EP1590494B1 - Procede permettant d'accroitre le rapport chrome-fer des produits chromites - Google Patents
Procede permettant d'accroitre le rapport chrome-fer des produits chromites Download PDFInfo
- Publication number
- EP1590494B1 EP1590494B1 EP04708695A EP04708695A EP1590494B1 EP 1590494 B1 EP1590494 B1 EP 1590494B1 EP 04708695 A EP04708695 A EP 04708695A EP 04708695 A EP04708695 A EP 04708695A EP 1590494 B1 EP1590494 B1 EP 1590494B1
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- EP
- European Patent Office
- Prior art keywords
- iron
- chlorination
- chromite
- recited
- temperature
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 66
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 75
- 150000003839 salts Chemical class 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 239000012141 concentrate Substances 0.000 claims abstract description 11
- 239000000155 melt Substances 0.000 claims abstract description 10
- 239000010409 thin film Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 75
- 239000011780 sodium chloride Substances 0.000 claims description 38
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 47
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 45
- 238000006243 chemical reaction Methods 0.000 description 38
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 30
- 239000011651 chromium Substances 0.000 description 28
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 229910052804 chromium Inorganic materials 0.000 description 17
- 238000002474 experimental method Methods 0.000 description 17
- ZUVVLBGWTRIOFH-UHFFFAOYSA-N methyl 4-methyl-2-[(4-methylphenyl)sulfonylamino]pentanoate Chemical compound COC(=O)C(CC(C)C)NS(=O)(=O)C1=CC=C(C)C=C1 ZUVVLBGWTRIOFH-UHFFFAOYSA-N 0.000 description 17
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 14
- 239000000460 chlorine Substances 0.000 description 14
- 239000000523 sample Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 229910052801 chlorine Inorganic materials 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 12
- 229910000604 Ferrochrome Inorganic materials 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical class [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 5
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000011636 chromium(III) chloride Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229960002089 ferrous chloride Drugs 0.000 description 4
- 229910052595 hematite Inorganic materials 0.000 description 4
- 239000011019 hematite Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical class Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000010587 phase diagram Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 230000002596 correlated effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 235000014413 iron hydroxide Nutrition 0.000 description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical class [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 3
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- -1 Fe2O3 Chemical compound 0.000 description 2
- 239000000654 additive Substances 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
- 238000004458 analytical method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 241000928106 Alain Species 0.000 description 1
- 241001033429 Canarium vulgare Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000011473 acid brick Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- NHYCGSASNAIGLD-UHFFFAOYSA-N chlorine monoxide Inorganic materials Cl[O] NHYCGSASNAIGLD-UHFFFAOYSA-N 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
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- 230000000875 corresponding effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052892 hornblende Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000003846 membrane cell process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/08—Chloridising roasting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
- C22B34/1209—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by dry processes, e.g. with selective chlorination of iron or with formation of a titanium bearing slag
Definitions
- the present invention relates to a method for increasing the chrome to iron ratio of chromites products. More particularly, it relates to a chlorination method for increasing the chrome to iron ratio of chromites products.
- the primary industrial source of chromium is the mineral chromite, which can be represented by the ideal formula FeO.Cr 2 O 3 .
- FeO can be partially substituted by other elements such as MgO, CaO, MnO and Cr 2 O 3 by Fe 2 O 3 and Al 2 O 3 .
- These substitutions are at the origin of different types of chromites distinguished, among other things, by their chrome to iron ratios.
- the chrome to iron ratios of chromites vary from 1.3 to 4.0 in many stratiform or podiform deposits. Chromites possessing chrome to iron ratios higher than 3, are rare in nature.
- Chromites are employed in the production of ferrochromium, a master alloy in the stainless steel industry.
- the primary process for the production of ferrochromium from chromites is described by the general reaction: metal oxide + reductant + energy ⁇ (ferro)metal + reductant oxide.
- the production of ferrochromium is an energy-intensive process and is generally conducted in an electrical furnace.
- Ferrochromiums can be divided in three classes based on their carbon content: high carbon ferrochromium containing between 4 to 10 % carbon; medium carbon ferrochromium containing between 0.5 to 4 % carbon; low carbon ferrochromium containing less than 0.5 % carbon.
- the chrome to iron ratio of the chromite ore used as a feed to the furnace controls the chromium content of the ferrochromium.
- the value of the ferrochromium is mainly based on its chromium and carbon contents. The highest prices are obtained for ferrochromium showing high concentration in chromium and low carbon content.
- the chromites economic values are set by their chrome to iron ratios: a chromite with a Cr/Fe ratio of 1.5 being worth less than a chromite with a Cr/Fe ratio of 4.
- the economic value of these chromium-enriched chromites is increased in their use as enriched product directly and as feed for ferrochromium production.
- European Patent No. 0 096 241 by Robinson and Crosby, describes the chlorination of chromites mixed with coke by Cl 2 at a temperature ranging between 1000° and 1100° C. The chromites are completely transformed into chlorides and volatilized. The iron chlorides and chromium chlorides are separated according to their respective boiling points. This specific process leads to the formation of pure CrCl 3 .
- Table 1 shows chemical analysis performed by an electron micro-probe of chromite grains extracted from Cr-3 chromite showing of the Menarik Complex. These results indicate important variations in the major oxides phases on a grain-to-grain basis. The average chemical composition of the Cr-3 mineralized zone is reported in the Table 2 with the heading Starting ore. Table 1. Chemical analysis of chromite grains by electron micro-probe, Menarik Cr-3 chromite Sample MgO Al 2 O 3 SiO 2 TiO 2 V 2 O 3 Cr 2 O 3 MnO FeO Cr/Fe No.
- the present invention generally provides a novel approach for the extraction of iron from chromites.
- it also provides a method for extracting iron from chromites without substantially affecting other major chemical components in chromites.
- the present invention is applicable to chromites products such as chromite ores and different types of chromite concentrates including alluvial chromites. If concentrates are used as feed to the invention, the concentrates can be obtained, after grinding of the ore, by the use of standard mineral processing technologies such as jigs, spirals, flotation units, and multi-gravity separator.
- the size of the chromite product used depends on the degree of freedom of the chromite grain-size in the matrix from which it is extracted.
- the present invention may comprise procedures allowing secure disposal of the iron extracted from the chromites.
- the method may then further comprises any of the steps of washing the FeCl 3 condensate with an aqueous solution to yield an aqueous solution rich in FeCl 3 ; reacting gaseous Cl 2 with metallic iron to yield an aqueous solution of FeCl 3 ; neutralizing the aqueous solution rich in FeCl 3 with NaOH by the reaction FeCl 3 (aq) + 3NaOH(aq) ⁇ Fe(OH) 3 (s) + 3NaCl(aq) to yield an aqueous solution containing NaCl and an iron hydroxides precipitate; separating the aqueous NaCl solution from the iron hydroxides precipitate to yield a clearer aqueous NaCl solution and a iron hydroxides cake filter, the iron oxide cake being disposable in a regulated tailing pound;
- the present invention comprises procedures allowing recycling of other principal chemical reactants employed in the process.
- the method then comprises burning CO with air to yield gaseous CO 2 ; electrolyzing the NaCl solution to yield Cl 2 , NaOH and H 2 ; recycling at least one of Cl 2 and NaOH as reactants for the chlorination and neutralization reactions; recycling H 2 as additional combustible for the chlorination furnace; and recovering the solid material from which the iron has been extracted by the chlorination reaction.
- the chlorination is performed in a furnace built with material resistant to chlorine, to yield a FeCl 3 gaseous stream and a solid material from which the iron has been extracted and whereby residual chlorine may exit the furnace.
- the present invention comprises means to minimize the production of Cr+6, a known carcinogen contaminant that may be produced in methods using HCl.
- the means include using a reducing atmosphere during the gas solid interactions.
- temperature sufficient to induce the formation of a thin film of a melt around the chromite product refers to a temperature that is sufficient to promote the formation of a FeCl 3 -NaCl system that is liquid. This temperature is at least 157 °C and preferably at least 250 °C.
- the terminology "temperature able to promote the selective chlorination of iron” refers to a temperature that is not sufficiently high to enable the chlorination of other oxides in the chromites. Hence, it is known that at a temperature of 1000°C and higher, all oxides contained in the chromites are chlorinated. In a specific embodiment, the temperature used for this purpose is not higher that 750°C. In a more specific embodiment, this temperature is not higher than 720°C.
- a method for increasing the chrome to iron ratio of a chromite product selected from the group consisting of ore and ore concentrate comprising the steps of mixing the chromite product with at least one salt so as to produce a mixture, whereby the concentration of salt in the mixture is selected to induce the selective chlorination of iron; and chlorinating the mixture in the presence of CO at a temperature sufficient to induce the formation of a thin film of a melt around the chromite product and at a temperature able to promote the selective chlorination of iron, whereby an iron impoverished chromite product is yielded having an increased chromite to iron ratio as compared to that of the chromite product.
- the temperature is between about 157° and about 750°C. In further embodiments, the temperature may be between about 250° and about 720°C. In more specific embodiments, the temperature is between about 670° and about 720°C.
- the at least one salt is selected from the group consisting of NaCl, KCI and MgCl 2 and a combination thereof. In a more specific embodiment, the salt is NaCl and forms about 5% to about 10% w/w of the mixture. In more specific embodiments, the salt forms about 5% w/w of the mixture. In other specific embodiments, the Cl 2 /CO ratio is between about 0.5 and about 1.5. In other specific embodiments, the mixture is dried before chlorination. In other embodiments, N 2 is used as a carrier gaz during chlorination. In other embodiments, the duration of the chlorination is about 30 minutes to about 2 hours. In other embodiments, the duration of the chlorination is about 2 hours.
- a method for increasing the chrome to iron ratio of a chromite product selected from the group consisting of ore and ore concentrate comprising the steps of mixing the chromite product with NaCl so that a mixture is produced having about 5% to about 10% NaCl w/w; and chlorinating the mixture in the presence of CO at a temperature sufficient to induce the formation of a thin film of a melt around the chromite product and at a temperature able to promote the selective chlorination of iron, whereby an iron impoverished chromite product is yielded having an increased chromite to iron ratio as compared to that of the chromite product.
- the temperature is between about 157° and about 750°C. In further embodiments, it may be between about 250° and about 720°C or between about 670° and about 720°C.
- the salt forms about 5% w/w of the mixture.
- the Cl 2 /CO ratio is between about 0.5 and about 1.5.
- the mixture is dried before chlorination.
- N 2 is used as a carrier gaz during chlorination.
- the duration of the chlorination is about 30 minutes to about 2 hours. In other embodiments, the duration of the chlorination is about 2 hours.
- a method for extracting iron from a chromite product selected from the group consisting of ore and ore concentrate comprising the steps of mixing the chromite product with at least one salt; and chlorinating the mixture in the presence of CO at a temperature sufficient to induce the formation of a thin film of a melt around the chromite product so as to promote the chlorination of iron, whereby an iron impoverished chromite product is yielded.
- the salt used is NaCl, it is optimally between 5% and 10% w/w in the mixture and the temperature is below 1000°C and preferably not more than 750°C.
- the method may simply seek to extract as much iron as possible and not preserve a high chrome content in the chromite or avoid chlorination of other oxides. Then the chlorination temperature used and the salt concentration used do not have to be selective and is desirably higher than 1000°C and 10% w/w, respectively.
- the feed (1) used can be ore or an ore concentrate obtained from an appropriate mineral processing technology.
- on the feed used is from a massive chromite layer obtained from the Menarik deposit (James Bay, Quebec).
- the average mineralogy of 29 massive chromite layers of the Menarik Complex is: chromite 45 %, chlorite 32 %, serpentine 13 %, magnetite 3 %, talc 1 %, hornblende 4 %, and traces of sulfides.
- the sample was hand picked from the chromite mineralized zone Cr-3 and subsequently ground to 125 ⁇ m.
- the chemical composition of this starting material, identified as feed (1) in Figure 1 is reported in Table 2 as starting ore for Examples 1 and 2, and in Table 3 as starting ore for Examples 3 to 6.
- NaCl (3) was added to the ground ore as a solution in order to obtain a concentration (w/w) of salt in the feed varying between .8% and 15% according to Examples 1 to 6 below.
- the NaCl salt addition provides one of the components for the formation of an eutectic point which the FeCl 3 produces via the carbochlorination of the chromite feed (reactions are reported under the carbochlorination heading below).
- the phase diagram for the system FeCl 3 -NaCl is illustrated at Figure 2.
- liquid NaFeCl 4 is formed from the reaction of FeCl 3 with NaCl.
- the chlorination temperature varies from 250° to 720° C.
- NaFeCl 4 is present as a liquid phase in the feed at all chlorination temperatures used.
- the salt addition is performed in order to produce a thin film of a melt around each grain of the feed.
- This interstitial melt contains the chlorination agent in a chemical form such as NaFeCl 4 .
- the thin film acts as a chlorination solvent increasing chlorine diffusion in the chromite.
- the chlorine gaseous atmosphere enclosed in the reactor regenerates the effective chlorination agent contained in the melt.
- other types of salts such as KCI and MgCl 2 can be used to produce a catalytic system for the carbochlorination of chromites.
- the drying step ensures a complete removal of water resulting from the salt addition and can be carried out at different temperatures and time periods.
- the mixture was dried at 180 °C for 30 minutes. After cooling, the charge was transferred in the chlorination reactor and pre-heated at the selected reaction temperature.
- ferrous chloride FeCl 2 Another significant reaction occurring according to the process of the present invention is the formation of ferrous chloride FeCl 2 during the carbochlorination phase.
- Ferrous chloride (FeCl 2 ) having a high melting point of 670° C, hence a temperature higher than that used during the carbochlorination according to certain embodiments of the present invention, a rapid chlorination of FeCl 2 into ferric chloride (FeCl 3 ) according to the reaction 2FeCl 2 + Cl 2 ⁇ 2FeCl 3 (g) may be desirable in these specific embodiments in order to avoid the production of a diffusion barrier by the formed solid ferrous chloride. This barrier may decrease the chlorine access to the reaction sites.
- carbochlorination is performed with a salt such as NaCl, KCI and MgCl 2 to produce a catalytic melt when NaCl combines with FeCl 2 and/or FeCl 3 so as to increase the volatilization (the removal) of iron as gaseous FeCl 3 from the carbochlorination reactor.
- a salt such as NaCl, KCI and MgCl 2
- the carbochlorination temperature was reached in the chlorination reactor (5) a mixture of Cl 2 and CO and, in specific embodiments, N 2 (not shown) was introduced in the reactor so as to induce carbochlorination. After a few minutes, FeCl 3 (g) (5) was expelled from the reactor. According to specific embodiments described Examples below, the temperature was varied from 250° to 720°C. However because of thermodynamics rules, it is expected that this temperature may be increased at least up to 750°C without loosing the selectivity of the chlorination towards iron. In specific embodiments, chlorine and carbon monoxide were used on a 1/1 basis. The flow rate was maintained at 1 ml per second.
- a mixture of Cl 2 , CO, and N 2 was employed, N 2 acting as a carrier gas.
- N 2 is not believe to play a role in any reaction involved in the method and may accordingly be dispensed of.
- the flow rates of the different gases were varied as well as the weight % of salt additives. Results (not shown) have shown that the optimal Cl 2 /CO flow rate ratio is between about 0.5 and about 1.5. Interesting results are nevertheless obtained outside this range but the Cr/Fe obtained progressively decreases with ratios below 0.5 or above 1.5 (results not shown).
- chlorination reactions were conducted in a simple horizontal static furnace.
- chlorination is realized in fluidized bed reactors constructed of acid resistant bricks enclosed in a metal shell. Since the salt addition results in the formation of a thin liquid film layer around the chromite grains, which increases their adherence properties, it may be desirable to avoid fluidized reactor in order to avoid problems associated with grains agglomeration and bed sedimentation.
- Alternatives to fluidized bed reactor include a vertical static reactor and a horizontal rotating reactor.
- inventions of the present invention may include the use of solid reducing agents like coal or coke instead of CO which may be onerous for industrial scale methods.
- solid reducing agents like coal or coke
- CO may be onerous for industrial scale methods.
- coal and coke react with oxygen to form CO so that the end result is similar to that obtained when CO is directly introduced in the chlorination reactor.
- Pelletizing-sintering procedures similar to the ones employed in the ferrochromium industry, can be performed before the chlorination step.
- Gaseous FeCl 3 (10) exits continuously the reactor during the reaction and the abrupt temperature drop outside the reactor causes its fast condensation in the top section of the condenser.
- the condenser is placed at an adequate distance from the furnace so as to keep its temperature below 50 °C so as to ensure FeCl 3 's condensation.
- FeCl 3 is highly soluble in water. A small volume of water is added to the condenser apparatus to wash the solid FeCl 3 .
- the FeCl 3 rich aqueous solution accumulates at the base of the condenser and is directed into a reservoir for subsequent neutralization.
- the other gases leaving the reactor are essentially Cl 2 , CO, CO 2 (12) and N 2 (not shown). These gases are apparently not affected by the presence of the condenser (8) and flow through it without experiencing any detectable change in their compositions or states and exit the condenser.
- the aqueous FeCl 3 solutions (10) and (20) coming from the condenser (8) and the washing tower are pumped in a neutralization reservoir (28).
- a solution of NaOH (not shown) is added to the reservoir.
- the ferric chloride reacts with NaOH to produce Fe(OH) 3 (30) according to the reaction: FeCl 3 (aq) + 3NaOH(aq) ⁇ Fe(OH) 3 (s) + 3NaCl(aq)
- the solid amorphous iron oxides are isolated from the liquid phase by an appropriate solid-liquid separation such as centrifugation or press filtration (31).
- the filtration cake is discharged to the tailings.
- the aqueous NaCl solution (32) is directed to an electrolysis cell (34).
- the NaCl solution (32), obtained from the neutralization step of the process, is electrolyzed by a chlor-alkali membrane cell process.
- the reaction involved is: 2NaCl(aq) + 2H 2 O ⁇ H 2 (g) + Cl 2 (g) + 2NaOH(aq)
- the gaseous Cl 2 and aqueous NaOH generated by the reaction are recycled in the process.
- the Cl 2 is returned (36) to the carbochlorination reactor (5) and the aqueous NaOH is directed (31) in the neutralization reservoir (28).
- the H 2 (g) produced (not shown) by this reaction can be employed as the main energy source or an additional energy source for the carbochlorination reactor (5). External supplies of NaCl can be used if needed.
- Tables 2- 5 The implementation and results of Examples provided herein are summarized in Tables 2- 5.
- Table 2 presents results according to the first set of experiments for which the Cl 2 /CO ratio flow rates, reaction time, and type and quantity of salt addition were kept constant during the experiments, while the temperature was varied. Examples 1 and 2 are derived from this first set of experiences.
- Tables 3 and 4 contain data for the second set of embodiments for which, temperature, reaction time and quantity of salt addition were varied. This second set of experiments is represented in Examples 3 to 6.
- the major and trace elements were analyzed by inductively couple plasma atomic emission spectroscopy, ICP-AES, after a fusion procedure specifically applicable to chromite. Sulfur was determined with a CNS analyzer. Table 3. Reaction conditions and results for the second set of experiments.
- This example comprises a set of 4 experiments. The results are presented in Table 2.
- This Example demonstrates the selectivity of the iron removal by carbochlorination versus chromium according to the method of the present invention. The other major elements are reported in Table 2 for indicative purposes only.
- the range of temperature tested varied from 250 to 550°C.
- the chlorinated sample were mixed with a NaCl brine and dried at 180°C for 30 minutes.
- the salt content of the chlorinated samples was 5 % (w/w).
- a 10 g sample of chromite ore was placed in a 10 ml porcelain beaker. The beaker was positioned in the center of 60 cm in length silica tube, with an internal diameter of 6 cm.
- the assembly beaker-silica tube was placed in the furnace and the temperature was raised at the chosen carbochlorination temperature.
- a Cl 2 , CO gas mixture was introduced in the furnace on a one to one ratio basis.
- the carbochlorination step was conducted for 60 minutes.
- a red brown chlorine vapor formed five minutes after the beginning of introducing the gases in the furnace. This vapor was expelled outside the reactor through the gases flow, where it condensed on the inside wall of the silica tube.
- the furnace-heating device and the gases flow were stopped. After a cooling period, the solid residue left in the porcelain beaker was analyzed for major and selected trace elements.
- the temperature of 673°C was selected as slightly superior to the melting point of FeCl 2 (670°C).
- the total reaction time varied from 0.5 hour to 2.0 hours with a time increment of a half hour for each of samples were T-2-9 to T-2-12 as in Example 4.
- the experimental conditions and the results for these experiments are reported in Table 3. It is postulated that FeCl 2 is formed at some point during the chlorination and subsequently transformed in FeCl 3 according to the reaction FeCl 2 + 1/2Cl 2 ⁇ FeCl 3 (g). At temperature below the melting point of FeCl 2 , the presence of this compound as a solid can act as a blocking agent between the chlorination agent and the chromites reaction sites.
- Chromium to iron ratio increase versus temperature and duration of the reaction
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Claims (22)
- Procédé pour augmenter le rapport chrome/fer d'un produit de chromite choisi dans le groupe constitué de minerais et de concentré de minerais, comprenant les étapes de :a. mélange du produit de chromite avec au moins un sel afin de produire un mélange, dans lequel la concentration en sel dans le mélange est choisie pour induire la chloration sélective du fer ; etb. chloration du mélange en présence de CO à une température suffisante pour induire la formation d'un film mince d'un bain autour du produit de chromite et à une température capable de promouvoir la chloration sélective du fer,de sorte qu'un produit de chromite appauvri en fer soit obtenu en ayant un rapport chromite/fer augmenté par rapport à celui du produit chromite.
- Procédé selon la revendication 1 dans lequel ladite température est comprise entre environ 157 et environ 750°C.
- Procédé selon la revendication 1 dans lequel le au moins un sel est choisi dans le groupe constitué de NaCl, KCl, MgCl2 et une combinaison de ces sels.
- Procédé selon l'une de quelconque revendications 1 et 2 dans lequel le sel est le NaCl et forme environ 5 % à environ 10 % en poids/poids du mélange.
- Procédé selon l'une de quelconque revendications 1 et 2 dans lequel le sel est le NaCl et forme environ 5 % en poids/poids du mélange.
- Procédé selon l'une quelconque des revendications 1 à 3 dans lequel la température est comprise entre environ 250 et environ 720°C.
- Procédé selon l'une quelconque des revendications 1 à 4 dans lequel la température est comprise entre environ 670 et environ 720°C.
- Procédé selon l'une quelconque des revendications 1 à 7 dans lequel le rapport Cl2/CO est compris entre environ 0,5 et environ 1,5.
- Procédé selon l'une quelconque des revendications 1 à 8 dans lequel le mélange est séché avant chloration.
- Procédé selon l'une quelconque des revendications 1 à 9 dans lequel on utilise le N2 comme gaz vecteur pendant le chloration.
- Procédé selon l'une quelconque des revendications 1 à 10 dans lequel la durée de chloration est d'environ 30 minutes à environ 2 heures.
- Procédé selon l'une quelconque des revendications 1 à 10 dans lequel la durée de chloration est d'environ 2 heures.
- Procédé pour augmenter le rapport chrome/fer d'un produit de chromite choisi dans le groupe constitué de minerai et de concentré de minerais, comprenant les étapes de :a. mélange du produit de chromite avec du NaCl de façon à produire un mélange ayant environ 5 % à environ 10 % en poids/poids de NaCl, etb. chloration du mélange en présence de CO à une température suffisante pour induire la formation d'un film mince d'un bain autour du produit de chromite et à une température capable de promouvoir la chloration sélective du fer,de sorte qu'un produit de chromite appauvri en fer soit obtenu ayant un rapport chromite/fer augmenté par rapport à celui du produit chromite.
- Procédé selon la revendication 13 dans lequel ladite température est comprise entre environ 157 et environ 750°C.
- Procédé selon l'une quelconque des revendications 13 et 14 dans lequel le sel est le NaCl et forme environ 5 % en poids/poids du mélange.
- Procédé selon l'une quelconque des revendications 13 à 15 dans lequel la température est comprise entre environ 670 et environ 720°C.
- Procédé selon l'une quelconque des revendications 13 à 16 dans lequel le rapport Cl2/CO est compris entre environ 0,5 et environ 1,5.
- Procédé selon l'une quelconque des revendications 13 à 17 dans lequel le mélange est séché avant chloration.
- Procédé selon l'une quelconque des revendications 13 à 18 dans lequel on utilise le N2 comme gaz vecteur pendant la chloration.
- Procédé selon l'une quelconque des revendications 13 à 19 dans lequel la durée de chloration est d'environ 30 minutes à environ 2 heures.
- Procédé selon l'une quelconque des revendications 13 à 20 dans lequel la durée de chloration est d'environ 2 heures.
- Procédé d'extraction du fer d'un produit de chromite choisi dans le groupe constitué de minerais et de concentré de minerais, comprenant les étapes de :a. mélange du produit de chromite avec au moins un sel, etb. chloration du mélange en présence de CO à une température suffisante pour induire la formation d'un film mince d'un bain autour du produit de chromite pour promouvoir la chloration du fer,de sorte qu'un produit de chromite appauvri en fer soit obtenu.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA 2418546 CA2418546A1 (fr) | 2003-02-06 | 2003-02-06 | Methode permettant d'accroitre le rapport chrome/fer de produits du type chromite |
CA2418546 | 2003-02-06 | ||
US44543703P | 2003-02-07 | 2003-02-07 | |
US445437P | 2003-02-07 | ||
PCT/CA2004/000165 WO2004070066A1 (fr) | 2003-02-06 | 2004-02-06 | Procede permettant d'accroitre le rapport chrome-fer des produits chromites |
Publications (2)
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EP1590494A1 EP1590494A1 (fr) | 2005-11-02 |
EP1590494B1 true EP1590494B1 (fr) | 2006-08-09 |
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EP04708695A Expired - Lifetime EP1590494B1 (fr) | 2003-02-06 | 2004-02-06 | Procede permettant d'accroitre le rapport chrome-fer des produits chromites |
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EP (1) | EP1590494B1 (fr) |
AT (1) | ATE335861T1 (fr) |
AU (1) | AU2004209574A1 (fr) |
DE (1) | DE602004001860D1 (fr) |
WO (1) | WO2004070066A1 (fr) |
Cited By (1)
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CN108101120A (zh) * | 2018-01-19 | 2018-06-01 | 四川大学 | 一种制备三氯化铁的新方法 |
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CA2435779A1 (fr) | 2003-07-22 | 2005-01-22 | Institut National De La Recherche Scientifique | Un procede de recuperation de metaux du groupe du platine dans des minerais et des concentres |
CN112798550B (zh) * | 2021-04-14 | 2021-07-13 | 四川大学 | 一种宽测量范围的激光吸收光谱燃烧诊断方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US2752301A (en) * | 1951-03-07 | 1956-06-26 | Walter M Weil | Recovery of chromium and iron values from chromium-iron ores |
AU1340276A (en) * | 1975-05-07 | 1977-11-03 | Ici Australia Limited | Removal of iron from ferruginous materials |
AU5806896A (en) * | 1996-05-31 | 1998-01-05 | Ug Plus International Inc. | Process for obtaining chromium enriched chromite from chromite ores |
-
2004
- 2004-02-06 EP EP04708695A patent/EP1590494B1/fr not_active Expired - Lifetime
- 2004-02-06 AU AU2004209574A patent/AU2004209574A1/en not_active Abandoned
- 2004-02-06 DE DE602004001860T patent/DE602004001860D1/de not_active Expired - Lifetime
- 2004-02-06 WO PCT/CA2004/000165 patent/WO2004070066A1/fr active IP Right Grant
- 2004-02-06 AT AT04708695T patent/ATE335861T1/de not_active IP Right Cessation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108101120A (zh) * | 2018-01-19 | 2018-06-01 | 四川大学 | 一种制备三氯化铁的新方法 |
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ATE335861T1 (de) | 2006-09-15 |
AU2004209574A1 (en) | 2004-08-19 |
DE602004001860D1 (de) | 2006-09-21 |
WO2004070066A1 (fr) | 2004-08-19 |
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