EP0109839A2 - Method of making graphite electrodes - Google Patents
Method of making graphite electrodes Download PDFInfo
- Publication number
- EP0109839A2 EP0109839A2 EP83307051A EP83307051A EP0109839A2 EP 0109839 A2 EP0109839 A2 EP 0109839A2 EP 83307051 A EP83307051 A EP 83307051A EP 83307051 A EP83307051 A EP 83307051A EP 0109839 A2 EP0109839 A2 EP 0109839A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrode
- boron
- boronated
- graphitized
- anthracite coal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B7/00—Heating by electric discharge
- H05B7/02—Details
- H05B7/06—Electrodes
- H05B7/08—Electrodes non-consumable
- H05B7/085—Electrodes non-consumable mainly consisting of carbon
Definitions
- the invention relates to a unique process for manufacturing graphite electrodes for electric arc furnace applications and the unique electrodes resulting from the practice of the process.
- the principal object of this invention is to provide a method for manufacturing electrodes acceptable for use in electric arc furnaces in which the starting carbonaceous source material is not necessarily entirely premium grade petroleum coke.
- This invention resides in subjecting a carbonaceous source material, other than premium petroleum coke,-and preferably anthracite coal, to the action of elemental boron or a boron compound, preferably boron carbide (B 4 C), whereby the highly disordered structure of the anthracite coal is transformed into one that is very graphitic in an otherwise conventional electrode manufacturing process.
- a carbonaceous source material other than premium petroleum coke,-and preferably anthracite coal
- the single figure of the drawing is a graph illustrating the improvement in oxidation resistance of electrodes employing in their manufacture boronated anthracite coal as compared to electrodes employing non-boronated anthracite coal.
- particles of a non-petroleum coke carbonaceous material are mixed together with the conventional pitch binder and lubricants, and to this mixture is added elemental boron or a boron containing compound.
- Acceptable carbonaceous source materials other than anthracite coal are bituminous coal, lignites and No. 2 and No. 3 cokes.
- the boron source is one which does not release a gaseous by-product when it is to be reacted with the carbonaceous material at the graphitization step in the manufacturing process.
- Such boron sources are elemental boron, boron carbide (B 4 C), silicon tetraboride (B 4 Si) and iron boride (FeB).
- the boron material can be incorporated with the carbonaceous material during calcination and in this procedure the boron compound may be an oxide such as boric acid (H 3 B0 3 ) or boric oxide (B 2 0 3 ) since the gaseous by-product formed would have no effect on the structural integrity of the finished electrode.
- the boron compound may be an oxide such as boric acid (H 3 B0 3 ) or boric oxide (B 2 0 3 ) since the gaseous by-product formed would have no effect on the structural integrity of the finished electrode.
- the B 4 C was Carborundum Company Technical Grade 325/F, containing seventy-two percent boron and a maximum particle size of 44 ⁇ m.
- the B 4 C and flour were blended in a ribbon blender for one hour prior to mixing with the other additions in a sigma-bladed heated mixer. A mix temperature of 158°C was achieved. The mix was then cooled to 110°C.and extruded at 105°C. Extrusion pressures varied between 390 and 500 psi for the control and between 400 and 800 psi for the boronated mix. The higher extrusion pressure for the boron-containing mix indicates that insufficient binder was present, which should probably be detremental to physical properties, especially strength. However, in spite of this, as shown in Table II, the boronated electrode had significantly higher strength than the control electrode.. Eight billets measuring six inches diameter by eighteen inches long were formed from each mix.
- the billets were packed with coke packing in saggers and baked at 2°C/hour to 500°C, at 10°C/hour to 900°C and held for approximately ten hours at the latter temperature.
- Baked billets were then impregnated with Ashland 240 petroleum pitch.
- the procedure entailed preheating the billets in an autoclave to 225°C and evacuating the chamber thereafter for one-half to one hour.
- the pitch was heated to 250°C and introduced and the system pressurized to 100 psi.
- the impregnated billets were packed in coke packing and rebaked at 10°C/hour to 750°C and held for twenty-hours at the latter temperature.
- the graphitization process consisted of heating inductively at a rate of 200°C/hour to 2000°C and at 400°C/hour to the final temperature of 3000°C. Hold time at 3000°C was one hour. During graphitization and cooling the stock is protected from oxidation by coke packing.
- an electrode made with boronated anthracite coal exhibits exceptional resistance to oxidation. This is an important characteristic for electrodes which must perform satisfactorily in the exacting environment of an electric arc furnace.
- the principal impurities in anthracite coal are compounds of iron, silicon, aluminum, and titanium, and they equate to approximately ten percent ash.
- Most naturally occurring carbonaceous materials have as impurities similar kinds of elements in varying levels. The vaporization of these materials during graphitization results in lower density, poorer structure and properties. The presence of boron has been observed to prevent their vaporization. Impurities in the boronated carbonaceous stock provide excellent protection against oxidation. This phenomenon is clearly shown as explained below in the single figure of the drawing. The data illustrated in this graph was generated as follows:
- the range of the amount of boron content to be added to the carbonaceous mix to be extruded into the finished electrode is between 0.1 and 5 percent by weight of the graphitized product, with about three percent being the preferred level of boron addition.
- the properties of the electrodes of the invention compare very favorably with those that are available from conventional processing using premium petroleum coke.
Abstract
Description
- The invention relates to a unique process for manufacturing graphite electrodes for electric arc furnace applications and the unique electrodes resulting from the practice of the process.
- Premium petroleum cokes are used extensively in the manufacture of electrodes for steelmaking with electric arc furnaces. The cost of such cokes is increasing very rapidly, however, and this could markedly affect the future growth of the use of electric arc furnaces and thus the market for electric arc electrodes. Less costly carbonaceous materials, such as anthracite coal, bituminous coal, lignites, so-called No. 2 and No. 3 cokes, etc., have been tested in the production of electrodes intended for use in electric arc furnaces but the properties of the resulting electrodes are sufficiently inferior when compared to electrodes made from premium petroleum coke that they have been unacceptable for use in electric furnaces. Efforts to upgrade the properties of electrodes made from other than wholly petroleum coke as the carbonaceous source material to acceptable levels have been unsuccessful to date.
- The principal object of this invention is to provide a method for manufacturing electrodes acceptable for use in electric arc furnaces in which the starting carbonaceous source material is not necessarily entirely premium grade petroleum coke.
- This invention resides in subjecting a carbonaceous source material, other than premium petroleum coke,-and preferably anthracite coal, to the action of elemental boron or a boron compound, preferably boron carbide (B4C), whereby the highly disordered structure of the anthracite coal is transformed into one that is very graphitic in an otherwise conventional electrode manufacturing process.
- The single figure of the drawing is a graph illustrating the improvement in oxidation resistance of electrodes employing in their manufacture boronated anthracite coal as compared to electrodes employing non-boronated anthracite coal.
- In the practice of the invention particles of a non-petroleum coke carbonaceous material are mixed together with the conventional pitch binder and lubricants, and to this mixture is added elemental boron or a boron containing compound. Acceptable carbonaceous source materials other than anthracite coal are bituminous coal, lignites and No. 2 and No. 3 cokes. Preferably the boron source is one which does not release a gaseous by-product when it is to be reacted with the carbonaceous material at the graphitization step in the manufacturing process. Such boron sources are elemental boron, boron carbide (B4C), silicon tetraboride (B4Si) and iron boride (FeB). It should also be appreciated that the boron material can be incorporated with the carbonaceous material during calcination and in this procedure the boron compound may be an oxide such as boric acid (H3B03) or boric oxide (B203) since the gaseous by-product formed would have no effect on the structural integrity of the finished electrode.
- Six-inch diameter coarse-grain anthracite coal electrodes were formed by extrusion. The anthracite coal was calcined at 2200°C prior to crushing and sizing. The coal particles, pitch, lubricants, and B4C additions to the mixes are indicated in Table I. The control mix had no boron, whereas the mix for the boronated stock was formulated to produce a finished product having approximately three weight percent boron.
- The B4 C was Carborundum Company Technical Grade 325/F, containing seventy-two percent boron and a maximum particle size of 44µm. The B4C and flour were blended in a ribbon blender for one hour prior to mixing with the other additions in a sigma-bladed heated mixer. A mix temperature of 158°C was achieved. The mix was then cooled to 110°C.and extruded at 105°C. Extrusion pressures varied between 390 and 500 psi for the control and between 400 and 800 psi for the boronated mix. The higher extrusion pressure for the boron-containing mix indicates that insufficient binder was present, which should probably be detremental to physical properties, especially strength. However, in spite of this, as shown in Table II, the boronated electrode had significantly higher strength than the control electrode.. Eight billets measuring six inches diameter by eighteen inches long were formed from each mix.
- The billets were packed with coke packing in saggers and baked at 2°C/hour to 500°C, at 10°C/hour to 900°C and held for approximately ten hours at the latter temperature.
- Baked billets were then impregnated with Ashland 240 petroleum pitch. The procedure entailed preheating the billets in an autoclave to 225°C and evacuating the chamber thereafter for one-half to one hour. The pitch was heated to 250°C and introduced and the system pressurized to 100 psi. The impregnated billets were packed in coke packing and rebaked at 10°C/hour to 750°C and held for twenty-hours at the latter temperature.
- The graphitization process consisted of heating inductively at a rate of 200°C/hour to 2000°C and at 400°C/hour to the final temperature of 3000°C. Hold time at 3000°C was one hour. During graphitization and cooling the stock is protected from oxidation by coke packing.
- Properties obtained on the control and boronated anthracite coal specimens are shown in Table II. With the exception of the CTE, all properties were measured on I"xl"x6" specimens cut in the extrusion direction (WG) and normal to the extrusion direction (AG). The data are averages of nine AG and eleven WG specimens. The CTE data are essentially room temperature values and these measurements were made on 0.25"x0.75"x6" bars.
- The data in Table II indicate the boronated material has properties superior to those for the control in both billet directions. The WG CTE and WG resistivity for the boronated coal are significant improvements.
- In addition to the foregoing advantages imparted by the employment of boronated anthracite coal over nonboronated anthracite coal, an electrode made with boronated anthracite coal exhibits exceptional resistance to oxidation. This is an important characteristic for electrodes which must perform satisfactorily in the exacting environment of an electric arc furnace.
- It appears that, uniquely, boron causes the anthracite coal or other carbonaceous stock to retain its impurities; even after graphitization.
- The principal impurities in anthracite coal are compounds of iron, silicon, aluminum, and titanium, and they equate to approximately ten percent ash. Most naturally occurring carbonaceous materials have as impurities similar kinds of elements in varying levels. The vaporization of these materials during graphitization results in lower density, poorer structure and properties. The presence of boron has been observed to prevent their vaporization. Impurities in the boronated carbonaceous stock provide excellent protection against oxidation. This phenomenon is clearly shown as explained below in the single figure of the drawing. The data illustrated in this graph was generated as follows:
- One-inch cubes of the control and-boronated anthracite coal stock were heated four hours in still air at temperatures between 800° and 1600°C. Material (carbon + ash) was weighed at the end of this time and the results are expressed as percent remaining in the figure. The oxide coating developed in the coal specimens is a very small percentage (2-5 percent) of the remaining mass. Even at 1600°C, a substantial portion of the remaining material is carbon. At 1200°C, the control is almost completely oxidized, whereas approximately sixty percent carbon is retained in the boronated specimen. Accordingly, consumption will be much less for a boronated anthracite coal electrode exposed to electric arc furnace conditions than it would be for the unboronated counterpart.
- The range of the amount of boron content to be added to the carbonaceous mix to be extruded into the finished electrode is between 0.1 and 5 percent by weight of the graphitized product, with about three percent being the preferred level of boron addition.
-
- As will be appreciated the properties of the electrodes of the invention compare very favorably with those that are available from conventional processing using premium petroleum coke.
- Finally, it should also be appreciated that new, and lower cost electrodes suitable for use in electrical arc furnaces will also be achieved in those instances where the non-petroleum coke carbonaceous stock material which has been subjected to boronation replaces only a portion of the petroleum coke stock material rather than replacing it entirely.
Claims (8)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US44309882A | 1982-11-19 | 1982-11-19 | |
US443098 | 1982-11-19 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0109839A2 true EP0109839A2 (en) | 1984-05-30 |
EP0109839A3 EP0109839A3 (en) | 1985-06-19 |
EP0109839B1 EP0109839B1 (en) | 1989-09-06 |
Family
ID=23759400
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19830307051 Expired EP0109839B1 (en) | 1982-11-19 | 1983-11-18 | Method of making graphite electrodes |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0109839B1 (en) |
JP (1) | JPS59108294A (en) |
DE (1) | DE3380551D1 (en) |
ES (1) | ES527373A0 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102015221853B4 (en) | 2015-11-06 | 2019-05-16 | Technische Universität Bergakademie Freiberg | Process for the preparation of carbonaceous ceramic components |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1396948B1 (en) * | 2009-12-16 | 2012-12-20 | Italghisa S P A | ELECTRODIC PASTE FOR GRAPHITE ELECTRODES WITHOUT "BINDER" WITH HYDROCARBURIC BASIS |
CN105025602A (en) * | 2015-07-13 | 2015-11-04 | 河北联冠电极股份有限公司 | Carbon nanometer ultramicro material large carbon electrode and preparation method thereof |
JP6482442B2 (en) * | 2015-09-30 | 2019-03-13 | クアーズテック株式会社 | Carbon electrode for melting quartz glass |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1285559A (en) * | 1961-03-15 | 1962-02-23 | Union Carbide Corp | Production of artificial graphite |
LU60219A1 (en) * | 1969-01-30 | 1970-03-23 | ||
FR2133802A1 (en) * | 1971-04-15 | 1972-12-01 | Lonza Ag | |
EP0063710A1 (en) * | 1981-04-23 | 1982-11-03 | Arc Technologies Systems, Ltd. | Electrode for arc furnaces, and method of using it |
-
1983
- 1983-11-18 ES ES527373A patent/ES527373A0/en active Granted
- 1983-11-18 EP EP19830307051 patent/EP0109839B1/en not_active Expired
- 1983-11-18 DE DE8383307051T patent/DE3380551D1/en not_active Expired
- 1983-11-18 JP JP58217623A patent/JPS59108294A/en active Granted
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1285559A (en) * | 1961-03-15 | 1962-02-23 | Union Carbide Corp | Production of artificial graphite |
LU60219A1 (en) * | 1969-01-30 | 1970-03-23 | ||
FR2133802A1 (en) * | 1971-04-15 | 1972-12-01 | Lonza Ag | |
EP0063710A1 (en) * | 1981-04-23 | 1982-11-03 | Arc Technologies Systems, Ltd. | Electrode for arc furnaces, and method of using it |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102015221853B4 (en) | 2015-11-06 | 2019-05-16 | Technische Universität Bergakademie Freiberg | Process for the preparation of carbonaceous ceramic components |
Also Published As
Publication number | Publication date |
---|---|
JPH0137839B2 (en) | 1989-08-09 |
EP0109839A3 (en) | 1985-06-19 |
DE3380551D1 (en) | 1989-10-12 |
EP0109839B1 (en) | 1989-09-06 |
ES8407284A1 (en) | 1984-08-16 |
ES527373A0 (en) | 1984-08-16 |
JPS59108294A (en) | 1984-06-22 |
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