EP0891431A1 - Entschwefelnde kalzium-karbidmischung - Google Patents

Entschwefelnde kalzium-karbidmischung

Info

Publication number: EP0891431A1
Authority: EP; European Patent Office
Prior art keywords: particle size; calcium carbide; pulverulent; powder; magnesium
Prior art date: 1996-04-04
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

Application number

EP97919467A

Other languages

English (en)

French (fr)

Other versions

EP0891431B1 (de

Inventor

Gilles Nussbaum

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

SKW BELLEGARDE Sas

Original Assignee

Pechiney Electrometallurgie SAS

Priority date (The priority date 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 date listed.)

1996-04-04

Filing date

1997-04-02

Publication date

1999-01-20

1997-04-02 Application filed by Pechiney Electrometallurgie SAS filed Critical Pechiney Electrometallurgie SAS

1999-01-20 Publication of EP0891431A1 publication Critical patent/EP0891431A1/de

1999-10-20 Application granted granted Critical

1999-10-20 Publication of EP0891431B1 publication Critical patent/EP0891431B1/de

2017-04-02 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

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)

EP97919467A 1996-04-04 1997-04-02 Entschwefelnde kalzium-karbidmischung Expired - Lifetime EP0891431B1 (de)

Applications Claiming Priority (3)

Application Number	Priority Date	Filing Date	Title
FR9604493A FR2747132B1 (fr)	1996-04-04	1996-04-04	Melange desulfurant a base de carbure de calcium
FR9604493		1996-04-04
PCT/FR1997/000592 WO1997038142A1 (fr)	1996-04-04	1997-04-02	Melange desulfurant a base de carbure de calcium

Publications (2)

Publication Number	Publication Date
EP0891431A1 true EP0891431A1 (de)	1999-01-20
EP0891431B1 EP0891431B1 (de)	1999-10-20

Family

ID=9491082

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP97919467A Expired - Lifetime EP0891431B1 (de)	1996-04-04	1997-04-02	Entschwefelnde kalzium-karbidmischung

Country Status (14)

Country	Link
EP (1)	EP0891431B1 (de)
AU (1)	AU2392897A (de)
BG (1)	BG63215B1 (de)
CZ (1)	CZ293175B6 (de)
DE (1)	DE69700665T2 (de)
ES (1)	ES2140232T3 (de)
FR (1)	FR2747132B1 (de)
HU (1)	HU222767B1 (de)
PL (1)	PL183768B1 (de)
RO (1)	RO117712B1 (de)
RU (1)	RU2166548C2 (de)
SK (1)	SK283419B6 (de)
UA (1)	UA49014C2 (de)
WO (1)	WO1997038142A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
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
BR102014017197A2 (pt) *	2014-07-11	2016-02-16	Tecnosulfur Sist De Tratamento 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
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

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DE418074C (de) *	1922-03-12	1925-08-25	Wilhelm Kroll Dr	Entschwefelungsmittel fuer Eisen- und Stahlbaeder
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
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
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
DE2531047B2 (de) *	1975-07-11	1978-07-06	Kloeckner-Werke Ag, 4100 Duisburg	Verfahren zum Entschwefeln von Roheisen
DE2709062A1 (de) *	1977-03-02	1978-09-07	Sueddeutsche Kalkstickstoff	Mittel und verfahren zur entschwefelung von eisenschmelzen
DE2716457C2 (de) *	1977-04-14	1985-11-21	Skw Trostberg Ag, 8223 Trostberg	Verfahren zum Einblasen von Entschwefelungsgemischen in Eisenschmelzen
JPS54136516A (en) *	1978-04-14	1979-10-23	Kobe Steel Ltd	Hot iron desulfurizing agent
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 UA UA98115805A patent/UA49014C2/uk unknown
- 1997-04-02 EP EP97919467A patent/EP0891431B1/de not_active Expired - Lifetime
- 1997-04-02 HU HU9902168A patent/HU222767B1/hu not_active IP Right Cessation
- 1997-04-02 ES ES97919467T patent/ES2140232T3/es not_active Expired - Lifetime
- 1997-04-02 SK SK1379-98A patent/SK283419B6/sk unknown
- 1997-04-02 PL PL97329220A patent/PL183768B1/pl not_active IP Right Cessation
- 1997-04-02 CZ CZ19983147A patent/CZ293175B6/cs not_active IP Right Cessation
- 1997-04-02 WO PCT/FR1997/000592 patent/WO1997038142A1/fr not_active Ceased
- 1997-04-02 AU AU23928/97A patent/AU2392897A/en not_active Abandoned
- 1997-04-02 DE DE69700665T patent/DE69700665T2/de not_active Expired - Fee Related
- 1997-04-02 RO RO98-01446A patent/RO117712B1/ro unknown
- 1997-04-02 RU RU98119951/02A patent/RU2166548C2/ru not_active IP Right Cessation
1998
- 1998-08-19 BG BG102700A patent/BG63215B1/bg unknown

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9738142A1 *

Also Published As

Publication number	Publication date
PL329220A1 (en)	1999-03-15
EP0891431B1 (de)	1999-10-20
CZ293175B6 (cs)	2004-02-18
RU2166548C2 (ru)	2001-05-10
DE69700665D1 (de)	1999-11-25
SK283419B6 (sk)	2003-07-01
HU222767B1 (hu)	2003-10-28
WO1997038142A1 (fr)	1997-10-16
FR2747132B1 (fr)	1998-06-19
FR2747132A1 (fr)	1997-10-10
BG63215B1 (bg)	2001-06-29
HUP9902168A3 (en)	2001-11-28
RO117712B1 (ro)	2002-06-28
SK137998A3 (en)	1999-05-07
UA49014C2 (uk)	2002-09-16
ES2140232T3 (es)	2000-02-16
HUP9902168A2 (hu)	1999-11-29
CZ314798A3 (cs)	1999-08-11
AU2392897A (en)	1997-10-29
DE69700665T2 (de)	2000-05-11
PL183768B1 (pl)	2002-07-31
BG102700A (en)	1999-03-31

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Publication	Publication Date	Title
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