NO151752B - PROCEDURE FOR THE PREPARATION OF VANADIUM CARBID ALLOWANCE BY VACUUM REDUCTION OF CARBON VANADIUM OXIDE - Google Patents
PROCEDURE FOR THE PREPARATION OF VANADIUM CARBID ALLOWANCE BY VACUUM REDUCTION OF CARBON VANADIUM OXIDE Download PDFInfo
- Publication number
- NO151752B NO151752B NO772268A NO772268A NO151752B NO 151752 B NO151752 B NO 151752B NO 772268 A NO772268 A NO 772268A NO 772268 A NO772268 A NO 772268A NO 151752 B NO151752 B NO 151752B
- Authority
- NO
- Norway
- Prior art keywords
- carbon
- mixture
- vanadium
- sulfur
- silicon
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 15
- 229910052720 vanadium Inorganic materials 0.000 title description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title description 3
- GSLNTGVHPTZSME-UHFFFAOYSA-N [O-2].[V+5].[C+4] Chemical compound [O-2].[V+5].[C+4] GSLNTGVHPTZSME-UHFFFAOYSA-N 0.000 title 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- 229910052717 sulfur Inorganic materials 0.000 claims description 26
- 239000011593 sulfur Substances 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 5
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 5
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 5
- 229910000681 Silicon-tin Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 229910000604 Ferrochrome Inorganic materials 0.000 description 4
- HJIYJLZFNBHCAN-UHFFFAOYSA-N [V].[C] Chemical compound [V].[C] HJIYJLZFNBHCAN-UHFFFAOYSA-N 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C35/00—Master alloys for iron or steel
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Silicon Compounds (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Description
Foreliggende oppfinnelse angår en fremgangsmåte ved fremstilling av vanadiumkarbidforlegering ved vakuumreduksjon av vanadiumoksyd med karbon under anvendelse av en råmaterialblanding som også inneholder svovel. The present invention relates to a method for the production of vanadium carbide prealloy by vacuum reduction of vanadium oxide with carbon using a raw material mixture which also contains sulphur.
Vanadium-karbonstoffer av den type, som er angitt ovenfor, fremstilles ved høytemperaturvakuumbrenning av vanadiumoksyd og karbon, slik som beskrevet f.eks. i NO-PS 115037. Vanadium-carbon substances of the type indicated above are produced by high-temperature vacuum combustion of vanadium oxide and carbon, as described e.g. in NO-PS 115037.
De vanadium-karbonstoffer, som er beskrevet i det ovenfor angitte patent, fremstilles ved en fremgangsmåte som omfatter blanding av V^O^ med karbon, sammenpressing av blandingen til briketter og vakuumbrenning av blandingen ved forhøyede temperaturer, f.eks. 1200-1400°C, ved trykk på mindre enn 0,3 mm Hg for å oppnå et produkt hvori i det vesentlige alt foreligger i form av bundet vanadium og karbon. Dette materiale er utstrakt anvendt som vanadiumadditiv for smeltet stål. Det er funnet at svovelinnholdet i et slikt vanadium-karbonprodukt er i størrelsesorden 1/3 av svovelinnholdet i utgangsblandingen av V203 og karbon, der svovelinnholdet i utgangsblandingen i det vesentlige skyldes svovelinnholdet i karbonkilden, f.eks. kull, sot o.l. The vanadium-carbon substances, which are described in the above-mentioned patent, are produced by a method which comprises mixing V^O^ with carbon, compressing the mixture into briquettes and vacuum burning the mixture at elevated temperatures, e.g. 1200-1400°C, at a pressure of less than 0.3 mm Hg to obtain a product in which essentially everything is present in the form of bound vanadium and carbon. This material is widely used as a vanadium additive for molten steel. It has been found that the sulfur content in such a vanadium-carbon product is of the order of 1/3 of the sulfur content in the starting mixture of V 2 O 3 and carbon, where the sulfur content in the starting mixture is essentially due to the sulfur content in the carbon source, e.g. coal, soot etc.
Fordi det er uønsket å tilsette svovelforurensninger til stål er det viktig å redusere svovelinnholdet for vanadium-karbonstoffer som beskrevet ovenfor, spesielt når karbonmaterialet med lavt svovelinnhold ikke lett er tilgjengelige. Because it is undesirable to add sulfur impurities to steel, it is important to reduce the sulfur content of vanadium-carbon materials as described above, especially when the low-sulfur carbon material is not readily available.
Av kjent teknikk skal det ellers henvises til NO-PS 20830 som beskriver en fremgangsmåte til bearbeidelse av ertser inneholdende svovel og jern henholdsvis svovelholdige jernforbindel-ser der man ved hjelp av elektrisk oppvarming reduserer disse stoffer i rå eller røstet tilstand sammen med kiselsyre eller kiselsyreholdige stoffer og karbon henholdsvis karbonholdige stoffer.til ferrosilisum, og der kiselsyremengden avpasses slik at det dannede silisium er tilstrekkelig til å kunne drive ut svovelet fullstendig av svovel- jernmateriale for anvendelse til andre formål. Of known technology, reference should otherwise be made to NO-PS 20830 which describes a method for processing ores containing sulfur and iron or sulphur-containing iron compounds in which these substances are reduced in their raw or roasted state together with silicic acid or silicic acid-containing substances by means of electric heating and carbon, respectively carbon-containing substances.to ferrosilicon, and where the amount of silicic acid is adjusted so that the formed silicon is sufficient to be able to drive the sulfur completely out of sulphur-iron material for use for other purposes.
US-PS 2939784 beskriver en fremgangsmåte for fremstilling av svovelfri ferrokromlegering med lavt karboninnhold fra en svovelholdig ferrokromlegering med høyt karboninnhold omfattende å knuse ferrokrom med høyt karboninnhold, blanding av dette materiale med minst ett svovelfritt materiale med tilsvarende partikkelstørrelse valgt blant elementært tinn, tinnlegeringer, tinnforbindelser og tinnholdige malmer i en mengde tilstrekkelig til å reagere med alt svovel,pelletiser-ing av blandingen og dekarburisering av det pelletiserte materiale under vakuumoppvarmingsbetingelser i et tidsrom tilstrekkelig til i fast tilstand å omsette tinnet i materi-alet med i det vesentlige alt svovel i ferrokromet med høyt karboninnhold for å danne en flyktig svovelforbindelse, og derefter å fordampe eventuelt resttinn. US-PS 2939784 describes a process for the production of low-carbon sulfur-free ferrochromium alloy from a high-carbon sulfur-containing ferrochromium alloy comprising crushing high-carbon ferrochromium, mixing this material with at least one sulfur-free material of corresponding particle size selected from elemental tin, tin alloys, tin compounds and tin-bearing ores in an amount sufficient to react with all the sulfur, pelletizing the mixture and decarburizing the pelletized material under vacuum heating conditions for a period of time sufficient to solid state the tin in the material with substantially all the sulfur in the ferrochrome with high carbon content to form a volatile sulfur compound, and then to evaporate any residual tin.
I henhold til dette angår foreliggende oppfinnelse According to this, the present invention relates
en fremgangsmåte ved fremstilling av vanadiumkarbidforlegering ved vakuumreduksjon av vanadiumoksyd med karbon under anvendelse av en råmaterialblanding som også inneholder svovel, og denne fremgangsmåte karakteriseres ved at det for å redusere svovelinnholdet i blandingen tilsettes minst ett materiale valgt blant silisium, silisiumdioksyd og tinn. a method for the production of vanadium carbide prealloy by vacuum reduction of vanadium oxide with carbon using a raw material mixture that also contains sulphur, and this method is characterized by the addition of at least one material selected from silicon, silicon dioxide and tin in order to reduce the sulfur content in the mixture.
En fremgangsmåte ifølge oppfinnelsen omfatter således innarbeiding i en blanding av vanadiumoksyd og karbon, som inneholder svovel som forurensning, en mindre mengde av minst et stoff valgt blant silisium, silisiumdioksyd og tinn, og vakuumreduksjon av nevnte blanding for å gi et stoff som i det vesentlige , dvs. minst 80 vekt-% , foreligger i form A method according to the invention thus comprises incorporating into a mixture of vanadium oxide and carbon, which contains sulfur as an impurity, a small amount of at least one substance selected from silicon, silicon dioxide and tin, and vacuum reduction of said mixture to give a substance which essentially , i.e. at least 80% by weight, is available in form
av VC eller V^C og som har et svovelinnhold betydelig lavere enn utgangsblandingen. of VC or V^C and which has a sulfur content significantly lower than the starting mixture.
Ved gjennomføring av en spesiell utførelsesform av oppfinnelsen blir en blanding av fint oppdelt V^O^ og karbon fremstilt og minst en av et fint oppdelt materiale valgt blant silisium, silisiumdioksyd og tinn, innarbeidet i blandingen. Den totale mengde valgt materiale er, når dette er tinn, fra 1-5 ganger vekten av svovelet i karbonbestanddelen i blandingen. Når det valgte materiale er silisium eller silisiumdioksyd er den totale mengde av tilstedeværende silisium 1-9 ganger vekten av svovelet i karbonbestanddelen i blandingen. Blandingen blir deretter brikettert og underkastes en tempera-turbehandling i et område mellom 1200 og 1400°C i en vakuumovn hvori blandingsbestanddelene omsettes, og reaksjonen full-føres ved et trykk på mindre enn 0,3 mm Hg, mens reaksjons-tiden må være tilstrekkelig til å forårsake at karbon omsettes med V^O^ og danner et produkt hvori minst 80 vekt-% foreligger i form av VC eller V2C. Svovelinnholdet i det således produ-serte materiale, vil være mindre enn 0,05 vekt-%. When carrying out a particular embodiment of the invention, a mixture of finely divided V^O^ and carbon is prepared and at least one of a finely divided material selected from silicon, silicon dioxide and tin is incorporated into the mixture. The total amount of material selected is, when this is tin, from 1-5 times the weight of the sulfur in the carbon component of the mixture. When the material selected is silicon or silicon dioxide, the total amount of silicon present is 1-9 times the weight of the sulfur in the carbon component of the mixture. The mixture is then briquetted and subjected to a temperature treatment in a range between 1200 and 1400°C in a vacuum furnace in which the mixture components react, and the reaction is completed at a pressure of less than 0.3 mm Hg, while the reaction time must be sufficient to cause carbon to react with V^O^ and form a product in which at least 80% by weight is present in the form of VC or V2C. The sulfur content in the thus produced material will be less than 0.05% by weight.
De følgende eksempler illustrerer oppfinnelsen ytter-ligere. Alle prosentandeler er beregnet på vekt. The following examples further illustrate the invention. All percentages are calculated by weight.
Eksempel 1. Sammenligningseksempel. Example 1. Comparison example.
Det ble fremstilt en blanding inneholdende 453,5 kg V2C>2 med en partikkelstørrelse på -2 ym, 152 kg petroleum-koksinneholdende 0,65% svovel med en partikkelstørrelse -2 ym^ 9,07 kg "Mogul"-bindemiddel og 23% vann på tørrbasis. Det ble fra denne blanding fremstilt briketter med en størrelse på 44,4 mm x 31,7 mm x 25,4 mm ved pressing i en K-G brikettvalse-presse og tørking ved 10 9°C. De resulterende briketter i meng-der på 1,36 kg ble chargert til en vakuumovn med indre dimen-sjoner 177,8 mm x 308,3 mm x 1016 mm. Trykket i ovnen ble re-dusert til 0,175 mm Hg og ovnen ble oppvarmet til 1400°C. På grunn av CO-utvikling, steg trykket til omkring 1,6 mm Hg. Etter ca. 8 timer ved 14 00°C sank trykket til 0,1 mm Hg og ovnsinn-holdet ble deretter avkjølt til romtemperatur under et positivt argontrykk. De oppnådde briketter inneholdt 8,49% bundet karbon og 0,18% svovel. A mixture was prepared containing 453.5 kg of V2C>2 with a particle size of -2 ym, 152 kg of petroleum coke containing 0.65% sulfur with a particle size of -2 ym^ 9.07 kg of "Mogul" binder and 23% water on a dry basis. Briquettes with a size of 44.4 mm x 31.7 mm x 25.4 mm were produced from this mixture by pressing in a K-G briquette roller press and drying at 10 9°C. The resulting briquettes in quantities of 1.36 kg were charged into a vacuum furnace with internal dimensions of 177.8 mm x 308.3 mm x 1016 mm. The pressure in the furnace was reduced to 0.175 mm Hg and the furnace was heated to 1400°C. Due to CO evolution, the pressure rose to about 1.6 mm Hg. After approx. 8 hours at 1400°C the pressure dropped to 0.1 mm Hg and the furnace contents were then cooled to room temperature under a positive argon pressure. The briquettes obtained contained 8.49% bound carbon and 0.18% sulphur.
Eksempel 2. Example 2.
Man fulgte i det vesentlige samme fremgangsmåte som i eks. 1 bortsett fra at blandingen inneholdt 1,7% silisium, beregnet på vekten av V^O^, med en partikkelstørrelse på mindre enn 0,074 mm. De resulterende briketter inneholdt 7,94% bundet karbon og 0,013% svovel. Essentially the same procedure was followed as in ex. 1 except that the mixture contained 1.7% silicon, calculated on the weight of V₂O₂, with a particle size of less than 0.074 mm. The resulting briquettes contained 7.94% bound carbon and 0.013% sulfur.
Eksempel 3. Example 3.
Man fulgte i det vesentlige samme fremgangsmåte som i eks. 1 bortsett fra at blandingen inneholdt 0,5% tinn, beregnet på vekten av V^O^ med en partikkelstørrelse mindre enn 0,15 mm. De resulterende briketter inneholdt 7,44% bundet karbon og 0,04 2% svovel. Essentially the same procedure was followed as in ex. 1 except that the mixture contained 0.5% tin, calculated on the weight of V₂O₂ with a particle size smaller than 0.15 mm. The resulting briquettes contained 7.44% bound carbon and 0.042% sulfur.
Eksempel 4. Example 4.
Man fulgte i det vesentlige samme fremgangsmåte som i eks. 1 bortsett fra at blandingen inneholdt 3,6% S±0^, beregnet på vekten av V2°3' me<^ en Partikkelstørrelse på mindre enn 0,074 mm. De resulterende briketter inneholdt 9,34% bundet karbon og 0,012% svovel. Essentially the same procedure was followed as in ex. 1 except that the mixture contained 3.6% S±0^, calculated on the weight of V2°3' me<^ a Particle size of less than 0.074 mm. The resulting briquettes contained 9.34% bound carbon and 0.012% sulfur.
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US70047276A | 1976-06-28 | 1976-06-28 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO772268L NO772268L (en) | 1977-12-29 |
| NO151752B true NO151752B (en) | 1985-02-18 |
| NO151752C NO151752C (en) | 1985-05-29 |
Family
ID=24813628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO772268A NO151752C (en) | 1976-06-28 | 1977-06-27 | PROCEDURE FOR THE PREPARATION OF VANADIUM CARBID ALLOWANCE BY VACUUM REDUCTION OF CARBON VANADIUM OXIDE |
Country Status (27)
| Country | Link |
|---|---|
| JP (1) | JPS532400A (en) |
| AR (1) | AR214412A1 (en) |
| AT (1) | AT361228B (en) |
| AU (1) | AU504846B2 (en) |
| BE (1) | BE856156A (en) |
| BR (1) | BR7704155A (en) |
| CA (1) | CA1096135A (en) |
| CH (1) | CH622289A5 (en) |
| CS (1) | CS207461B2 (en) |
| DD (1) | DD131743A5 (en) |
| DE (1) | DE2727559A1 (en) |
| DK (1) | DK284377A (en) |
| ES (1) | ES460122A1 (en) |
| FI (1) | FI69317C (en) |
| FR (1) | FR2356734A1 (en) |
| GB (1) | GB1580492A (en) |
| HU (1) | HU176035B (en) |
| IN (1) | IN147296B (en) |
| IT (1) | IT1079718B (en) |
| LU (1) | LU77619A1 (en) |
| MX (1) | MX145912A (en) |
| NO (1) | NO151752C (en) |
| PH (1) | PH13010A (en) |
| PL (1) | PL111609B1 (en) |
| SE (1) | SE440795B (en) |
| YU (1) | YU40002B (en) |
| ZA (1) | ZA773579B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ229777A (en) * | 1989-12-30 | 1991-08-27 | Nz Government | Method for manufacturing ceramic-metal composites |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2576763A (en) * | 1950-03-22 | 1951-11-27 | Climax Molybdenum Co | Vanadium containing briquettes |
| FR1422683A (en) * | 1965-01-26 | 1965-12-24 | Union Carbide Corp | Adding agent containing vanadium and its manufacturing process |
| FR1471448A (en) * | 1966-03-10 | 1967-03-03 | Vanadium Corp Of America | Manufacturing process of vanadium carbide briquettes |
| FR1562736A (en) * | 1967-05-29 | 1969-04-04 | ||
| US3982924A (en) * | 1971-05-26 | 1976-09-28 | Reading Alloys, Inc. | Process for producing carbide addition agents |
-
1977
- 1977-06-14 ZA ZA00773579A patent/ZA773579B/en unknown
- 1977-06-17 CA CA280,822A patent/CA1096135A/en not_active Expired
- 1977-06-18 DE DE19772727559 patent/DE2727559A1/en not_active Ceased
- 1977-06-23 YU YU1561/77A patent/YU40002B/en unknown
- 1977-06-27 GB GB26795/77A patent/GB1580492A/en not_active Expired
- 1977-06-27 AR AR268200A patent/AR214412A1/en active
- 1977-06-27 DD DD7700199724A patent/DD131743A5/en unknown
- 1977-06-27 BE BE178819A patent/BE856156A/en not_active IP Right Cessation
- 1977-06-27 IN IN955/CAL/77A patent/IN147296B/en unknown
- 1977-06-27 CH CH785677A patent/CH622289A5/en not_active IP Right Cessation
- 1977-06-27 NO NO772268A patent/NO151752C/en unknown
- 1977-06-27 ES ES460122A patent/ES460122A1/en not_active Expired
- 1977-06-27 LU LU77619A patent/LU77619A1/xx unknown
- 1977-06-27 FI FI771991A patent/FI69317C/en not_active IP Right Cessation
- 1977-06-27 FR FR7719641A patent/FR2356734A1/en active Granted
- 1977-06-27 IT IT49992/77A patent/IT1079718B/en active
- 1977-06-27 JP JP7643677A patent/JPS532400A/en active Granted
- 1977-06-27 HU HU77UI262A patent/HU176035B/en unknown
- 1977-06-27 SE SE7707391A patent/SE440795B/en not_active IP Right Cessation
- 1977-06-27 AT AT452477A patent/AT361228B/en not_active IP Right Cessation
- 1977-06-27 AU AU26488/77A patent/AU504846B2/en not_active Expired
- 1977-06-27 MX MX169642A patent/MX145912A/en unknown
- 1977-06-27 PL PL1977199196A patent/PL111609B1/en unknown
- 1977-06-27 PH PH19917A patent/PH13010A/en unknown
- 1977-06-27 BR BR7704155A patent/BR7704155A/en unknown
- 1977-06-27 CS CS774235A patent/CS207461B2/en unknown
- 1977-06-27 DK DK284377A patent/DK284377A/en not_active Application Discontinuation
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