _ ' -.,1-' ------sliding sea , . ,,,,,,f,,,, l = .i.!,,$,< 4:,( = ,,:-. ¨
ti,_¨ C0,112 i 4,,, PROD oar 4. igv.- O
- - ecialed Hi HTS LTS
goo _ /
L, Sliding seal It , - -LA i , i-_ 14: Condenser . -õ_.;_., -' Figure 2. A two reactor to produce Aluminum from alumina Page 1 of 2 v Hydrogen for the process is produced by shift conversion of CO.H2 CO2 produced is processed in figure 6 The process explained in the flow sheet is applicable to the production of Si from SiO2 And Al and Si from mixed charge of A1203 +Si02 .
This process and equipment is applicable to the production of Cr from its oxides and other high melting oxides.
Direct production of aluminum and Silicon from their Ore There are two main types of aluminum ores which are processed for the production of aluminum at present:
Bauxites. These are high quality aluminum containg raw materials containing higher percentage alumina and about 10-15 silica. It may contain variable percentage of iron oxide calcium oxide magnesium oxide and others. High quality alumina is prepared by low temperature high pressure treatment which produces high environmental pollution.
High purity alumina is reduced to aluminum by electrolysis process (Hall ¨Heroult Process) using about 15 Mwh per ton of aluminum. Energy utilization is very high and process requires a second time purification process.
Nephlines. These aluminum raw materials have more silica than alumina and have similar type impurities as bauxites, generally have some sodium potassium Alkalies.
Enrichment process involves high temperature alkali heating where by Sodium aluminate and sodium silicate are obtained which are separated by Calcium treatment. Calcium silicate is separated. Generally 100,000 ton aluminum produces 750000 ton low quality cement.
A new process is introduced where all type of commercially exploited aluminum ore can be utilized. The purified material obtained is A1203 + Si02 which then used to produce Al and Si and their compound and alloys.
Nothing is discarded Fe, Mg, Ca are separated and product gases CO2 and H20 are changed to hydrocarbon gases and chemicals.
This process applies for aluminum production from purified alumina. The process can be extended to obtain aluminum and silicon from purified ore mixture of alumina and silica.
The following description is with reference to figure .
Small particles or powder alumina is charged through double locked hopper.
After the hopper calculated amount of oxygen is metered in ( 02) and then in a domed type reactor Hydrogen (H2) is introduced in down ward falling charge.
In this dome high temperature is achieved almost nearly 1800 C there being some excess H2. With the introduction of 02 and H2 with the charge in this reactor we are achieving exothermic conditions for the reaction:
A1203 +3 H+3 112 +3/2 02 ¨> 2A1 + 6H20 More 112 is introduced with electrodes discharge the heat energy is more than the heat of formation of A1203 (AH=-400 K.cal/ kg.mole). Refractory is graphite bricks which are cooled by conventional plate and stave coolers. Hydrogen in the reaction is in excess of any oxygen content. The system has the set up to go higher than 2100 C.
Product metal starts cooling down from the exit level.
The contribution from electric heating is small over- here, but can be increased if contribution from gases is desired to be decreased.
In place of hydrogen CO +H2 can be used as A14C3 is not formed above temperature of 1400C. Our product gases leave the system much above 1400C
Temperature of the exit gases is drastically cooled at the exit point (800-900C) and then it under-goes shift reaction by introduction of Co,H2 gases and heat recovery is done down to approximately 75C. Any blown out particles are retained and water is recycled and bleeds out.
Hydrogen is recovered and recycled with some additional H2 The system is approximately same when it is desired to process the combined oxides like A1203 + Si02 to Al and Si. This idea extends to direct alloys production of aluminum and some new materials and pure elements like Si, Mg. Ca Aluminum Production of A1203 9 Si02 and Na2CO3 Composition of Nephline ore is as following.
A1203 Si 02 Fe203 Ca0 Mg0 Na20 K20 H20 Kg per 26 39 5 7.9 - 11.8 2.7 92.5 7.6 100Kg Kg 2.6 6.5 0.31 1.4 1.9 0.4 4.2 moles per Kg -AH 298 AS 298 m.pt (C ) K.cal /mole cal/mole -degree A1203 400.9 12.2 2050 Na20 99.2 17.9 1132 Na Al 02 269.8 16.9 1560 Si02 217.6 9.91 1722 Na2 SiO3 371 27.2 1088 Na2CO3 279.3 33.1 850 Ca0 151.6 9.5 2615 Ca2SiO3 21.3 19.6 1544 Heat consumed by A1203 Cp approximate heat capacity K.cal/C mole -27 Si02 11 Fe203 35 Ca0 12 Na20 25 Total heats required to reach temperature 1550 C. = 283,092 K.cal Gases required 283092/60,000= 4.718 Kg, mole (CO,H2) Gases required to reduce.31 kg Fe203, =.1. kg.mole (CO,H2 ) Material and energy of chemical reactions 2.6(A1203 400.9 12.2) +
2.6(Na20 99.2 17.9) =5.2(Na Al 02 269.8 16.9) Heats evolved =- 105,000 K.cal
6.5(Si 02 217.6 9.91)+
6.5(Na20 99.2 17.9 = 6.5 (Na2 SiO3 371 27.2 Heat evolved = - 357,500 Kcal 1.4(Ca0 151.6 9.5) +
1.4(Si02 217.6 9.91) =1.4Ca2SiO3 388. 19.6) Heat evolved = 28/ K.cal Changing 6.2.1 Kg.mole Na2CO3( 279.3 K.cal) to 6.2 Kg.mole Na20( 99.2 Kg.mole) 6.2x 86. K.cal =533,000 k,cal Net heats Heat required to heat the charge =+283,992 K.cal Net heats from reactions =-490,000 Heats required to decompose Na2CO3 =584,000 Heat required by Na20 to reach 1550C = 263,500 Heat taken up by reaction gases CO,H2 and 02 = 183,750 823,000 k.cal 13,4 Kg mole CO,H2 and 6.7 02 Material balance summary Input out put A1203=2.6 Na Al 02=5.2 Si02 =6.2 Na2 SiO3 =6.2 Ca0 =1.4 Ca2SiO3 = 1.4 Fe203 -.31 , .Fe=.31 Na2CO3 -3.1 Na2CO3 5.1kg.mo le Na20 =6.2 Saving Na2CO3 =1.9 Total gases consumed per ton of Nephline ore =21.4 kg.mole That is approximately 200 kg fuel mix (counting only C and Hydrogen C=84 Kg ,112-14 kg Obtaining A1203 SiO2 Ca2SiO3 and Na2CO3 From the primary high temperature reactor the following streams are Obtained.
1. Product gases 22 Kg mole (CO2, H20) at 1550 C Cp=10 K.cal/kg.mole C
Recoverable heat contents exit temperature 75C
Electricity recovered =373 Kwh 2. Slag stream comprising = Na Al 02 = 5.2Kg mole, heat content =155,x1500 K.cal Na2 SiO3= 6.5 Kg.mole, heat content =260, //
Ca2SiO3 =!.4 kg mole , heat content = 76,4; // //
= 749,500 K.cal 3. Liquid metals Fe .31 kg.mole 4,187 K.cal Heat is recovered by gases N2 and changed to electricity by turbo-generator (860 K.cal =kwh) =
750,000 x.60% =517 Kwh Slag cooled to 70 C is dissolved in water and soluble ingredients Na Al 02 , Na2 SiO3 is filtered from insoluble Ca2SiO3 Solution is concentrated by turbine off hot gasses nitrogen and off gases from stair ways furnace.
Na Al 02 , Na2 SiO3 is separated into Na Al 02 m.pt =1550C and is left in the furnace, Na2 SiO3 is filtered off at 1088C..
Na Al 02+ CO2 9 from top gases) ¨ Na2CO3 + A1203, Na2 SiO3 + CO2 ¨ Na2CO3 + SiO2 Na2CO3 + A1203, SiO2 are changed to powder form in their ball mills Input out put summary Input Ore weight =930 Kg Out put A1203 260 kg SiO2 306 kg Ca2SiO3 218 kg Na2CO3 117 kg 921 kg Electricity produced 890 kW
Iron= =31 Kg Thermodynamic properties of A1203 Solid properties Liquid Properties Std Enthalpy change -1675.7 -1620.57 Of formation AHf K.J/mol Std molar entropy 50.92 67.24 J/mol.K
Heat Capacity, Cp 70.04 192.5 J/mol K
Production aluminum using all hydrogen and Oxygen gases.
Aluminum ores:
Compositions Raw A1203 SiO2 Fe203 CaO Na2O 1(20 S Moisture material Nephline 26.5 39.6- 4.6-5. 7.9 11.8 2.7 2 Ore 49.5 Boehmite 43-45 15-16 14-15 1.4 0.2 1.5 Bauxite Nephline 28- 44 3.5 1.4-1.5 12.8 7.6 0.12 Conc 28.6 Diaspore 53-54 3.7 22.1- 3.7-3.9 - 0.9-1.1 8-9 Bauxite 23.6.
Bohemite 46-47 8.4.9.3 19.1- 5-9 0.8-1.1 2-3 Bauxite 19.6 Nephline 28- 44 3.5 1.4-1.5 12.8 7.6 0.12 conc. 28.6 Dias pore 53-54 3.7 22-23 3.7-3.9 - 0.9-1.0 8.9 Bauxite Boehemite 44-47 8.4-9..3 19.1- 5.9 0.8-1.1 2-3 Bauxite 19.6 Conventionally aluminum is produced from alumina in an all graphite furnace called Hall Heroult process. The essential ingredient is Aluminum Fluoride cryolite AlF3- Na3A1F6 which being Fluorite compound is dangerous for health.
Alumina is itself produced from Bauxite. In many countries like Russia alumina is produced from Nephline which produce lot of CaSiO4 .100, 000 tons of aluminum produce 750,000 tons of low quality cement.
We can use any of the ore given in table I with simultaneous Fe and Al production and production of Ca, Mg, Si and alkalies.
A modified Downs cell is use full part of our new process essential parts of which are given below. Figure 3 Graphite or dolomite vessel with carbon cathode and anode 1 Iron wire-mesh to separate cathode and anode area 2 Siphon for Na metal to external vessel 3 Entering steam to vessel 3 4 Hydrogen Chloride to external handling system NaC1 entering to vessel 3.
6 Reacting NaC1 with H2 producing Na and HCI
6.5(Na20 99.2 17.9 = 6.5 (Na2 SiO3 371 27.2 Heat evolved = - 357,500 Kcal 1.4(Ca0 151.6 9.5) +
1.4(Si02 217.6 9.91) =1.4Ca2SiO3 388. 19.6) Heat evolved = 28/ K.cal Changing 6.2.1 Kg.mole Na2CO3( 279.3 K.cal) to 6.2 Kg.mole Na20( 99.2 Kg.mole) 6.2x 86. K.cal =533,000 k,cal Net heats Heat required to heat the charge =+283,992 K.cal Net heats from reactions =-490,000 Heats required to decompose Na2CO3 =584,000 Heat required by Na20 to reach 1550C = 263,500 Heat taken up by reaction gases CO,H2 and 02 = 183,750 823,000 k.cal 13,4 Kg mole CO,H2 and 6.7 02 Material balance summary Input out put A1203=2.6 Na Al 02=5.2 Si02 =6.2 Na2 SiO3 =6.2 Ca0 =1.4 Ca2SiO3 = 1.4 Fe203 -.31 , .Fe=.31 Na2CO3 -3.1 Na2CO3 5.1kg.mo le Na20 =6.2 Saving Na2CO3 =1.9 Total gases consumed per ton of Nephline ore =21.4 kg.mole That is approximately 200 kg fuel mix (counting only C and Hydrogen C=84 Kg ,112-14 kg Obtaining A1203 SiO2 Ca2SiO3 and Na2CO3 From the primary high temperature reactor the following streams are Obtained.
1. Product gases 22 Kg mole (CO2, H20) at 1550 C Cp=10 K.cal/kg.mole C
Recoverable heat contents exit temperature 75C
Electricity recovered =373 Kwh 2. Slag stream comprising = Na Al 02 = 5.2Kg mole, heat content =155,x1500 K.cal Na2 SiO3= 6.5 Kg.mole, heat content =260, //
Ca2SiO3 =!.4 kg mole , heat content = 76,4; // //
= 749,500 K.cal 3. Liquid metals Fe .31 kg.mole 4,187 K.cal Heat is recovered by gases N2 and changed to electricity by turbo-generator (860 K.cal =kwh) =
750,000 x.60% =517 Kwh Slag cooled to 70 C is dissolved in water and soluble ingredients Na Al 02 , Na2 SiO3 is filtered from insoluble Ca2SiO3 Solution is concentrated by turbine off hot gasses nitrogen and off gases from stair ways furnace.
Na Al 02 , Na2 SiO3 is separated into Na Al 02 m.pt =1550C and is left in the furnace, Na2 SiO3 is filtered off at 1088C..
Na Al 02+ CO2 9 from top gases) ¨ Na2CO3 + A1203, Na2 SiO3 + CO2 ¨ Na2CO3 + SiO2 Na2CO3 + A1203, SiO2 are changed to powder form in their ball mills Input out put summary Input Ore weight =930 Kg Out put A1203 260 kg SiO2 306 kg Ca2SiO3 218 kg Na2CO3 117 kg 921 kg Electricity produced 890 kW
Iron= =31 Kg Thermodynamic properties of A1203 Solid properties Liquid Properties Std Enthalpy change -1675.7 -1620.57 Of formation AHf K.J/mol Std molar entropy 50.92 67.24 J/mol.K
Heat Capacity, Cp 70.04 192.5 J/mol K
Production aluminum using all hydrogen and Oxygen gases.
Aluminum ores:
Compositions Raw A1203 SiO2 Fe203 CaO Na2O 1(20 S Moisture material Nephline 26.5 39.6- 4.6-5. 7.9 11.8 2.7 2 Ore 49.5 Boehmite 43-45 15-16 14-15 1.4 0.2 1.5 Bauxite Nephline 28- 44 3.5 1.4-1.5 12.8 7.6 0.12 Conc 28.6 Diaspore 53-54 3.7 22.1- 3.7-3.9 - 0.9-1.1 8-9 Bauxite 23.6.
Bohemite 46-47 8.4.9.3 19.1- 5-9 0.8-1.1 2-3 Bauxite 19.6 Nephline 28- 44 3.5 1.4-1.5 12.8 7.6 0.12 conc. 28.6 Dias pore 53-54 3.7 22-23 3.7-3.9 - 0.9-1.0 8.9 Bauxite Boehemite 44-47 8.4-9..3 19.1- 5.9 0.8-1.1 2-3 Bauxite 19.6 Conventionally aluminum is produced from alumina in an all graphite furnace called Hall Heroult process. The essential ingredient is Aluminum Fluoride cryolite AlF3- Na3A1F6 which being Fluorite compound is dangerous for health.
Alumina is itself produced from Bauxite. In many countries like Russia alumina is produced from Nephline which produce lot of CaSiO4 .100, 000 tons of aluminum produce 750,000 tons of low quality cement.
We can use any of the ore given in table I with simultaneous Fe and Al production and production of Ca, Mg, Si and alkalies.
A modified Downs cell is use full part of our new process essential parts of which are given below. Figure 3 Graphite or dolomite vessel with carbon cathode and anode 1 Iron wire-mesh to separate cathode and anode area 2 Siphon for Na metal to external vessel 3 Entering steam to vessel 3 4 Hydrogen Chloride to external handling system NaC1 entering to vessel 3.
6 Reacting NaC1 with H2 producing Na and HCI
7 H2 entering the reactor vessel.
Brief production data for different size electrolysis plant.
Production size Production rate $/kg %Cost electricity equip 20 Kg H2 per hr. 1910 58 32 100 Kg H2 per hr. 80 32 55 1000 Kg H2 per hr. 4 17 73 Source: Electrolytic Hydrogen production National Renewable Energy Laboratory 1617 Cole Boulevard, Golden, Colorado The following ores can be also process in the set up shown in figure 2.
Ore -AHf K.cal/mol ASf calknolK Melting point C
Cr2O3 270 94 2400 Cr 1857 SiO2 217 9.9 1742 Si 1412 Ti203 363 18 1780 Ti 1670 Mn203 228 26. 1545 Mn 1244 Water solution of Na Al 02 , Na2 SiO3 is evaporated into dry solids mixture and charged into refractory lined furnace preheated to 1000 C and to this furnace is also introduced melted aluminum. Figure 1.1.
Na Al 02 Molecular weight =81.9 Density =1.5 gm/cm3 Cp = 73.6 J/mole-k Melting point =1650 C AHf = 1133.2 kJ/mole AS. = 70.4 j/mole-k Na2 SiO3 Molecular weight = Soluble in water 222gm/m1 at 25 C
Density = 2.6 gm/cm3 Cp= 111.8 J/mole-k Melting point = 1088 C AHf = 1561.4 kJ/mole AS. =113.7 j/mole-k AF =-1427 kJ/mole Na20 Molecular weight= 61.9 Density 2.27 Cp= 72.9 J/mole-k Melting point =1132C boiling point= 1950 C
AHf= 416 kJ/mole AS. =72 j/mole-k =-377 kJ/mole Na
Brief production data for different size electrolysis plant.
Production size Production rate $/kg %Cost electricity equip 20 Kg H2 per hr. 1910 58 32 100 Kg H2 per hr. 80 32 55 1000 Kg H2 per hr. 4 17 73 Source: Electrolytic Hydrogen production National Renewable Energy Laboratory 1617 Cole Boulevard, Golden, Colorado The following ores can be also process in the set up shown in figure 2.
Ore -AHf K.cal/mol ASf calknolK Melting point C
Cr2O3 270 94 2400 Cr 1857 SiO2 217 9.9 1742 Si 1412 Ti203 363 18 1780 Ti 1670 Mn203 228 26. 1545 Mn 1244 Water solution of Na Al 02 , Na2 SiO3 is evaporated into dry solids mixture and charged into refractory lined furnace preheated to 1000 C and to this furnace is also introduced melted aluminum. Figure 1.1.
Na Al 02 Molecular weight =81.9 Density =1.5 gm/cm3 Cp = 73.6 J/mole-k Melting point =1650 C AHf = 1133.2 kJ/mole AS. = 70.4 j/mole-k Na2 SiO3 Molecular weight = Soluble in water 222gm/m1 at 25 C
Density = 2.6 gm/cm3 Cp= 111.8 J/mole-k Melting point = 1088 C AHf = 1561.4 kJ/mole AS. =113.7 j/mole-k AF =-1427 kJ/mole Na20 Molecular weight= 61.9 Density 2.27 Cp= 72.9 J/mole-k Melting point =1132C boiling point= 1950 C
AHf= 416 kJ/mole AS. =72 j/mole-k =-377 kJ/mole Na
8 Molecular weight =23 Density = 6.9 gm/cm3 Cp= 28.2 J/mole-k Melting point -97 C
Boiling pont =882C
AHf =2.6 kJ/mole AH, =97K j/mole-k at 1200C..
6Na Al 02. 3 Na20 = 3 A1203 , +2 Al =6Na +4 A1203 AFI =;287 k cal Over all reaction 3 Na2 SiO3 +6Na Al 02 +8A1 = 7 A1203 , + 3 Si +12 Na Na is volatilized from the top of th furnace 3Si + 7 A1203 is discharged from the bottom of the furnace Si is separated through a filter and A1203 goes to reduction furnace.
Captions on figure 1.
1 ore with adjustment in composition 1. (CO, 112) and combustion air From the furnace material heated at 1550 C comes and is reacted with Na2O + Al 02 , SiO3 , Ca2SiO3 ,Mg2S103 =No Al 02 , Na2 SiO3 , Ca2SiO3 ,Mg2SiO3 Na is volatilized from reactor 6 it is changed to Na2O and introduced in exit high temperature furnace.
3.. Na Al 02 , Na2 S103 , Ca2S103,Mg2SiO3 4 . Na Al 02 , Na2 SiO3 5. Magnetic separation of Fe203 . 6. , Ca2SiO3 , Mg2S103 6.1. In Ca2SiO3 ,Mg2SiO3 reactor add Al 6.2. from the top of the reactor Ca and Mg are volatilized and fractionally condensed, 6.3 From the bottom of the reactor liquid Si and solid particulate A1203 is obtained. Si is high purity material sold in the material.A1203 goes the other stream of alumina.
Boiling pont =882C
AHf =2.6 kJ/mole AH, =97K j/mole-k at 1200C..
6Na Al 02. 3 Na20 = 3 A1203 , +2 Al =6Na +4 A1203 AFI =;287 k cal Over all reaction 3 Na2 SiO3 +6Na Al 02 +8A1 = 7 A1203 , + 3 Si +12 Na Na is volatilized from the top of th furnace 3Si + 7 A1203 is discharged from the bottom of the furnace Si is separated through a filter and A1203 goes to reduction furnace.
Captions on figure 1.
1 ore with adjustment in composition 1. (CO, 112) and combustion air From the furnace material heated at 1550 C comes and is reacted with Na2O + Al 02 , SiO3 , Ca2SiO3 ,Mg2S103 =No Al 02 , Na2 SiO3 , Ca2SiO3 ,Mg2SiO3 Na is volatilized from reactor 6 it is changed to Na2O and introduced in exit high temperature furnace.
3.. Na Al 02 , Na2 S103 , Ca2S103,Mg2SiO3 4 . Na Al 02 , Na2 SiO3 5. Magnetic separation of Fe203 . 6. , Ca2SiO3 , Mg2S103 6.1. In Ca2SiO3 ,Mg2SiO3 reactor add Al 6.2. from the top of the reactor Ca and Mg are volatilized and fractionally condensed, 6.3 From the bottom of the reactor liquid Si and solid particulate A1203 is obtained. Si is high purity material sold in the material.A1203 goes the other stream of alumina.
9 6.4 Ca and Mg is used treat with CO2and H20 hydrocarbon gases are obtained and Ca0 and Mg0 are obtained.
5. Product cooling by heat recovery 6. Na Al 02 , Na2 SiO3 dissolving in water.
7.Drying of. Na Al 02 , Na2 SiO3 8. High temperature reactor with charging of preheated Na Al 02 , Na2 SiO3, 8.1.charging of melted Al at 1000C.
8.2.0ut going from top is Na 8.3.0ut going from the bottom is Liquid Si and particulate A1203 8.4.Liquid Si is separated through porous refractory filter 8.5.Purified Alumina is continuously charged to Al producing reactor.
Alumina is given low temperature Chlorine wash.
element melting Boiling Density Metal Melting Density AH AS
point C point C g/cm3 oxide point C g/cm3 kJ/mole J/mole-K
Ca 839 1484 1.37 Ca0 2613 3.35 624.6 39.1 Mg 650 1095 1.59 Mg0 2800 3.5 592. 26.
Al 660 2467 2.37 A1203 2072 3.75 1625 50.9 Si 1411 3280 2.57 Si02 1713 2.64 911 42 Na 97 800 0.927 Na20 1132 407 140 Fe 1535 7.01 Fe203 1600 5.17 808.7 120 Ni 1472 7.9 Ni0 6.67 Cr 1860 2672 6.3 Cr203 2415 5,22 1128 81 A1203 , SiO2, CaO ,MgO are difficult to reduce by reducing gases H2,C0 in standard conditions.
Si C14 +4 Na= 4 NaC1+ Si AH = -246 K.cal 3Si02+ 6H2 + 2N2 = Si3 N4 +6 H20 AH = + 122 Kcal It will produce 2 Si3N4 A1C13+ 3Na = 3NaC1+ Al AH = -135 K.cal A1203 + 3H2 +N2 = 2A1N +3 H20 AH = + 140 It will produce 1 Al N
Mg C12 +Na = Mg +2 NaCl AH = -50 K.cal.
1/3 [ 3Mg0 +3 H2 N2 = Mg3N2 +3 I420 AH = +130 K,cal]
1/3 Mg3N2will be produced Ca C12 +Na = Ca +2 NaCl AH = - 10 K.cal.
1/3 [ 3Ca0 +3 H2 + N2 = Ca3N2 +3 H20 All = +165 K,cal]
1/20 Ca3N2will be produced Ca C12- is used in C2H2 production Price of slag products and the nitride produced Products per ton of steel Alibaba price $per kg total value $
Silicon= 116 $3/kg 348 Si3N4 140 $6/Kg 840 Al 13 $2/Kg 26 AIN 40 $/10/kg 400 Mg3N2 3-5 $ 15/kg 50 Benzene $ Kg.mole $ 5/kg 1840 $3504 Thermodynamic properties Na20 I
Melting point = 1132 C NaC1 Density = 2.27 Melting point =801 C
Sublimation temperature = 1920 C Density = 2.1 Specific heat = 72.95 J/ mole ¨C Vapor point-1413 C
AHf = 377 Kj/mole Specific heat = 36.7 j/mole-c As = 416 j/mole c AH =411 Ki/mole AS= 72.1 j/mole c HC1 Al2 03 Density =1.4 Density =3.2 Specific Heat 0.9 melting point 2072C
Melting point = -114 C AH =400. K.cal/mole Boiling point = -85 C AS= 12.2 k.cal/mole \c All = 92 Kj/mole AS =186 j/mole C Si 02 Melting point = 1770C
AH = 217 K.cal/mole AS = 9-2 K,cal/mole ¨C
Heat recoveries from exit gases and electricity generation them.
1. Low pressure compressor 2. Intercooler 3 Turbines 4 Drive compressors 5. Combustor 6 Fuels 7. Power turbine 8. Gear box 9. Incoming hot gases
5. Product cooling by heat recovery 6. Na Al 02 , Na2 SiO3 dissolving in water.
7.Drying of. Na Al 02 , Na2 SiO3 8. High temperature reactor with charging of preheated Na Al 02 , Na2 SiO3, 8.1.charging of melted Al at 1000C.
8.2.0ut going from top is Na 8.3.0ut going from the bottom is Liquid Si and particulate A1203 8.4.Liquid Si is separated through porous refractory filter 8.5.Purified Alumina is continuously charged to Al producing reactor.
Alumina is given low temperature Chlorine wash.
element melting Boiling Density Metal Melting Density AH AS
point C point C g/cm3 oxide point C g/cm3 kJ/mole J/mole-K
Ca 839 1484 1.37 Ca0 2613 3.35 624.6 39.1 Mg 650 1095 1.59 Mg0 2800 3.5 592. 26.
Al 660 2467 2.37 A1203 2072 3.75 1625 50.9 Si 1411 3280 2.57 Si02 1713 2.64 911 42 Na 97 800 0.927 Na20 1132 407 140 Fe 1535 7.01 Fe203 1600 5.17 808.7 120 Ni 1472 7.9 Ni0 6.67 Cr 1860 2672 6.3 Cr203 2415 5,22 1128 81 A1203 , SiO2, CaO ,MgO are difficult to reduce by reducing gases H2,C0 in standard conditions.
Si C14 +4 Na= 4 NaC1+ Si AH = -246 K.cal 3Si02+ 6H2 + 2N2 = Si3 N4 +6 H20 AH = + 122 Kcal It will produce 2 Si3N4 A1C13+ 3Na = 3NaC1+ Al AH = -135 K.cal A1203 + 3H2 +N2 = 2A1N +3 H20 AH = + 140 It will produce 1 Al N
Mg C12 +Na = Mg +2 NaCl AH = -50 K.cal.
1/3 [ 3Mg0 +3 H2 N2 = Mg3N2 +3 I420 AH = +130 K,cal]
1/3 Mg3N2will be produced Ca C12 +Na = Ca +2 NaCl AH = - 10 K.cal.
1/3 [ 3Ca0 +3 H2 + N2 = Ca3N2 +3 H20 All = +165 K,cal]
1/20 Ca3N2will be produced Ca C12- is used in C2H2 production Price of slag products and the nitride produced Products per ton of steel Alibaba price $per kg total value $
Silicon= 116 $3/kg 348 Si3N4 140 $6/Kg 840 Al 13 $2/Kg 26 AIN 40 $/10/kg 400 Mg3N2 3-5 $ 15/kg 50 Benzene $ Kg.mole $ 5/kg 1840 $3504 Thermodynamic properties Na20 I
Melting point = 1132 C NaC1 Density = 2.27 Melting point =801 C
Sublimation temperature = 1920 C Density = 2.1 Specific heat = 72.95 J/ mole ¨C Vapor point-1413 C
AHf = 377 Kj/mole Specific heat = 36.7 j/mole-c As = 416 j/mole c AH =411 Ki/mole AS= 72.1 j/mole c HC1 Al2 03 Density =1.4 Density =3.2 Specific Heat 0.9 melting point 2072C
Melting point = -114 C AH =400. K.cal/mole Boiling point = -85 C AS= 12.2 k.cal/mole \c All = 92 Kj/mole AS =186 j/mole C Si 02 Melting point = 1770C
AH = 217 K.cal/mole AS = 9-2 K,cal/mole ¨C
Heat recoveries from exit gases and electricity generation them.
1. Low pressure compressor 2. Intercooler 3 Turbines 4 Drive compressors 5. Combustor 6 Fuels 7. Power turbine 8. Gear box 9. Incoming hot gases
10. Out gases for H20 Energy recovery from exit gases of aluminum producing reactor.
Theory of aluminum production:
Name of Electronic Molar mass/ density Melting 6,Hfl/AS*
Heat metal or structure Enthalpy per point/boiling KJ//mole/j/mole-capacity/thermal oxide atom 0 point K conductivity Ca 2.8.8.2 40 1.65 842C/1484 8.54 /154.7 25.5 CaO 56/56 3,34 2613/2850 635/40 25.9 Mg 2,8.2 24 1.73 650/1091 8.48/128 24.8 MgO 40.3 3.6 2625/3600 601.6/28.9 37.2 Al 2.8.3 26 2.7 660/2470 10.71/284.7 24.2 A1203 101.1 3.97 2072/2977 1675.5/50.9 30/w/m-k Si 2.8.4 28 2.3 1414/3265 51.2/383 19.7 SiO2 60 3.64 1713/2950 14 w/m-k Fe 2.8.14.2 57.89 7.8 1535/12862 13,8/340 25.1 Fe2O3 159.8 5.3 1535/1565, 824.7/67.49 103.9j Heat of fusion/heat of vaporization for elements In the following a new process and equipment is presented for the production of aluminum and silicon from the single ore of these elements. The ore could be bauxite, Nephline or ceramic clay, A preliminary adjustment of the ore is performed for some ease of processing.
A stoichiometric adjustment is made for the requiement of silicon for the formation of calcium silicate and magnesium silicate. The quantity of silicon is adjusted according the production requirement of silicon. The sodium oxide is added according to the requirement to form sodium silicate.
Addition of Na2O is made according to the requirement of a1203 to form sodium aluminate (NaA102).The addition of alkali is done as caustic compound or Na and oxygen.
This adjustment of composition is done in a refractory lined vessel called a furnace or reactor.
This so called reactor has input means for introducing solid charge and gaseous material for the production of heat energy inside the reactor.
This reactor has input control and measurement of input materials.
Above said reactor has mean to discharge of liquid and gaseous product at prescribed rate and temperature and pressure to desired channels. Fiure 1 From the output channel product gases are led to energy recovery equipment and recycling.
The liquid mass is introduced to lower vessels for energy recovery purpose and lowering of temperature for processing purposed.
The output gases are CO2 and H20 but may contain N2. The output mass is Naa102. Na2SiO3 , Ca2SiO4, Mg2SiO4. Which may be called slag.
Heat extraction from high temperature slag is by means of a graphite heat exchanger.
Heat is also extracted from gases and joined in the main heat extraction line.
Another discharge line is below slag extraction line. Fe liquid is discharged from this line and it will contain all elements melting before iron.
Sodium salts are formed by metal oxides not melted with or before Fe. All sodium salts of metal are water soluble/
All slag mass is dropped in a water trough from where water soluble salts are separated from water in-soluble Production of Aluminum This process applies for aluminum production from purified alumina. The process can be extended to obtain aluminum and silicon from purified ore mixture of alumina and silica.
When it desired to produce aluminum alloys desired alloying metal oxide are added to to alumina.
When alloying element contain volatile elements these are added to element in high temperature aluminum vessel in line.
The following description is with reference to figure 2.
Small particles or powder alumina is charged through double locked hopper.
After the hopper calculated amount of oxygen is metered in ( 02) and then in the same line preheated H2 , the combined mass enters high temperature portion where refractory is water cooled. High temperature melted charge (1600C) fall in adown ward falling portion. A small distance after ward threre is exit for product gases. This is at high temperature but is cooled by coold lines from other part, In this top region high temperature is achieved almost nearly 1600 C there being some excess 112. With the introduction of 02 and H2 with the charge in this reactor we are achieving exothermic conditions for the reaction:
A1203 +3 H2+ 4 H2 +3/2 02 2A1+ 6H20 + H2 More 112 is introduced with electrodes discharge the heat energy is more than the heat of formation of A1203 (AH=-400 K.cal/ kg.mole). Refractory is graphite bricks which are cooled by conventional plate and stave coolers. Hydrogen in the reaction is in excess of any oxygen content. The system has the set up to go higher than 2100 C.
The liquid aluminum is falling down ward to graphite heat exchanger. The graphite shell is water cooled, hot water joining the exit stream from alumina reduction. Appreciable amount of hydrogen flow upward cooling the Aluminum and then taking part in very high temperature reduction at about 2100 C and then going in exit stream Product metal starts cooling down from the exit level.
The contribution from electric heating is small over- here ( 300 Kwh per ton of Al), but can be increased if contribution from gases is desired to be decreased.
In place of hydrogen CO +142 can be used as A14C3 is not formed above temperature of 1400C. Our products leave the system much above 1400C
Temperature of the exit gases (approximately 1500 C) is cooled to 700C by passing these gases through energy recovery system and then it under-goes shift reactions by introduction of CO,112 gases and heat recovery is done down to approximately 75C. Any blown out particles are retained and water is recycled and bleeds out. Hydrogen is recovered and recycled. More H2 is produced than used in reduction process.
CO2 is generated in the shift reaction. It is processed to hydrocarbon gases with considerable revenue generation.
The system is approximately same when it is desired to process the combined oxides like A1203 + SiO2 to Al and Si. This idea extends to direct alloys production of aluminum and some new materials and pure elements like Si, Mg. Ca Oxygen is introduced in alumina feed line figure 2. As it reach high temperature region the following reaction start taking place A1203+ 3/202 ¨> 2A103 This starts reacting with H2 2A103 +2 H2-- 2A10 + 2H20 The system will include Al, A10, A120 and A1202 .This mass may be at 1600C.
Our processing temperature 2072 C will be be the design target. Which in operation could be lowered.
AH298 K.Cal/MOle S298 cal/deg mole Al2 03 -400.4 12.16 A10 138 48.96 A120 -248 59.75 The furnace design is it can reach more than 2100 C .it is inter-connect of two portions 1. Top part with double lock charging hoper the charge entering an inclined refractory portion where oxygen and heated hydrogen enters, and above given reactions take place.
A high temperature mass falls down ward and enters second part of the furnace (1550 C).
2. This is high temperature part of the furnace where hydrogen is added and heat is introduced through electrodes Temperature may be raised to 2300 C. It is steel shell lined with graphite bricks. This refractory is cooled by stave coolers. All changes which are required to take place have taken place, the liquid aluminum drops to lower part of the furnace.
This is a heat exchanger where heat is extracted from the mass by entering Hydrogen.
The preheated hydrogen enter to part 1. This hydrogen is coming from shift reaction from exit gases and is obtained by reaction H2 , CO + H20 of exit gases= H2+ CO2 Shift reactions.
A conventional high temperature (HT) sweet shifting operates between 400 to 700C and uses chromium or copper promoted iron based catalysts. Synthetic gas is added to exit water stream after it has lowered is temperature to 700. After first stage of shift reaction has been performed energy is extracted and gaseous mixture goes for CO2 removal.
Then second stage of shift reaction is performed and again CO2 is removed and energy is extracted. A conventional low temperature (LT) shift, typically used to remove CO contents below 1%,operates between 300 -400 C. and uses a copper ¨zinc-aluminum catalyst. Low temperature sifting catalysts are extremely sensitive to sulfur and chlorine.
Processing of aluminum ore with HC1 High purity elements and their important compounds are obtained by this treatment of aluminum ore.
Starting with the output mass of ore treatment with caustic alkali and high heating as following:
Naa102. Ca2SiO4, Mg2SiO4. Na2SiO3 Na2SiO3+ 6 HC1 = SiC14 + 2NaC1 +3 H20 AH =-159. K,cal 2NaA102. +8 HCl = 2A1C13 +2 NaCl +4 H2O AH =-182 II
Ca2SiO4 + 8 HCl = 2CaC12 + SiC14 +4 H2O AH = -198 //
Mg2SiO4. + HCl = 2MgC12 + SiC14 +4 H20 AH = -180 //
This is highly exothermic reaction By performing this reaction two volatile compound SiC14 and AlC13 are obtained -AH m. pt. C b. pt. C
SiC14 158 -70 57 AlC13 139 193 181 And three compounds are left behind CaCl2, MgC12, NaC1 -AH m. pt. C b. pt. C
MgCl2 153 714 1418 CaCl2 190 772 NaC1 98.6 801 1465 These are separated due to their different melting points In the preparation of HC1 sodium was produced, that sodium is used to obtain elements Si, Al.
Mg Ca. Sodium Chloride produced is recycled. See Figure 4, A much more profitable process is shown in figure 5 where calculations are attached-with.
The products Si3N4, ALN, Mg3N2 may be directly attached with extrusion rolling or casting set up.
Figure 6 Utilization of CO2 Using the Ca and Mg obtained above and carbon and carbon gases CO and CO2 a new field Of organic chemistry can be started. Production of C2H2 is shown in figure 67 Production of C3114 is similar when using Mg.
CO2 can be recycled in the gaseous production system as a source of C and 02.
And CO2 +
Biomass = CO +H2 H2 +CO2= methanol Production of Al, Si from mixed material SiO2 and A1203 Figure 7 SiO2 and A1203 +10 Na = Al +Si + 5Na20 On the first step of stair case furnace Al is liquid (660 C) is filtered out the mass goes to next step of stair case furnace llooC.
Na2O is filtere out leaving Si. System can be extended further.
Two production lines: one based on hydrogen other based on Cl. Both have attractive feature and low production costs A production system based on H2and Cl is exemplified by refractory oxides. It can be enxtended to other high melting oxides like titanium oxide, chromium oxides and others.
List of drawing Figure 1. Processing of ore to produce A203, SiO2 Page lof 2 Figure 1.Captions on Figure 1 Page 2of 2 Figure 2. A two reactor to produce Aluminum from alumina Page 1 of 2 Hydrogen for the process is produced by shift conversion of CO.H2 CO2 produced is processed in figure 6 The process explained in the flow sheet is applicable to the production of Si from SiO2 And Al and Si from mixed charge of A1203 +Si02 .
This process and equipment is applicable to the production of Cr from its oxides and other high melting oxides., Figure 2. Parallel plate discharge opening and closing remote controlled Page 2 of 2 Figure 3. Production of Al, Si, Mg, Ca and Fe from aluminum Ore. Page 1 of 2 Figure 3. Production of Al, Si, Mg, Ca and Fe from aluminum Ore. Page 2 of 2 Figure 4. Production of Al and Si from mixed material A1203 +Si02 . .The drawing is extension of figure 2 Figure 5. This further extension of figure 4 for the production of Si and Si3N4 and production of Al and AIN. And other Chlorides.
Figure 6. A Process and apparatus for cyclic production of Ca for the production of C2H2 from CO,CO2 . CaO formed by reaction with CO,CO2 is regenerated by H2,C12 gases or HC1. CaC12 formed is reacted with Na forming NaC1 and Ca. Both NaC1 and Ca are recycled.
C2H2 is bases of new field of chemistry.
This process and apparatus is used for Mg and production of C3I-14 Figure 6. Production of NH4C1 from NH3 and HC1. Process is desired for disposal of Chlorine when required for the production of NaOH.
Figure 7. Production of Al and Si from mixed material A203, SiO2 Figure 8. Extrusion casting of flats, profiles for metals and alloys, Silicon Nitride, aluminum nitride Page lof 4 Figure 8 Continued presentations of profiles Page 2 of 4 Figure 8 Continued presentation of flats page 3 of 4 Figure 8 Pressure casting of net shapes page 4 of 4 Figure 9. Raw materials charging setup with measurement and amount transmitting.
Theory of aluminum production:
Name of Electronic Molar mass/ density Melting 6,Hfl/AS*
Heat metal or structure Enthalpy per point/boiling KJ//mole/j/mole-capacity/thermal oxide atom 0 point K conductivity Ca 2.8.8.2 40 1.65 842C/1484 8.54 /154.7 25.5 CaO 56/56 3,34 2613/2850 635/40 25.9 Mg 2,8.2 24 1.73 650/1091 8.48/128 24.8 MgO 40.3 3.6 2625/3600 601.6/28.9 37.2 Al 2.8.3 26 2.7 660/2470 10.71/284.7 24.2 A1203 101.1 3.97 2072/2977 1675.5/50.9 30/w/m-k Si 2.8.4 28 2.3 1414/3265 51.2/383 19.7 SiO2 60 3.64 1713/2950 14 w/m-k Fe 2.8.14.2 57.89 7.8 1535/12862 13,8/340 25.1 Fe2O3 159.8 5.3 1535/1565, 824.7/67.49 103.9j Heat of fusion/heat of vaporization for elements In the following a new process and equipment is presented for the production of aluminum and silicon from the single ore of these elements. The ore could be bauxite, Nephline or ceramic clay, A preliminary adjustment of the ore is performed for some ease of processing.
A stoichiometric adjustment is made for the requiement of silicon for the formation of calcium silicate and magnesium silicate. The quantity of silicon is adjusted according the production requirement of silicon. The sodium oxide is added according to the requirement to form sodium silicate.
Addition of Na2O is made according to the requirement of a1203 to form sodium aluminate (NaA102).The addition of alkali is done as caustic compound or Na and oxygen.
This adjustment of composition is done in a refractory lined vessel called a furnace or reactor.
This so called reactor has input means for introducing solid charge and gaseous material for the production of heat energy inside the reactor.
This reactor has input control and measurement of input materials.
Above said reactor has mean to discharge of liquid and gaseous product at prescribed rate and temperature and pressure to desired channels. Fiure 1 From the output channel product gases are led to energy recovery equipment and recycling.
The liquid mass is introduced to lower vessels for energy recovery purpose and lowering of temperature for processing purposed.
The output gases are CO2 and H20 but may contain N2. The output mass is Naa102. Na2SiO3 , Ca2SiO4, Mg2SiO4. Which may be called slag.
Heat extraction from high temperature slag is by means of a graphite heat exchanger.
Heat is also extracted from gases and joined in the main heat extraction line.
Another discharge line is below slag extraction line. Fe liquid is discharged from this line and it will contain all elements melting before iron.
Sodium salts are formed by metal oxides not melted with or before Fe. All sodium salts of metal are water soluble/
All slag mass is dropped in a water trough from where water soluble salts are separated from water in-soluble Production of Aluminum This process applies for aluminum production from purified alumina. The process can be extended to obtain aluminum and silicon from purified ore mixture of alumina and silica.
When it desired to produce aluminum alloys desired alloying metal oxide are added to to alumina.
When alloying element contain volatile elements these are added to element in high temperature aluminum vessel in line.
The following description is with reference to figure 2.
Small particles or powder alumina is charged through double locked hopper.
After the hopper calculated amount of oxygen is metered in ( 02) and then in the same line preheated H2 , the combined mass enters high temperature portion where refractory is water cooled. High temperature melted charge (1600C) fall in adown ward falling portion. A small distance after ward threre is exit for product gases. This is at high temperature but is cooled by coold lines from other part, In this top region high temperature is achieved almost nearly 1600 C there being some excess 112. With the introduction of 02 and H2 with the charge in this reactor we are achieving exothermic conditions for the reaction:
A1203 +3 H2+ 4 H2 +3/2 02 2A1+ 6H20 + H2 More 112 is introduced with electrodes discharge the heat energy is more than the heat of formation of A1203 (AH=-400 K.cal/ kg.mole). Refractory is graphite bricks which are cooled by conventional plate and stave coolers. Hydrogen in the reaction is in excess of any oxygen content. The system has the set up to go higher than 2100 C.
The liquid aluminum is falling down ward to graphite heat exchanger. The graphite shell is water cooled, hot water joining the exit stream from alumina reduction. Appreciable amount of hydrogen flow upward cooling the Aluminum and then taking part in very high temperature reduction at about 2100 C and then going in exit stream Product metal starts cooling down from the exit level.
The contribution from electric heating is small over- here ( 300 Kwh per ton of Al), but can be increased if contribution from gases is desired to be decreased.
In place of hydrogen CO +142 can be used as A14C3 is not formed above temperature of 1400C. Our products leave the system much above 1400C
Temperature of the exit gases (approximately 1500 C) is cooled to 700C by passing these gases through energy recovery system and then it under-goes shift reactions by introduction of CO,112 gases and heat recovery is done down to approximately 75C. Any blown out particles are retained and water is recycled and bleeds out. Hydrogen is recovered and recycled. More H2 is produced than used in reduction process.
CO2 is generated in the shift reaction. It is processed to hydrocarbon gases with considerable revenue generation.
The system is approximately same when it is desired to process the combined oxides like A1203 + SiO2 to Al and Si. This idea extends to direct alloys production of aluminum and some new materials and pure elements like Si, Mg. Ca Oxygen is introduced in alumina feed line figure 2. As it reach high temperature region the following reaction start taking place A1203+ 3/202 ¨> 2A103 This starts reacting with H2 2A103 +2 H2-- 2A10 + 2H20 The system will include Al, A10, A120 and A1202 .This mass may be at 1600C.
Our processing temperature 2072 C will be be the design target. Which in operation could be lowered.
AH298 K.Cal/MOle S298 cal/deg mole Al2 03 -400.4 12.16 A10 138 48.96 A120 -248 59.75 The furnace design is it can reach more than 2100 C .it is inter-connect of two portions 1. Top part with double lock charging hoper the charge entering an inclined refractory portion where oxygen and heated hydrogen enters, and above given reactions take place.
A high temperature mass falls down ward and enters second part of the furnace (1550 C).
2. This is high temperature part of the furnace where hydrogen is added and heat is introduced through electrodes Temperature may be raised to 2300 C. It is steel shell lined with graphite bricks. This refractory is cooled by stave coolers. All changes which are required to take place have taken place, the liquid aluminum drops to lower part of the furnace.
This is a heat exchanger where heat is extracted from the mass by entering Hydrogen.
The preheated hydrogen enter to part 1. This hydrogen is coming from shift reaction from exit gases and is obtained by reaction H2 , CO + H20 of exit gases= H2+ CO2 Shift reactions.
A conventional high temperature (HT) sweet shifting operates between 400 to 700C and uses chromium or copper promoted iron based catalysts. Synthetic gas is added to exit water stream after it has lowered is temperature to 700. After first stage of shift reaction has been performed energy is extracted and gaseous mixture goes for CO2 removal.
Then second stage of shift reaction is performed and again CO2 is removed and energy is extracted. A conventional low temperature (LT) shift, typically used to remove CO contents below 1%,operates between 300 -400 C. and uses a copper ¨zinc-aluminum catalyst. Low temperature sifting catalysts are extremely sensitive to sulfur and chlorine.
Processing of aluminum ore with HC1 High purity elements and their important compounds are obtained by this treatment of aluminum ore.
Starting with the output mass of ore treatment with caustic alkali and high heating as following:
Naa102. Ca2SiO4, Mg2SiO4. Na2SiO3 Na2SiO3+ 6 HC1 = SiC14 + 2NaC1 +3 H20 AH =-159. K,cal 2NaA102. +8 HCl = 2A1C13 +2 NaCl +4 H2O AH =-182 II
Ca2SiO4 + 8 HCl = 2CaC12 + SiC14 +4 H2O AH = -198 //
Mg2SiO4. + HCl = 2MgC12 + SiC14 +4 H20 AH = -180 //
This is highly exothermic reaction By performing this reaction two volatile compound SiC14 and AlC13 are obtained -AH m. pt. C b. pt. C
SiC14 158 -70 57 AlC13 139 193 181 And three compounds are left behind CaCl2, MgC12, NaC1 -AH m. pt. C b. pt. C
MgCl2 153 714 1418 CaCl2 190 772 NaC1 98.6 801 1465 These are separated due to their different melting points In the preparation of HC1 sodium was produced, that sodium is used to obtain elements Si, Al.
Mg Ca. Sodium Chloride produced is recycled. See Figure 4, A much more profitable process is shown in figure 5 where calculations are attached-with.
The products Si3N4, ALN, Mg3N2 may be directly attached with extrusion rolling or casting set up.
Figure 6 Utilization of CO2 Using the Ca and Mg obtained above and carbon and carbon gases CO and CO2 a new field Of organic chemistry can be started. Production of C2H2 is shown in figure 67 Production of C3114 is similar when using Mg.
CO2 can be recycled in the gaseous production system as a source of C and 02.
And CO2 +
Biomass = CO +H2 H2 +CO2= methanol Production of Al, Si from mixed material SiO2 and A1203 Figure 7 SiO2 and A1203 +10 Na = Al +Si + 5Na20 On the first step of stair case furnace Al is liquid (660 C) is filtered out the mass goes to next step of stair case furnace llooC.
Na2O is filtere out leaving Si. System can be extended further.
Two production lines: one based on hydrogen other based on Cl. Both have attractive feature and low production costs A production system based on H2and Cl is exemplified by refractory oxides. It can be enxtended to other high melting oxides like titanium oxide, chromium oxides and others.
List of drawing Figure 1. Processing of ore to produce A203, SiO2 Page lof 2 Figure 1.Captions on Figure 1 Page 2of 2 Figure 2. A two reactor to produce Aluminum from alumina Page 1 of 2 Hydrogen for the process is produced by shift conversion of CO.H2 CO2 produced is processed in figure 6 The process explained in the flow sheet is applicable to the production of Si from SiO2 And Al and Si from mixed charge of A1203 +Si02 .
This process and equipment is applicable to the production of Cr from its oxides and other high melting oxides., Figure 2. Parallel plate discharge opening and closing remote controlled Page 2 of 2 Figure 3. Production of Al, Si, Mg, Ca and Fe from aluminum Ore. Page 1 of 2 Figure 3. Production of Al, Si, Mg, Ca and Fe from aluminum Ore. Page 2 of 2 Figure 4. Production of Al and Si from mixed material A1203 +Si02 . .The drawing is extension of figure 2 Figure 5. This further extension of figure 4 for the production of Si and Si3N4 and production of Al and AIN. And other Chlorides.
Figure 6. A Process and apparatus for cyclic production of Ca for the production of C2H2 from CO,CO2 . CaO formed by reaction with CO,CO2 is regenerated by H2,C12 gases or HC1. CaC12 formed is reacted with Na forming NaC1 and Ca. Both NaC1 and Ca are recycled.
C2H2 is bases of new field of chemistry.
This process and apparatus is used for Mg and production of C3I-14 Figure 6. Production of NH4C1 from NH3 and HC1. Process is desired for disposal of Chlorine when required for the production of NaOH.
Figure 7. Production of Al and Si from mixed material A203, SiO2 Figure 8. Extrusion casting of flats, profiles for metals and alloys, Silicon Nitride, aluminum nitride Page lof 4 Figure 8 Continued presentations of profiles Page 2 of 4 Figure 8 Continued presentation of flats page 3 of 4 Figure 8 Pressure casting of net shapes page 4 of 4 Figure 9. Raw materials charging setup with measurement and amount transmitting.
Claims (23)
1. I have invented new process for the production of aluminum, silicon, their allied refractory metals and equipment for the production of these elements and on line production of their alloys and compounds
2. The raw material used are various type of ores. A preliminary adjustment of the ore component is performed for ease of processing. A stoichiometric adjustment is made with sodium and oxygen or a caustic compound.
3. Adjustment of composition is done in a refractory lined vessel called reactor or furnace.
This so called reactor has input means for introducing solid charge and gaseous reactants and measurements control means for the production inputs Above said reactor has means to discharge of liquid and gaseous product from various points at prescribed rate, temperature and pressure to connected channels.
This so called reactor has input means for introducing solid charge and gaseous reactants and measurements control means for the production inputs Above said reactor has means to discharge of liquid and gaseous product from various points at prescribed rate, temperature and pressure to connected channels.
4. From the output channel product gases are led to energy recovery equipment and further utilization of exit gases.
The liquid mass (slag) is introduced to lower vessels for further energy recovery purpose and lowering of temperature for processing purposed.
The output gases are CO2 and H2O but may contain N2. The output mass is NaalO2. Na2SiO3, Ca2SiO4, Mg2SiO4.
The liquid mass (slag) is introduced to lower vessels for further energy recovery purpose and lowering of temperature for processing purposed.
The output gases are CO2 and H2O but may contain N2. The output mass is NaalO2. Na2SiO3, Ca2SiO4, Mg2SiO4.
5. Heat extraction from high temperature slag is by means of a graphite heat exchanger.
Heat extracted from gases is joined in the main heat extraction line given above.
Heat extracted from gases is joined in the main heat extraction line given above.
6. Another discharge line is below slag line. Fe liquid is discharged from this line and it will contain all elements melting before iron.
7. Sodium salts are formed by metal oxides not melted with or before Fe. All sodium salts of metal are water soluble/
8. All slag mass is dropped in a water trough from where water soluble salts (Na Salts) are separated from water insoluble.
9. This process applies for aluminum production from purified alumina. The process can be extended to obtain aluminum and silicon from purified ore mixture of alumina and silica.
When it desired to produce aluminum alloys desired alloying metal oxide are added to to alumina.
When it desired to produce aluminum alloys desired alloying metal oxide are added to to alumina.
10. When alloying element contain volatile elements these are added as elements in high temperature aluminum vessel in line.
11. Small particles or powder alumina is charged through double locked hopper.
After the hopper calculated amount of oxygen is metered in (O2) and then in the same line preheated H2, the combined mass enters high temperature portion where refractory is water cooled. High temperature melted charge (1600C) fall in adown ward falling portion. A small distance after ward there is exit for product gases. These exit gases are at high temperature but are cooled by cold lines from other part of system, In this top region high temperature is achieved at nearly 1600 C there being some excess H2 in the charge. With the introduction of O2 and H2 with the charge in this reactor we are achieving exothermic conditions for the reaction:
Al2O3 +3 H2 + 4 H2 +3/2 O2 .fwdarw. 2A1 + 6H2O + H2 More H2 is introduced with electrodes discharge, the heat energy produced is more than the heat of formation of Al2O3 (.increment.H=-400 K.cal/ kg.mole). Refractory is graphite bricks which are cooled by conventional plate and stave coolers. Hydrogen in the reaction is in excess of any oxygen content. The system has the set up to go higher than 2100 C.
After the hopper calculated amount of oxygen is metered in (O2) and then in the same line preheated H2, the combined mass enters high temperature portion where refractory is water cooled. High temperature melted charge (1600C) fall in adown ward falling portion. A small distance after ward there is exit for product gases. These exit gases are at high temperature but are cooled by cold lines from other part of system, In this top region high temperature is achieved at nearly 1600 C there being some excess H2 in the charge. With the introduction of O2 and H2 with the charge in this reactor we are achieving exothermic conditions for the reaction:
Al2O3 +3 H2 + 4 H2 +3/2 O2 .fwdarw. 2A1 + 6H2O + H2 More H2 is introduced with electrodes discharge, the heat energy produced is more than the heat of formation of Al2O3 (.increment.H=-400 K.cal/ kg.mole). Refractory is graphite bricks which are cooled by conventional plate and stave coolers. Hydrogen in the reaction is in excess of any oxygen content. The system has the set up to go higher than 2100 C.
12.The liquid aluminum is falling down ward to graphite heat exchanger. The graphite shell is water cooled, hot water joining the exit stream from alumina reduction.
Appreciable amount of hydrogen flow upward cooling the Aluminum and then taking part in very high temperature reduction at about 2100 C and going in exit stream .Product metal starts cooling down from the exit level.
Appreciable amount of hydrogen flow upward cooling the Aluminum and then taking part in very high temperature reduction at about 2100 C and going in exit stream .Product metal starts cooling down from the exit level.
13.The contribution from electric heating is small over- here ( 300 Kwh per ton of Al), but can be increased if contribution from gases is desired to be decreased.
14.In place of hydrogen CO +H2 can be used as Al4C3 is not formed above temperature of 1400C. Our products leave the system much above 1400C
15.Temperature of the exit gases (approximately 1500 C) is cooled to 700C by passing these gases through energy recovery system and then it under-goes shift reactions by introduction of CO,H2 gases and heat recovery is done down to approximately 75C. Any blown out particles are retained and water is recycled and bleeds out. Hydrogen is recovered and recycled. More H2 is produced than used in reduction process.
16.CO2is generated in the shift reaction. It is processed to hydrocarbon gases with considerable revenue.
17.The system is approximately same when it is desired to process the combined oxides like Al2O3 + SiO2 to AI and Si. This idea extends to direct alloys production of aluminum and some new materials and pure elements like Si, Mg. Ca
18. Oxygen is introduced in alumina feed line figure 2. As it reach high temperature region the following reaction start taking place Al2O3+ 3/2O2 .fwdarw. 2AlO3 This starts reacting with H2 2AlO3 +2 H2.fwdarw. 2AlO + 2H2O
The system will include Al, AlO, Al2O and Al2O2 .This mass may be at 1600C.
Our processing temperature 2072 C will be the design target.while operational requirement could be lower.
The system will include Al, AlO, Al2O and Al2O2 .This mass may be at 1600C.
Our processing temperature 2072 C will be the design target.while operational requirement could be lower.
19. The furnace design (reactor) is it can reach more than 2100 C .it is inter-connect of two portions Top part with doble lock charging hoper the chrge entering an inclined refractory portion where oxgen and heated hydrogen enters, and above given reactions take place. A high temperature mass falls down ward and enters second part of the furnace (1650 C).
Lower part is high temperature part of furnace where hydrgen is added and heat is introduced through electrodes Temperature may be raised to 2300 C. It is steel shell lined with graphite bricks. This refractory is cooled by stave coolers. All changes which are required to take place have taken place the liquid aluminum drops to lower part of furnace.
This is a heat exchange where heat is extracted from liquid metal by entering hydrogen.
The preheated hydrogen enters part 1. This hydrogen is coming from shift reaction from exit gases and is obtained by reaction H2 , CO + H2O of exit gases= H2+ CO2
Lower part is high temperature part of furnace where hydrgen is added and heat is introduced through electrodes Temperature may be raised to 2300 C. It is steel shell lined with graphite bricks. This refractory is cooled by stave coolers. All changes which are required to take place have taken place the liquid aluminum drops to lower part of furnace.
This is a heat exchange where heat is extracted from liquid metal by entering hydrogen.
The preheated hydrogen enters part 1. This hydrogen is coming from shift reaction from exit gases and is obtained by reaction H2 , CO + H2O of exit gases= H2+ CO2
20. A conventional high temperature (HT) sweet shifting operates between 400 to 700C and uses chromium or copper promoted iron based catalysts. Synthetic gas is added to exit water stream after it has lowered its temperature to 700. After first stage of shift reaction has been performed energy is extracted then gaseous mixture goes for CO2 removal.
Then second stage of shift reaction is performed and again CO2 is removed and energy is extracted. A conventional low temperature (LT) shift , typically used to remove CO contents below 1%,operates between 300 -400 C. and uses a copper ¨zinc-aluminum catalyst. Low temperature sifting catalysts are extremely sensitive to sulfur and chlorine.
Then second stage of shift reaction is performed and again CO2 is removed and energy is extracted. A conventional low temperature (LT) shift , typically used to remove CO contents below 1%,operates between 300 -400 C. and uses a copper ¨zinc-aluminum catalyst. Low temperature sifting catalysts are extremely sensitive to sulfur and chlorine.
21.High purity elements and their important compounds are obtained by HCl treatment of aluminum ore.
Starting with the out put mass of ore treatment with caustic alkali and high heating as following:
NaalO2., Ca2SiO4, Mg2SiO4. Na2SiO3,+ HCl SiCl4 +AlCl3 are volatilized And three compounds are left behind CaCl2, MgCl2, NaCl These are separated due to their different melting points In the preparation of HCl sodium was produced, that sodium is used to obtain elements Si, Al.
Mg, Ca. Sodium Chloride produced is recycled.
Starting with the out put mass of ore treatment with caustic alkali and high heating as following:
NaalO2., Ca2SiO4, Mg2SiO4. Na2SiO3,+ HCl SiCl4 +AlCl3 are volatilized And three compounds are left behind CaCl2, MgCl2, NaCl These are separated due to their different melting points In the preparation of HCl sodium was produced, that sodium is used to obtain elements Si, Al.
Mg, Ca. Sodium Chloride produced is recycled.
22.A much more profitable process is: To produce Si3N4., ALN, Mg3N2 22.Using the Ca and Mg and CO and CO2 a new field Of organic chemistry is started, the production of C2H2 and C3H4 CO2 is recycled in the gaseous production system as a source of C and O2. CO2 and Biomass is used to produce CO +H2 . H2 +CO2 is used to produce methanol
23.Production of Al, Si from mixed material SiO2 and Al2O3 is done by reaction of Na..
On the first step of stair case furnace Al is liquid (660 C ) is filtered out the mass goes to next step of stair case furnace at 1100C.
Na2O is filtered out leaving Si. System can be extended further.
A production system based on H2 and Cl is exemplified by production of Al and Si from their oxides. It can be extended to other high melting oxides like titanium oxide.
chromium oxide and others.
On the first step of stair case furnace Al is liquid (660 C ) is filtered out the mass goes to next step of stair case furnace at 1100C.
Na2O is filtered out leaving Si. System can be extended further.
A production system based on H2 and Cl is exemplified by production of Al and Si from their oxides. It can be extended to other high melting oxides like titanium oxide.
chromium oxide and others.
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| CA2988445A CA2988445A1 (en) | 2017-12-12 | 2017-12-12 | Direct production of aluminum and silicon from their ore |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112499658A (en) * | 2020-12-08 | 2021-03-16 | 矿冶科技集团有限公司 | Treatment method of aluminum electrolysis waste carbon slag and obtained regenerated cryolite |
| CN114965879A (en) * | 2022-05-12 | 2022-08-30 | 中国铝业股份有限公司 | Method for determining carbon dioxide emission in aluminum electrolysis process and related equipment |
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2017
- 2017-12-12 CA CA2988445A patent/CA2988445A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112499658A (en) * | 2020-12-08 | 2021-03-16 | 矿冶科技集团有限公司 | Treatment method of aluminum electrolysis waste carbon slag and obtained regenerated cryolite |
| CN114965879A (en) * | 2022-05-12 | 2022-08-30 | 中国铝业股份有限公司 | Method for determining carbon dioxide emission in aluminum electrolysis process and related equipment |
| CN114965879B (en) * | 2022-05-12 | 2023-10-24 | 中国铝业股份有限公司 | Method for determining carbon dioxide emission in aluminum electrolysis process and related equipment |
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