Production of ferroboron

TECHNICAL FIELD
This invention relates to a process for producing ferroborons. In one embodiment, ferroboron is produced from colemanite or other borates.
BACKGROUND ART
Present technologies produce boron alloys by means of smelting processes that utilize either carbon or aluminum as the reducing agent for boron anhydride, B.sub.2 O.sub.3. The rapidly expanding field is essentially associated with the development of amorphous metals having very low magnetic losses, with typical alloys being Fe--Ni--B and Fe--B--Si. These alloys find their applications in motor and transformer cores and the electronic industry in general.
The standard smelting processes for producing ferroboron alloys seem to have in common a low boron yield that perhaps reflects the relatively high cost of producing the alloy.
The normal starting material for producing ferroboron is boric acid which, upon dehydration, converts to boron anhydride, B.sub.2 O.sub.3. This boron oxide is very stable and can be reduced to metallic boron with carbon, aluminum or magnesium.
Smelting is the general approach to ferroboron production, but process yields are only around 40%. Besides the yield drawback of present smelting practices, carbon reduction produces ferroboron containing approximately 2% carbon; aluminum reduction produces ferroboron containing approximately 1.5% aluminum; and magnesium reduction has inherent high magnesium losses and slag-metal separation difficulties.
DISCLOSURE OF INVENTION
In my scheme to ferroboron alloys production, I have taken an entirely different approach to lower the energy requirements and improve the overall boron yield. My process relies on solid state reactions among colemanite, aluminum and iron to generate primarily ferroborn sintered within a matrix of calcium aluminates. Liberation of the alloy from this matrix and subsequent smelting is seen as an alternative to present smelting practices.
The solid ferroboron is made at low temperatures by solid and liquid state reactions in order to save on energy. It takes advantage of the exothermic heat of reaction to the fullest. The subsequent smelting of the alloy requires, in general, energy only for a fraction of the total feed to the process. Another advantage is that my process does not require highly refined starting materials such as boric acid.
This process consists of reacting a borate with aluminum powder in the presence of iron powder to produce solid ferroboron alloys by solid and liquid state reactions in the temperature range from 700.degree. to 1200.degree. C. hereupon identified as "solid state reactions". Typical reactions are:
2CaO.3B.sub.2 O.sub.3 +6Al+6Fe.revreaction.6FeB+3Al.sub.2 O.sub.3 +2CaO
2CaO.3B.sub.2 O.sub.3 +9Mg+6Fe.revreaction.6FeB+2CaO+9MgO
When reducing borates with aluminum, the addition of CaO is beneficial in producing more desirable calcium aluminate species for the mineral processing of the calcine produced or the subsequent smelting of the total sintered mass.
The calcine produced is then crushed and ground to liberate the ferroboron alloys from the calcium aluminates. The ground calcine is then subjected to magnetic separation to recover a concentrate containing the boron-iron alloys. The tails are discarded. The granular magnetic concentrate is then smelted and refined to satisfy end use specifications. This is scheme A in the Figure.
Iron is used as collector for boron, and its proportion can be varied depending upon the grade of ferroalloy required. However, the proportion of iron may be adjusted in order not to sacrifice boron recovery. The aluminum requirement is, in general, 2.5 grams per gram boron present in the process feed as borates. However, the aluminum addition can be reduced in order to decrease the residual Al level in the FeB alloy or it can be increased to improve boron recovery. Instead of Fe as collector, Fe.sub.2 O.sub.3 and/or Fe.sub.3 O.sub.4 and/or FeO can be used with an attendant increase in Al and/or Mg requirements as reductants. The process then is carried out by direct smelting. This is also the case when CaO is added to adjust the CaO-Al.sub.2 O.sub.3 ratio between 0.85 and 1.06. This is scheme B in the FIGURE.
The B.sub.2 O.sub.3 may be supplied by many different borate compounds. The following is a list of some of the more readily available borate compounds:
______________________________________Mineral or Chemical Name Chemical Formula______________________________________Boric acid H.sub.3 BO.sub.3Anhydrous boric acid B.sub.2 O.sub.3Anhydrous borax Na.sub.2 O.2B.sub.2 O.sub.35 Mol borax Na.sub.2 O.2B.sub.2 O.sub.3.5H.sub.2 OBorax Na.sub.2 O.2B.sub.2 O.sub.3.10H.sub.2 ODehydrated Rasorite Na.sub.2 O.2B.sub.2 O.sub.3Probertite Na.sub.2 O.2CaO.5B.sub.2 O.sub.3.10H.sub.2 OUlexite Na.sub.2 2CaO.5B.sub.2 O.sub.3.16H.sub.2 OColemanite 2CaO.3B.sub.2 O.sub.3.5H.sub.2 OCalcined colemanite 2CaO.3B.sub.2 O.sub.3.H.sub.2 OSodium Perborate NaBO.sub.2.H.sub.2 O.sub.2.3H.sub.2 O______________________________________
Because of the disadvantages of relatively large amounts of water or soda in many of these compounds, ulexite, colemanite and especially calcined colemanite are preferred.

BRIEF DESCRIPTION OF THE DRAWING
The FIGURE shows a flow sheet of the process according to this invention.

BEST MODE OF CARRYING OUT INVENTION
Thermodynamic Properties
Colemanite is a mineral of composition 2CaO.3B.sub.2 O.sub.3.5H.sub.2 O that upon calcination converts to 2CaO.3B.sub.2 O.sub.3.
The free energy and heat of formation of calcined colemanite were estimated as a linear combination of the properties of two other calcium borates as follows (Kcal):
______________________________________Species .DELTA.G.sub.f 298 .DELTA.H.sub.f 298CaO.B.sub.2 O.sub.3 -457.7 -483.3CaO.2B.sub.2 O.sub.3 -752.4 -798.82CaO.3B.sub.2 O.sub.3 -1.210 -1.282Reduction by Aluminum2CaO.3B.sub.2 O.sub.3 + 6Al .revreaction.2CaO + 3Al.sub.2 O.sub.3 + 6B .DELTA. G = -213 Kcal (Feasible) .DELTA. H = -220 Kcal (Exothermic)______________________________________
The stoichiometric aluminum requirement is 2.5 units per unit weight of boron.
Reduction by Magnesium
2CaO.3B.sub.2 O.sub.3 +9Mg.revreaction.9MgO+2CaO+6B
.DELTA.G=-303 Kcal (Feasible)
.DELTA.H=-386 Kcal (Exothermic)
The stoichiometric magnesium requirement is 3.37 units per unit weight of boron.
Process Impact of Physical Properties
Some of the physical properties of elements and compounds of interest in the reduction of borates are given in Table 1. These properties, in general, will affect the efficiency of the reduction process, the selection of reductant and the choice of equipment to perform the reduction reaction.
To be sure, the presence of water, carbonates and air leakages in the system, for example, will oxidize more drastically Mg than Al. Carbonates will contribute to the level of carbon in the ferroboron alloy depending upon the temperature of reaction. The low melting temperature of colemanite, magnesium and aluminum will induce sintering which brings up the questions of choice between loose or briquetted feed and type of reactor. The low boiling point of magnesium adds to this metal total loss and to the careful design of equipment to prevent fire hazards.
The advantages of aluminum over magnesium concerning its reduced oxidation and volatization losses, and the more favorable stoichiometric requirements and slag characteristics. These facts determined our primary thrust in using aluminum as the reducing agent for colemanite and borates in general.
TABLE 1______________________________________SOME PHYSICAL PROPERTIES OF ELEMENTS ANDCOMPOUNDS OF INTERESTIN FERROBORON PRODUCTIONSpecies Process Temperature, .degree.C.______________________________________2CaO.3B.sub.2 O.sub.3.5H.sub.2 O Dehydration 315-4052CaO.3B.sub.2 O.sub.3 Fusion 646CaCO.sub.3 Decomposition 860-1,010Mg.sub.(s) Fusion 650Mg.sub.(1) Boiling 1,110Al.sub.(s) Fusion 660Al.sub.(1) Boiling 2,060______________________________________
Ferroboron Test Procedures
The invention was designed according to the flowsheet shown in the FIGURE. The effort was concentrated on the "solid state" reaction scheme which is identified as branch A on the conceptual flowsheet.
The operating procedures of the "solid state" reaction were as follows:
Materials Specifications. The reduction process was carried out using calcined colemanite as process feed, aluminum powder as reducing agent and iron powder as the collector to form the ferroboron alloys.
The particle size of the calcined colemanite was essentially -65 mesh, and its chemical assays are given below.
______________________________________Sample: Calcined ColemaniteChemical Assay: Wt. %B CaO MgO Fe SiO.sub.2 Al.sub.2 O.sub.3 CO.sub.2 LOI______________________________________13.39 35.1 0.34 0.16 1.27 0.16 12.46 12.60______________________________________
The particle size of the aluminum powder was -325 mesh, and the iron powder was investigated in two particle size ranges: -100 mesh and -325 mesh.
The iron ore used for this purpose was the Carol Lake spiral concentrate, sample No. 82-6, ground to -150 mesh and having the following chemistry:
______________________________________ Assay: Wt. %Sample Fe.sub.T SiO.sub.2 Al.sub.2 O.sub.3 CaO MgO LOI______________________________________Carol Conc. 66.18 4.35 0.13 0.14 0.4 0.32______________________________________
The general procedures are as follows:
Loose Charges
1. The calcined colemanite is thoroughly blended with the required amounts of iron and aluminum powders. 2. The loose charges are placed in alumina crucibles and loaded inside the Pereny furnace which had been heated to the desired temperature.
3. After loading several crucibles, the furnace temperature is allowed to come back to the set point temperature. The reaction is then allowed to proceed for a specified length of time.
4. The reaction in step 3 is carried out either under a nitrogen or a CO/CO.sub.2 atmosphere. A total gas flow of 7 lpm was used in all cases. For the tests under the reducing atmosphere, the gas was 70% CO and 30% CO.sub.2.
5. At the end of the reaction period, the rucibles are transferred to a water cooled chamber flushed with 5 lpm nitrogen.
6. The cool reacted charge is crushed to -35 mesh and wet ground at 50% pulp density and 20% ball charge for a specified length of time. The slurry is filtered and the solution sampled for analysis. The filter cake is dried at 110.degree. C. overnight.
7. The dried cake is broken down to -100 mesh and a sample of about 25 grams is taken using a mechanical splitter.
8. The 25-g sample is slurried and fed through a series arrangement of two magnetic separators. The first separator is a Davis Tube operating at 6,000 gauss while the second, a Carpco separator, is opeated at 10,000 gauss.
9. The magnetic and non-magnetic products are dried, pulverized and submitted for chemical and X-ray analyses.
10. A material balance on boron is calculated for each test.
Briquetted Charges
1. The calcined colemanite is thoroughly blended with the required amounts of iron and aluminum powders.
2. The blend is briquetted by applying a pressure of 30,000 psi in a single die mold.
3. The briquettes are then allowed to react using either the Pereny furnace, a rotary glass drum or an induction furnace.
4. The testing procedure is contined as in the case for loose charges.
Similar experimental procedures were followed for loose and briquetted charges when iron oxides and/or CaO were used as components of the blend.
The use of Fe.sub.2 O.sub.3, and iron oxides in general, had the dual purpose of generating the metallic iron to collect the boron produced by aluminum reduction, as well as providing for some FeO to flux the slag to reasonable melting temperatures. The effect of CaO was to provide a fluxing action by shifting the CaO--Al.sub.2 O.sub.3 ratio within the range of 0.85 to 1.1.
To carry out the ferroboron generating reactions, the reactors used were a muffle furnace for crucible test, a rotary glass drum to simulate the rotary kiln operation with briquetted charges and an induction furnace for the smelting of briquetted charges.
INDUSTRIAL APPLICABILITY
The following examples are given to illustrate the advantages of the invention but should not be construed as limiting in scope.
EXAMPLE SET 1
The effects of temperature and addition levels of Al and Fe on loose charges under a nitrogen atmosphere are summarized in Table 2. These data simply indicate that ferroboron alloys can be made at temperatures well below the fusion temperature of the slag forming constituents. Major constituents of the Davis Tube Concentrate, DTC, were FeB and Fe.sub.2 B.
EXAMPLE SET 2
These tests summarize the reduction performance of several borate species at high levels of iron addition under a nitrogen atmosphere. These tests were carried out on loose charges, and the results are given in Table 3.
EXAMPLE SET 3
These tests describe the reduction behavior of colemanite under a strongly reducing CO--CO.sub.2 atmosphere at high levels of iron. The difference between a stagnant and a dynamic atmosphere is characterized by the results of crucibles and rotary glass drum respectively. The data are given in Table 4.
This data shows that because of the high oxygen affinity of aluminum, the use of even a reducing direct fired fossil fuel reactor is not possible, but external firing with an internal inert atmosphere remains a choice.
EXAMPLE SET 4
These tests describe the effects of temperature and the addition levels of Al, Fe and CaO under a reducing CO--CO.sub.2 atmosphere. The high levels of iron produce 4 to 6% ferroboron alloys in the Davis tube concentrate, DTC. These data are given in Table 5.
EXAMPLE SET 5
These tests summarize the behavior of colemanite reduction with Mg under a reducing CO--CO.sub.2 atmosphere in the presence of metallic iron or ferric iron oxide. For more efficient use of the Mg reductant, the reaction must be carried out in an inert atmosphere to avoid unnecessary Mg combustion. The experimental data are given in Table 6.
EXAMPLE SET 6
These tests describe the behavior of colemanite reduction by aluminum in the presence of ferric oxide and coal under a reducing CO--CO.sub.2 atmosphere. The data are given in Table 7. These results indicate that the use of iron oxides requires the technique of direct smelting due to low melting point of the fluxed charge. The possibility of partially substituting aluminum with carbon is not a feasible approach.
EXAMPLE SET 7
These tests show the feasibility of ferroboron production from colemanite by direct smelting in the presence of iron oxides and/or calcium oxide under a nitrogen atmosphere. The data are shown in Table 8.
TABLE 2__________________________________________________________________________FERROBORON FROM COLEMANITE USING LOOSE CHARGESTests Performed in Alumina Crucibles Atmosphere: Nitrogen (7 1 pm thru Pereney)Reaction Time = 90 Minutes Colemanite Weight: 100 Grams MILL Magnetic Boron Assays: Reagents, Cal- Vol- Separation gpl or Wt. % BoronTest Temp., Grams cine ume, Wt. Dist.: % Solu- Boron Distribution: AccountedNo. C Al Fe Grams Liters DTC DTT tion DTC DTT Solution DTC DTT %__________________________________________________________________________2-1 732 45 40 182.3 1.5 42.11 57.89 0.1 11.9 5.6 1.79 59.64 38.57 108.52-2 800 40 30 162.87 1.6 31.38 68.62 0.1 7.47 6.4 2.32 33.99 63.69 79.52-3 800 50 30 183.21 1.3 36.21 63.79 0.13 9.50 6.4 2.20 44.72 53.08 99.642-3.sup.(1) 800 50 30 41.73 20.36/37.91 0.13 5.12 6.55/4.52 3.16 39.92 24.91/32.01 69.072-4 800 40 50 187.6 1.5 47.66 52.34 0.11 6.82 6.08 2.50 49.27 48.23 86.362-5 800 50 50 201.4 1.7 48.72 51.28 0.13 5.75 5.28 3.85 48.89 47.26 80.832-6 900 36.6 40 170.5 1.9 32.36 67.64 0.10 14.9 4.48 2.36 59.96 37.68 96.982-7 900 53.41 40 192.0 1.8 33.62 66.38 0.04 11.4 5.76 0.93 49.59 49.48 105.512-8 900 45 21.83 164.3 1.9 51.50 48.50 0.08 10.2 4.32 2.03 70.04 27.93 87.322-9 900 45 56.82 201.0 1.2 30.72 69.28 0.07 9.73 5.6 1.21 42.99 55.80 99.212-10 900 45 40 176.33 1.9 45.37 54.63 0.09 10.2 4.8 2.30 62.36 35.34 92.52-11 900 45 40 177.18 1.5 33.37 66.63 0.06 10.4 4.96 1.31 50.55 48.14 86.392-12 900 45 40 177.3 1.7 35.20 64.70 0.09 9.97 4.32 2.37 54.35 43.28 80.942-13 900 45 40 177.0 2.0 33.62 66.38 0.05 10.4 4.8 1.47 51.55 46.98 85.22-14 900 45 40 177.47 1.6 46.50 53.50 0.06 10.2 3.84 1.39 68.80 29.81 86.852-15 900 45 40 177.75 1.6 42.43 57.57 0.08 9.5 4.16 1.95 61.50 36.55 82.52-16 1000 40 30 163.86 1.8 32.11 67.89 0.08 10.9 4.64 2.12 51.52 46.36 78.862-16.sup.(3) 1.0 28.42 -- /71.58 0.11 11.8 --/3.18 4.31 57.00 38.69 72.02-17 1000 50 30 174.42 1.5 33.05 66.95 0.05 8.14 4.96 1.23 44.20 54.57 75.422-18 1000 40 50 183.57 1.4 47.02 52.98 0.09 9.97 4.48 1.75 65.22 33.03 93.462-18.sup.(3) 1.0 43.15 --/56.85 0.11 10.10 --/2.79 3.82 70.52 25.66 84.672-19 1000 50 50 197.22 1.2 40.13 59.87 0.08 7.92 5.6 1.45 47.96 50.59 92.692-20 1068 45 40 178.66 1.5 41.17 58.8 0.05 9.88 4.10 1.14 62.06 36.80 83.212-21 1068.sup.(2) 45 40 183.97 1.4 37.90 62.10 0.06 9.89 5.51 1.16 51.67 47.17 94.822-21 1068.sup.(1) 45 40 1.4 41.82 11.75/46.43 0.06 7.62 5.6/3.99 1.45 55.12 11.38/32.05 75.46__________________________________________________________________________ Notes: .sup.(1) These calcines were reground and evaluated through a Davis TubeCarpco separation. The figures under DTT separated by a slash actuall represent the Carpco concentrate and tail respectively. Reground in 3" .times. 6" with 12% ball charge @ 50% pulp density for 15 minutes. .sup.(2) Beginning with this test, the iron used as collector for boron was -100 mesh rather than -325 M previously used. .sup.(3) Reground in 6" .times. 6" mill with 20% ball charge @ 50% pulp density for 15 minutes. DTC = Davis Tube Concentrate DTT = Davis Tube Tail
TABLE 3__________________________________________________________________________FERROBORN FROM SEVERAL BORATESTests Performed in Alumina Crucibles Using Excess IronReaction Time = 90 Minutes Atmosphere: NitrogenCharges: Loose Borate Weight: 100 Grams MILL* Boron Assays: Reagents, Grind Magnetic Separation gpl or Wt. % Boron Distribution: BoronTest Temp., Grams Calcine Solution, Wt. Dist.: % MILL MILL AccountedNo. C Al Fe Grams Liters DTC DTT Solution DTC DTT Solution DTC DTT %__________________________________________________________________________3-22.sup.(1) 900 45 100 238.7 3.5 80.63 19.37 0.04 5.18 3.56 2.80 83.43 13.77 83.963-23.sup.(1) 900 45 150 290.53 2.2 84.09 15.91 0.06 4.28 2.72 3.17 86.44 10.39 84.643-24.sup.(2) 900 45 150 275.44 2.4 82.80 17.20 0.4 3.41 1.78 23.47 69.04 7.49 81.193-25.sup.(3) 900 45 150 280.46 2.2 76.04 23.96 0.07 3.84 3.23 4.00 75.89 20.11 98.22__________________________________________________________________________ Notes: .sup.(1) Tests 322 and 323 were run using 100g colemanite analyzing 14.0% boron. .sup.(2) Test 324 was run using 100g Na.sub.2 B.sub.4 O.sub.7.10H.sub.2 O analyzing 11.8% boron. .sup.(3) Test 325 was run using 100g probertite analyzing 10.7% boron. Significant swelling of the charge occured. *Calcines were actually ground in 6" .times. 6" mill with 20% ball charg @ 50% pulp density for 30 minutes. DTC = Davis Tube Concentrate DTT = Davis Tube Tail
TABLE 4__________________________________________________________________________FERROBORON FROM COLEMANITE Atmosphere: 70% CO & 30% CO.sub.2Reaction Time = 90 Minutes Colemanite Weight: 100 grams MILL* Rea- Grind Magnetic Separation Boron Assays: gents, Cal- Vol- Wt. Distribution: % gpl or Wt. % Boron Distribution: BoronTest Temp., Grams cine ume, Carpco Carpco MILL Carpco MILL Carpco AccountedNo. .degree.C. Al Fe Grams Liters DTC Conc. Tail Sol. DTC Conc. Tail Sol. DTC Conc. Tail %__________________________________________________________________________A. Loose Charges Reacting in Crucibles.4-26 800.sup.(1) 35100 230.48 1.4 78.26 7.39 14.35 0.14 5.54 5.951.42 3.79 83.78 8.50 3.93 83.364-26 800.sup.(6) 2.4 65.44 0.39 34.17 0.14 5.26 4.87 6.15 63.39 30.46 86.804-27 800.sup.(1) 40100 235.4 1.2 83.46 7.87 8.67 0.08 5.54 5.952.09 1.79 86.12 8.72 3.37 89.354-28 900 35100 233.41 1.45 66.39 0.52 33.09 0.14 5.44 4.50 3.96 70.97 25.07 83.574-29 900 40100 240.1 1.0 63.35 0.49 36.16 0.13 4.94 3.93 2.76 67.03 30.21 79.394-30 900.sup.(2) 40100 229.96 1.15 62.38 1.25 36.37 0.06 4.60 5.49 1.38 58.63 39.99 81.364-31 800.sup.(3) 35100 228.08 1.1 40.99 0.46 58.55 0.11 0.88 7.19 2.54 9.13 88.33 76.544-32 800 40100 238.47 1.15 63.84 0.46 35.7 0.13 4.54 3.90 3.35 65.44 31.21 74.5B. Briquetted Charges Reacting in Rotary Glass Drum, RGD.4-7.sup.(4) 800 40100 234.61 4.6 41.20 12.54 46.26 0.07 1.84 5.995.47 7.4 17.07 17.29 58.24 72.8 RGD4-8.sup.(4) 900 40100 233.91 3.1 37.67 1.09 61.24 0.15 1.26 4.83 11.89 12.49 75.62 63.63 RGDC. Test to Elucidate Behavior of Section B Above, Uring Briquettes inCrucibles & Rotary Drum.4-47.sup.(5) 900 40100 252.38 85.60 0.42 13.98 4.97 2.57 92.25 7.75 83.554-47.sup.(6) 2.6 59.98 0.52 39.50 0.14 5.09 4.16 7.2 60.33 32.47 87.264-9.sup.(5) 900 40100 232.0 76.21 0.51 23.28 4.61 4.30 77.94 22.06 75.204-9.sup.(6) 7.5 42.07 0.62 57.31 0.07 2.18 6.41 10.24 18.14 71.62 80.05__________________________________________________________________________ RGD Notes: .sup.(1) Heat of reaction temporarily overheated calcine to 1000.degree. C. (2 minutes). .sup.(2) Test reaction time was 15 minutes. .sup.(3) Charge reacted partially. .sup.(4) Calcines were ground in 6" .times. 3" steel mill with 12% ball charges @ 50% pulp density for 30 minutes. .sup.(5) Calcines were dry ground in Shatterbox. .sup.(6) Calcines were reground in 6" .times. 6" steel mill with 20% ball charge @ 25% pulp density for 15 minutes. *Calcines were generally ground in 6" .times. 6" steel mill with 20% ball charge @ 50% pulp density for 30 minutes DTC = Davis Tube Concentrate
TABLE 5__________________________________________________________________________FERROBORON FROM COLEMANITEWITH CaO ADDITIONReaction Time = 90 Minutes Atmosphere: 70% CO & 30% CO.sub.2Charges: Loose Colemanite Weight: 100 grams Magnetic MILL* Separation Grind Wt. Distribution: Boron Assays: Boron Reagents, Cal- Vol- % gpl or Wt. % Boron Distribution: Ac-Test Temp., Grams cine ume, CARPCO MILL CARPCO MILL CARPCO countedNo. .degree.C. Al Fe CaO Grams Liters DTC Conc. Tails Sol. DTC Conc. Tail Sol. DTC Conc. %ail__________________________________________________________________________5-39 900 35 75 23 229.60 1.3 50.63 0.7448.63 0.06 5.75 --4.85 1.45 54.80 --43.75 87.195-40 900 35 100 23 255.78 1.3 54.75 0.7644.49 0.07 4.58 --5.27 1.83 51.07 --47.10 89.945-41 900 40 75 35 261.17 1.0 61.34 0.0838.58 0.03 4.58 --3.76 0.7 65.52 --33.78 79.755-42 900 40 100 35 281.67 1.4 63.87 0.3935.74 0.04 4.29 --4.17 1.31 64.06 --34.63 85.855-43 1000 35 75 23 241.28 1.2 43.67 0.3555.98 0.16 5.02 --4.59 3.88 44.45 --51.67 83.745-44 1000 35 100 23 266.39 1.2 59.13 --40.87 0.17 4.88 --4.85 4.03 56.89 --39.08 94.085-45 1000 40 75 35 262.08 1.0 44.59 0.0655.35 0.18 4.73 --4.76 3.65 42.87 --53.48 90.145-46 1000 40 100 35 284.12 1.2 49.98 0.2249.8 0.12 4.15 --5.53 2.89 41.82 --55.29 99.20__________________________________________________________________________ *Calcines were actually ground in 6" .times. 6" steel mill with 20% ball charge @ 50% pulp density for 30 minutes. DTC = Davis Tube Concentrate
TABLE 6__________________________________________________________________________FERROBORON FROM COLEMANITEMAGNESIUM REDUCTION.sup.(1)Reaction Time = 90 MinutesCharges: Loose Atmosphere: 70% CO & 30% CO.sub.2 Magnetic MILL* Separation Reagents, Grind Wt. Distribution: Boron Assays: Boron Grams Cal- Vol- % gpl or Wt. % Boron Distribution: Ac-Test Temp., Carol cine ume Carpco MILL Carpco MILL Carpco countedNo. .degree.C. MgFeConc. Grams Liters DTC Conc. Tail Sol DTC Conc. Tail Sol. DTC Conc. %ail__________________________________________________________________________6-48 900 47.2 100 -- 263.06 1.2 49.44 --50.56 0.22 2.77 --3.81 7.42 38.47 --54.11 63.86-49.sup.(2) 900 56.5 -- 75 162.6? 1.0 65.20 --34.8 0.11 3.55 --2.40 3.38 71.00 --25.62 74.746-50.sup.(3) 900 64.0 -- 60 174.34? 1.0 61.86 --38.14 0.15 5.42 --2.32 3.42 76.41 --20.17 67.30__________________________________________________________________________ NOTES: .sup.(1) A very violent reaction developed, more likely as a result of th reaction between Mg, Fe.sub.2 O.sub.3 and the CO/CO.sub.2 atmosphere. The crucibles were shattered and a satisfactory recovery of the calcines was not possible, especially for tests 649 and 50. .sup.(2) Colemanite weight was 50 grams rather than the standard 100 grams. .sup.(3) Colemanite weight was 80 grams rather than the standard 100 grams. *Calcines were actually ground in a 6" .times. 6" steel mill with 20% bal charge @ 50% pulp density for 30 minutes. DTC = Davis Tube Concentrate
TABLE 7__________________________________________________________________________FERROBORON FROM COLEMANITE IN THEPRESENCE OF IRON OXIDES & COAL Atmosphere: 70% CO & 30% CO.sub.2Reaction Time = 60 Minutes Colemanite Weight: 100 Grams Magnetic Reagents, Grams MILL* Separation Co- Grind Wt. Distribution: Boron Assays: Boron Car- lom- Cal- Vol- % gpl or Wt. % Boron Distribution: Ac-Test Temp., ol bian cine ume Carpco MILL Carpco MILL Carpco countedNo. .degree.C. Al Conc Coal Grams Liters DTC Conc. Tail Sol. DTC Conc. Tail Sol. DTC Conc. %ail__________________________________________________________________________A. Loose charge of feed blend was reacted in the Pereney furnace usingopen crucibles.7-33 900.sup.(1) 83.5 150 -- Lost (Test was lost due to broken crucible by violent reaction.)(90Min.)7-34 900.sup.(1) 59.0 75.0 -- 221.0 1.25 30.10 --69.9 0.10 11.0 --2.04 2.57 68.10 --29.33 75.7(90Min.)B. Briquetted charge of feed blend was reacted in the Pereney furnaceusing open crucibles. Only a fraction of the blend was used.7-35 900.sup.(1) 83.5 150 -- Lost Met- But- 98.4 7.82 55.00 al ton7-36 900 59 75 -- 164.41 1.68 8.39 --91.61 0.10 7.66 --2.00 1.52 9.6 27.36 78.64 Met- But- 56.54 95.39 -- 4.61 12.10 --9.45 59.28 -- 2.24 al ton Overall Recoveries 1.52 68.88 29.67-37 900 35 150 45 261.85 2.2 14.85 --85.15 0.08 2.75 -- 5.88 3.15 7.3 --89.55 102.57-38 900 35 75 22.5 202.28 1.9 31.98 5.262.82 0.14 7.33 --3.91 4.88 50.03 --45.09 76.8__________________________________________________________________________ NOTES: .sup.(1) The thermite reaction was quite violent, resulting in fusion of the charge and loss of Test 733 and 35 due to reacted crucible. *Calcines were ground in the 6" .times. 6" steel mill with 20% ball charg @ 50% pulp density for 30 minutes. DTC = Davis Tube Concentrate
TABLE 8__________________________________________________________________________FERROBORON BY DIRECT SMELTING Atmosphere: Nitrogen Blend Products Wt. Assays: Boron BoronTest Temp., Carol Amount Distri- gpl or Wt. Distri- AccountedNo. .degree.C. Colemanite Al Fe Conc. CaO CaF.sub.2 Name Grams bution % B Al bution %__________________________________________________________________________8-1.sup.(1) 1650 40 20 20 -- -- 20 Calcine 88.7 DTC 43.94 10.9 -- 75.9 DTT 56.06 2.08 -- 18.58-2.sup.(1) 1650 40 20 20 -- 20 20 DTC 39.74 10.4 -- CTT 60.26 2.08 --83.sup.(2) 1650 (Composite of DTC from Tests 2-6 thru 21) HD. Compo 52.9 100.0 8.93 0.64 Met. Button 13.38-4.sup.(3) 1350 100 83.5 -- 150 -- -- Calcine 367.04 Met. Button 109.39 29.8 7.31 7.09 59.69 94.8 DTC 3.43 2.46 2.31 Carpco Tail 66.76 2.01 36.78 Grind Vol. 1.5.sup.(1) 0.03 1.228-5.sup.(3) 1600 100 35 75 -- 23 -- Calcine 294.18 100.3 Met. Button 80.12 27.24 10.8 0.265 61.43 DTC 2.62 7.56 4.14 Carpco Tail 70.14 2.32 33.98 Grind Vol. 1.1.sup.(1) 0.02 0.45__________________________________________________________________________ NOTES: .sup. (1) Attempts to smelt without the use of CaO and/or FeO. The charge showed signs of incipient fusion but the crucibles broke and tests were lost. Partial evaluation was done to get an indication of possible recovery. .sup.(2) This was an attempt to smelt a Davis Tube concentrate composite. A metal bottom was recovered but the charge did not melt and the crucible was destroyed by heat & chemical reation. .sup.(3) These were smelting tests using fluxes to drop the melting point of the slag. A double crucible arrangement was used in these tests in an effort to obtain a material balance. DTC = Davis Tube Concentrate DTT = Davis Tube Tail

Number	Name	Date
3030204	Staggers et al.	Apr 1962
4197218	McKaveney	Apr 1980
4397691	Hamada	Aug 1983

Production of ferroboron

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