WO1997038142A1 - Melange desulfurant a base de carbure de calcium - Google Patents
Melange desulfurant a base de carbure de calcium Download PDFInfo
- Publication number
- WO1997038142A1 WO1997038142A1 PCT/FR1997/000592 FR9700592W WO9738142A1 WO 1997038142 A1 WO1997038142 A1 WO 1997038142A1 FR 9700592 W FR9700592 W FR 9700592W WO 9738142 A1 WO9738142 A1 WO 9738142A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- particle size
- calcium carbide
- pulverulent
- powder
- magnesium
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 239000005997 Calcium carbide Substances 0.000 title claims abstract description 13
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 title claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011777 magnesium Substances 0.000 claims abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 7
- 229910000805 Pig iron Inorganic materials 0.000 claims abstract description 7
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 7
- 239000004571 lime Substances 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 9
- 230000003009 desulfurizing effect Effects 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 abstract description 9
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- 239000004411 aluminium Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 229910001018 Cast iron Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- MVXMNHYVCLMLDD-UHFFFAOYSA-N 4-methoxynaphthalene-1-carbaldehyde Chemical compound C1=CC=C2C(OC)=CC=C(C=O)C2=C1 MVXMNHYVCLMLDD-UHFFFAOYSA-N 0.000 description 1
- -1 ELKEM METALS Chemical class 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/02—Dephosphorising or desulfurising
- C21C1/025—Agents used for dephosphorising or desulfurising
Definitions
- the invention relates to a desulfurizing mixture based on calcium carbide intended to be injected using a lance into the liquid cast iron obtained at the blast furnace before passing it to the converter.
- the Applicant has found that a desulfurizing mixture based on micronized powder of calcium carbide and containing both magnesium powder and aluminum powder, the latter in a well defined concentration range, allows a significant reduction iron losses during desulfurization.
- the subject of the invention is therefore a desulfurizing mixture of refining pig iron consisting of at least 50% (by weight) of powdered calcium carbide with a particle size ⁇ 0.2 mm, from 1 to 20% of powdered magnesium with a particle size ⁇ 0.8 mm and from 5 to 15% of aluminum powder with a particle size ⁇ 0.8 mm, with optionally other powder additives such as lime, calcium carbonate, carbonaceous products and / or coating agents in a total amount of at most 30%.
- the mixture according to the invention is based on technical calcium carbide, which generally contains around 80% by weight of C 2 Ca, the rest being lime, ground to a particle size less than 0.2 mm, with less than 25% of particles in the particle size range 0.1 - 0.2 mm
- This carbide can be added with lime in addition to that resulting from the manufacture of technical carbide, calcium carbonate, carbon products such as carbon black , graphite or anthracite, or other products intended to improve the flowability of the mixture or to release gases allowing a good distribution of the desulfurizer in the hot melt. It is also possible to add up to 2% of a binder for coating the grains, for example hydrogenated castor oil as described in patent EP 0511121 of the applicant.
- the magnesium is added to the mixture in the form of a powder or granules of pure metal or of a magnesium-based alloy with a particle size ⁇ 0.8 mm.
- the grains can also be coated, like those of calcium carbide, with an organic product, for example based on saturated aliphatic acids or their esters as described in patent EP 0485309 of the applicant.
- the mixing of the powders or granules is advantageously carried out in a mixer operating under neutral gas, for example nitrogen.
- the mixtures according to the invention have a desulfurization efficiency at least equal to that of mixtures where aluminum is replaced in equal quantity by magnesium and therefore do not cause any overconsumption of product, which is quite unexpected since aluminum, unlike magnesium, is not by itself a desulfurizer.
- a slag is formed which is more fluid, easier to clean and whose cleaning leads to much lower iron losses.
- dross does not contain any products harmful to the environment such as sodium oxide.
- the tests were carried out on pockets of 300 t of cast iron.
- the initial sulfur content was close to 250 ppm, while the final content was around 55 ppm.
- the effectiveness of a desulfurizer is defined by the ratio of the number of moles removed from the cast iron to the number of moles of desulfurizer injected, that is to say, in the present case, moles of C 2 Ca and Mg, raluminium not being in itself a desulfurizing product.
- the iron loss is defined by the ratio of the mass of pig iron contained in dross to the mass of pig iron contained in the desulfurization pocket. The following results were obtained for the 3 mixtures, which are the average of 20 tests carried out under conditions as close as possible.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69700665T DE69700665T2 (de) | 1996-04-04 | 1997-04-02 | Entschwefelnde kalzium-karbidmischung |
AU23928/97A AU2392897A (en) | 1996-04-04 | 1997-04-02 | Desulphurising calcium carbide blend |
UA98115805A UA49014C2 (uk) | 1996-04-04 | 1997-04-02 | Десульфуюча суміш на основі карбіду кальцію |
RO98-01446A RO117712B1 (ro) | 1996-04-04 | 1997-04-02 | Amestec desulfurant pe baza de carbura de calciu |
CZ19983147A CZ293175B6 (cs) | 1996-04-04 | 1997-04-02 | Odsiřovací směs na bázi karbidu vápníku |
PL97329220A PL183768B1 (pl) | 1996-04-04 | 1997-04-02 | Mieszanka odsiarczająca na bazie karbidu |
EP97919467A EP0891431B1 (fr) | 1996-04-04 | 1997-04-02 | Melange desulfurant a base de carbure de calcium |
HU9902168A HU222767B1 (hu) | 1996-04-04 | 1997-04-02 | Kalciumkarbid-alapú kéntelenítő keverék |
SK1379-98A SK283419B6 (sk) | 1996-04-04 | 1997-04-02 | Odsírovacia zmes na báze karbidu vápnika |
BG102700A BG63215B1 (bg) | 1996-04-04 | 1998-08-19 | Десулфурираща смес на основата на калциев карбид |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9604493A FR2747132B1 (fr) | 1996-04-04 | 1996-04-04 | Melange desulfurant a base de carbure de calcium |
FR96/04493 | 1996-04-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997038142A1 true WO1997038142A1 (fr) | 1997-10-16 |
Family
ID=9491082
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1997/000592 WO1997038142A1 (fr) | 1996-04-04 | 1997-04-02 | Melange desulfurant a base de carbure de calcium |
Country Status (14)
Country | Link |
---|---|
EP (1) | EP0891431B1 (cs) |
AU (1) | AU2392897A (cs) |
BG (1) | BG63215B1 (cs) |
CZ (1) | CZ293175B6 (cs) |
DE (1) | DE69700665T2 (cs) |
ES (1) | ES2140232T3 (cs) |
FR (1) | FR2747132B1 (cs) |
HU (1) | HU222767B1 (cs) |
PL (1) | PL183768B1 (cs) |
RO (1) | RO117712B1 (cs) |
RU (1) | RU2166548C2 (cs) |
SK (1) | SK283419B6 (cs) |
UA (1) | UA49014C2 (cs) |
WO (1) | WO1997038142A1 (cs) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016004493A1 (pt) * | 2014-07-11 | 2016-01-14 | Tecnosulfur Sistema De Tratamiento De Metais Liquidos S/A. | Composição dessulfurante e seu processo de produção, método de acondicionamento e de aplicação em panelas de pequeno porte para produção de ferros fundidos |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19857733A1 (de) * | 1998-12-15 | 2000-06-21 | Almamet Gmbh | Entschwefelungsmittel |
FR2789697B1 (fr) * | 1999-02-12 | 2001-04-06 | Pechiney Electrometallurgie | Melange desulfurant a base de carbure de calcium et/ou de chaux |
CN101367025B (zh) * | 2008-08-13 | 2011-07-27 | 陈宏� | 一种循环流化床锅炉钙基复合催化干法脱硫剂及其制备方法 |
CN107245549B (zh) * | 2017-06-15 | 2018-12-18 | 王强 | 一种电解铝厂铝灰的高效利用工艺 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE418074C (de) * | 1922-03-12 | 1925-08-25 | Wilhelm Kroll Dr | Entschwefelungsmittel fuer Eisen- und Stahlbaeder |
DE2447918A1 (de) * | 1974-10-08 | 1976-04-29 | Gammal Tarek Prof Dr Ing El | Verfahren zur desoxidation und/oder entschwefelung von eisenschmelzen durch oxidfreie caalmg(c)-legierung |
FR2317361A1 (fr) * | 1975-07-11 | 1977-02-04 | Kloeckner Werke Ag | Procede pour desulfurer de la fonte brute |
DE2709062A1 (de) * | 1977-03-02 | 1978-09-07 | Sueddeutsche Kalkstickstoff | Mittel und verfahren zur entschwefelung von eisenschmelzen |
JPS54136516A (en) * | 1978-04-14 | 1979-10-23 | Kobe Steel Ltd | Hot iron desulfurizing agent |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3929464A (en) * | 1973-08-31 | 1975-12-30 | Union Carbide Corp | Desulfurization of molten ferrous metals |
SU466280A1 (ru) * | 1974-01-09 | 1975-04-05 | Донецкий Научно-Исследовательский Институ Черной Металлургии | Способ десульфурации чугуна |
SU532633A1 (ru) * | 1975-07-09 | 1976-10-25 | Грузинский Ордена Ленина И Трудового Красного Знамени Политехничнский Институт Имени В.И.Ленина | Смесь дл десульфурации чугуна и стали |
DE2716457C2 (de) * | 1977-04-14 | 1985-11-21 | Skw Trostberg Ag, 8223 Trostberg | Verfahren zum Einblasen von Entschwefelungsgemischen in Eisenschmelzen |
DE2934193A1 (de) * | 1979-08-23 | 1981-03-26 | Denki Kagaku Kogyo K.K., Tokio/Tokyo | Mittel zur entschwefelung von geschmolzenem eisen. |
US4462823A (en) * | 1982-12-11 | 1984-07-31 | Foseco International Limited | Treatment agents for molten steel |
CA1240842A (en) * | 1984-05-16 | 1988-08-23 | Heinrich Rellermeyer | Method, process and composition for desulfurizing pig-iron melts |
DE3908071A1 (de) * | 1989-03-13 | 1990-09-20 | Hoechst Ag | Mittel und verfahren zum entschwefeln von metallschmelzen |
US4941914A (en) * | 1989-05-18 | 1990-07-17 | Elkem Metals Company | Desulfurization agent |
FR2668776B1 (fr) * | 1990-11-05 | 1994-05-13 | Pechiney Electrometallurgie | Produit pour desulfuration des fontes ou aciers liquides a base de magnesium enrobe. |
-
1996
- 1996-04-04 FR FR9604493A patent/FR2747132B1/fr not_active Expired - Fee Related
-
1997
- 1997-04-02 ES ES97919467T patent/ES2140232T3/es not_active Expired - Lifetime
- 1997-04-02 AU AU23928/97A patent/AU2392897A/en not_active Abandoned
- 1997-04-02 WO PCT/FR1997/000592 patent/WO1997038142A1/fr active IP Right Grant
- 1997-04-02 RO RO98-01446A patent/RO117712B1/ro unknown
- 1997-04-02 UA UA98115805A patent/UA49014C2/uk unknown
- 1997-04-02 PL PL97329220A patent/PL183768B1/pl not_active IP Right Cessation
- 1997-04-02 HU HU9902168A patent/HU222767B1/hu not_active IP Right Cessation
- 1997-04-02 DE DE69700665T patent/DE69700665T2/de not_active Expired - Fee Related
- 1997-04-02 SK SK1379-98A patent/SK283419B6/sk unknown
- 1997-04-02 RU RU98119951/02A patent/RU2166548C2/ru not_active IP Right Cessation
- 1997-04-02 EP EP97919467A patent/EP0891431B1/fr not_active Expired - Lifetime
- 1997-04-02 CZ CZ19983147A patent/CZ293175B6/cs not_active IP Right Cessation
-
1998
- 1998-08-19 BG BG102700A patent/BG63215B1/bg unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE418074C (de) * | 1922-03-12 | 1925-08-25 | Wilhelm Kroll Dr | Entschwefelungsmittel fuer Eisen- und Stahlbaeder |
DE2447918A1 (de) * | 1974-10-08 | 1976-04-29 | Gammal Tarek Prof Dr Ing El | Verfahren zur desoxidation und/oder entschwefelung von eisenschmelzen durch oxidfreie caalmg(c)-legierung |
FR2317361A1 (fr) * | 1975-07-11 | 1977-02-04 | Kloeckner Werke Ag | Procede pour desulfurer de la fonte brute |
DE2709062A1 (de) * | 1977-03-02 | 1978-09-07 | Sueddeutsche Kalkstickstoff | Mittel und verfahren zur entschwefelung von eisenschmelzen |
JPS54136516A (en) * | 1978-04-14 | 1979-10-23 | Kobe Steel Ltd | Hot iron desulfurizing agent |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 004, no. 002 (C - 069) 9 January 1980 (1980-01-09) * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016004493A1 (pt) * | 2014-07-11 | 2016-01-14 | Tecnosulfur Sistema De Tratamiento De Metais Liquidos S/A. | Composição dessulfurante e seu processo de produção, método de acondicionamento e de aplicação em panelas de pequeno porte para produção de ferros fundidos |
Also Published As
Publication number | Publication date |
---|---|
ES2140232T3 (es) | 2000-02-16 |
DE69700665D1 (de) | 1999-11-25 |
DE69700665T2 (de) | 2000-05-11 |
SK283419B6 (sk) | 2003-07-01 |
HUP9902168A3 (en) | 2001-11-28 |
PL329220A1 (en) | 1999-03-15 |
HU222767B1 (hu) | 2003-10-28 |
PL183768B1 (pl) | 2002-07-31 |
EP0891431A1 (fr) | 1999-01-20 |
UA49014C2 (uk) | 2002-09-16 |
SK137998A3 (en) | 1999-05-07 |
RU2166548C2 (ru) | 2001-05-10 |
CZ314798A3 (cs) | 1999-08-11 |
HUP9902168A2 (hu) | 1999-11-29 |
BG102700A (en) | 1999-03-31 |
FR2747132A1 (fr) | 1997-10-10 |
BG63215B1 (bg) | 2001-06-29 |
AU2392897A (en) | 1997-10-29 |
CZ293175B6 (cs) | 2004-02-18 |
RO117712B1 (ro) | 2002-06-28 |
FR2747132B1 (fr) | 1998-06-19 |
EP0891431B1 (fr) | 1999-10-20 |
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