EP0092562A1 - Chlorination of an aluminous material - Google Patents
Chlorination of an aluminous materialInfo
- Publication number
- EP0092562A1 EP0092562A1 EP82903251A EP82903251A EP0092562A1 EP 0092562 A1 EP0092562 A1 EP 0092562A1 EP 82903251 A EP82903251 A EP 82903251A EP 82903251 A EP82903251 A EP 82903251A EP 0092562 A1 EP0092562 A1 EP 0092562A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- stage
- chloride
- aluminium
- chlorine
- carbon monoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 22
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 53
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 230000008569 process Effects 0.000 claims abstract description 46
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 40
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 33
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000460 chlorine Substances 0.000 claims abstract description 32
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 31
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 25
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 21
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 19
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 19
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 18
- 230000009467 reduction Effects 0.000 claims abstract description 18
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 14
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 8
- NHYCGSASNAIGLD-UHFFFAOYSA-N chlorine monoxide Inorganic materials Cl[O] NHYCGSASNAIGLD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 21
- 239000004411 aluminium Substances 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012808 vapor phase Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 37
- 238000006722 reduction reaction Methods 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 239000000155 melt Substances 0.000 description 7
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- 229910003074 TiCl4 Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 238000006298 dechlorination reaction Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 230000008022 sublimation Effects 0.000 description 3
- 238000004131 Bayer process Methods 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910003910 SiCl4 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 alkali-metal salts Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- SURLGNKAQXKNSP-DBLYXWCISA-N chlorin Chemical compound C\1=C/2\N/C(=C\C3=N/C(=C\C=4NC(/C=C\5/C=CC/1=N/5)=CC=4)/C=C3)/CC\2 SURLGNKAQXKNSP-DBLYXWCISA-N 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/02—Halides of titanium
- C01G23/022—Titanium tetrachloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
- C01F7/58—Preparation of anhydrous aluminium chloride
- C01F7/60—Preparation of anhydrous aluminium chloride from oxygen-containing aluminium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/06—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
Definitions
- TITLE Chlorination of an aluminous material
- This invention relates to a process for the chlorination of an aluminous material, particularly bauxite. More specifically this invention relates to a process for the chlorination of an aluminous material such as bauxite to give aluminium chloride of sufficient purity for it to be suitable for use as the cell feed for the electrolysis of aluminium chloride to give aluminium metal. According to another aspect the invention provides a process whereby by-products of the primary production of aluminium chloride from an aluminous material such as bauxite may be easily recovered and, if desired, converted into valuable components for recycling.
- Carbochlorination of bauxite to produce aluminium chloride has been fairly widely used industrially over the past 60 years or so.
- the best known examples are the processes employing the treatment of bauxite with chlorine and carbon, or with mixtures of chlorine and carbon monoxide or phosgene. These processes, however, relied on sources of bauxite with a very low content of iron oxide.
- pure gibbsite was used when supplies of bauxite low in iron oxide were no longer available. This would not be economically acceptable for the production of aluminium chloride for use as electrolytic cell-feed.
- a disadvantage of an earlier proposal is the lack of any satisfactory step either for the separation of iron chlorides from aluminium chloride, or for the recovery of chloride values from the iron chloride in conjunction with the conversion of the iron residue to an environmentally acceptable or saleable form.
- One suggested method for the removal of iron chloride from the aluminium chloride has involved the use of metallic aluminium to reduce ferric chloride, FeCl_ , to ferrous
- the present invention thus provides a multi ⁇ stage process for the production of aluminium chloride which comprises
- the selective reduction in stage (C) whereby aluminium chloride is separated from ferric chloride may be accomplished using carbon monoxide as the reducing agent or metallic iron.
- the process according to the invention is particularly economical in that reactants required for one stage of the multi-stage process can be generated from another stage.
- carbon monoxide which is preferably employed in the first stage (A) for the chlorination of the aluminous material is obtained in a further reaction stage (E) by reaction of the carbon dioxide off-gas from the condensation stage with a suitable source of carbon at _an elevated temperature.
- the carbon monoxide obtained from the carbon dioxide off-gas in stage ( ⁇ ) may also be used in a subsequent reaction stage, (C) according to one embodiment, where the aluminium and ferric chlorides are separated by reduction with carbon monoxide.
- the ferrous chloride resulting from the separation of the aluminium chloride is subjected to a further reaction stage (D) where the ferrous chloride is oxidised with oxygen or an oxygen-containing gas at an ' elevated temperature preferably in the presence of at least one salt of an alkali metal or alkaline earth metal.
- This oxidation reaction produces iron oxide and chlorine which is recycled to the initial chlorination stage (A) .
- the oxidation reaction of stage (D) may be operated under conditions such that the iron oxide produced is in the form of an industrially useful form of iron oxide suitable, for example, for pigmentary application or for use as a filler.
- the iron oxide, or a part thereof, obtained in stage (D) , by dechlorination of ferrous chloride may be subjected to further reduction in stage (F) , for example using carbon monoxide, to give the metal which may be recycled to stage (C) when the separation of the ferric and aluminium chloride (C) is accomplished using metallic iron.
- stage (F) for example using carbon monoxide
- the carbon monoxide required for this reaction may be obtained from the carbon monoxide generation stage (E) as previously described.
- the present invention not only provides a process for the production of aluminium chloride suitable for use as feed for an electrolysis cell but also provides a process whereby chlorine values can be recovered from iron chloride by-product and used in the initial chlorination stage of the invention.
- the invention moreover provides a multi-stage process whereby reactants -such as carbon monoxide, phosgene and metallic iron can be generated from one process stage and recycled for use in another stage.
- reactants -such as carbon monoxide, phosgene and metallic iron can be generated from one process stage and recycled for use in another stage.
- the invention also lends itself to the production of a potentially valuable by-product, iron oxide.
- the process comprises the following reaction stages:- Stage A
- bauxite (identified as BX . in the flowsheets) is chlorinated using chlorination reagents which comprise chlorine together with carbon monoxide, or phosgene (C0C1-) , or mixtures of chlorine, carbon. onoxide and phosgene. Chlorin ⁇ ation of the alumina content of the bauxite then occurs according to the following chemical equations:
- the Fe ⁇ O.., TiO- and SiO- contents of the bauxite are similarly chlorinated to give FeCl,, TiCl 4 and SiCl. respectively.
- the chlorination reaction may be carried out in either a fixed-bed type of reactor, as has been de ⁇ scribed in the literature for example by Wurster (Zeitschrift fur Angewandte Chemie 1930, 43, 877-880) and Hille and Durrwachter (Angewandte Chemie, I960, pp. 73-79) , or it may be performed in a fluid-bed reactor.
- the bauxite is ' preferably calcined prior to the chlorination
- the temperature chosen for calcination will depend to some extent on the increase in reactivity and decrease in water content desired, but is likely to be in the temperature range 600 - 1100°C.
- the temperature employed for chlorination will depend on the reaction rate obtainable, compared with the service life of containment refractories, but will generally fall within the range 550°C-1100°C..
- the chlorination reaction may be carried out batchwise or continuously.
- a second stage (B) some of the chlorides by-produced in the first stage (A) , and particularly titanium and silicon tetrachlorides (ii) , are removed by condensation.
- the product gases leaving the chlorination reactor (Stage A) comprise a mixture of carbon dioxide, aluminium chloride (AlCl,) , ferric chloride (FeCl 3 ) , titanium tetrachloride (TiCl.) , and silicon tetrachloride (SiCl.) .
- Stage (B) is a two- stage condenser, the operating principle of which is based on the difference in volatilities between FeCl, (boiling-point 315°C) , AlCl., (Sublimation temperature 177.8°C), TiCl 4 (boiling-point 136.4°C) and SiCl 4 (boiling-point 57.6°C). Due to the well-known vapour-phase association between FeCl., and AlCl., to give FeAlCl fi , it is not possible to separate these two species by a simple condensation step.
- the first stage of the condenser is maintained at a temperature below 177.8°C (the sublimation temperature of AlCl,) , but substantially above the boiling-point of TiCl. (136.4°C).
- the first stage of the condenser may take any suitable form.
- a preferred form of condenser particularly suitable for the continuous deposition in solid form of FeCl,- and AlCl,-containing species from the vapour-phase comprises a fluidised- bed of a suitable inert material, maintained at a suitable temperature to ensure substantially complete removal of the FeCl, and AlCl,-containing species from the vapour-phase.
- a fluidised- bed of a suitable inert material maintained at a suitable temperature to ensure substantially complete removal of the FeCl, and AlCl,-containing species from the vapour-phase.
- continuous removal of the product can be achieved by maintaining a continous bed overflow.
- the second stage of the condenser may again take any suitable form, and is maintained at a temperature low enough to ensure substantially complete removal of the remaining chlorides, TiCl. and SiCl ⁇ ,, from the vapour-phase. Condensation of TiCl 4 and SiCl.
- separation of TiCl. and SiCl d may be provided for by operating the second stage of the condenser at a temperature within the range between the boiling-points fo SiCl. and iCl ⁇ (57.6°C and 136.4°C respectively) with a number of fractionating stages.
- the output from Stage (B) therefore comprises three distinct product streams, viz. (i) a solid mixture of AlCl, and FeCl., from the first stage, (ii) liquid TiCl. and SiCl ⁇ from the second stage, and (iii) carbon dioxide gas from the second stage.
- Stage C a solid mixture of AlCl, and FeCl.
- ferric chloride is separated from the desired aluminium chloride. Separation of the FeCl, from the AlCl, is accomplished by chemical reduction of the FeCl, to F Cl 2 , which has a much lower volatility than FeCl, and therefore can be separated by deposition as a solid
- the reducing agent used is carbon monoxide.
- the reduction step is represented by the following chemical equation:
- the reaction may be carried out in the vapour-phase, at a temperature. above the boiling-point of FeCl, (315°C) but below the melting-point of eCl 2 (673°C) . Within this temperature range, reduction of FeCl, to FeCl- according to equation (3) results in the deposition of FeCl- in solid form from the vapour-phase, leaving substantially iron-free AlCl 3 in the vapour-phase, suitable for feeding to the electrolytic cell.
- silica envelope 4 and side-arm 6 were heated by means of electrically-powered heating tape
- AlCl, for reaction (3) may be obtained by the vaporisation of the mixed condensed FeCl, - AlCl, solids from Stage (B) , and feeding the resulting vapour
- the desired reactor configuration may take several possible forms.
- a particularly suitable form is a cyclone reactor, into which the carbon monoxide gas and mixed FeCl- - AlCl, vapours
- This reactor configuration provides for continuous operation, with good mixing of the reacting gases and a relatively long residence time per unit of reaction volume, and facilitates the discharge of the solid FeCl- from the bottom of the
- Reaction 3 may also be performed by contacting carbon ,_ monoxide gas with the solid FeCl., -AlCl,, followed by
- Equation (3) It may be preferable to initiate the reaction exemplified in Equation (3) , whether performed as a vapour-solid reaction or as a homogeneous vapour-phase reaction, by the presence of sulphur or a sulphur chloride, as described in U.S. Patent 4,140,746.
- the separation of FeCl, from A1C1 3 according to this invention based on Equation (3) has the advantage, not found with other methods of * separating FeCl, from AlCl,, of providing phosgene, C0C1 2 , as a useful by-product for recycle to the bauxite chlorination reactor (Stage A).
- Stage (E) the requirement of a source of carbon monoxide for use as the reducing agent is met, as will be described later under Stage (E) , by the passage of carbon dioxide (obtained from Stage (A) and after passing through the two-stage condenser (Stage B) over heated carbon.
- the method of separating FeCl, from AlCl, according to this embodiment of the invention is therefore eminently suitable when seen in the context of the overall process, the aim of which is to provide AlCl, of eletroclytic cell-feed purity, starting with the chlorination of an " aluminous material such as bauxite.
- Stage (D) chlorine values are recovered from the ferrous chloride produced in Stage (C) , and, recycled to the chlorination Stage (A) .
- the fourth Stage (D) may also be used to by-produce an industrially useful form of iron oxide.
- the ferrous chloride by-product from Stage (C) is subjected in Stage (D) to oxidation with oxygen or an oxygen-containing -gas at an elevated temperature in the presence of at least one salt of an alkali metal or alkaline earth metal.
- the preferred salts are those with which ferrous chloride forms melts which are most suitable to meet the particular requirements of the oxidation process
- Sodium chloride is one of the preferred salts and is used to exemplify, in the following reaction equations, the nature of the oxidation reaction.
- other salts may also be used to satisfy the specific requirements of the process according to the invention and to achieve the specific properties which may be required of the iron oxide produced as a co- product.
- suitable salts include sodium sulphate, sodium carbonate, sodium metaborate, sodium tetraborate, sodium chlorate, potassium chloride, potassium carbonate, lithium chloride, magnesium chloride, magnesium sulphate, calcium carbonate and calcium chloride and mixtures thereof.
- the oxidation reaction according to the present invention is postulated in the following equations using, as example, sodium chloride as the salt.
- the apparatus comprises a gas-tight silica envelope 1 having a silica crucible base 2 and being
- _CHH provided with a tube 3 for input of oxidising gas (0 2 or air) , a sheathed thermocouple 4 and outlet 5 for the C1-/0- off-gases.
- the apparatus is adapted to be heated by means of a resistance-wound tube furnace 6.
- a mixed charge of FeCl- and an alkali (or alkaline) earth metal salt 7 was melted and brought up to the desired reaction temperature under nitrogen in the gas-tight silica envelope 1, which was heated by the resistance-wound tube-furnace 6.
- the melt temperature was measured by means of the sheathed thermocouple 4 immersed in the melt 7.
- Oxidation was then commenced by bubbling oxygen or air through the melt via tube 3 at a measured flow-rate for a timed period, the off-gas 5 being scrubbed with sodium hydroxide solution.
- the reactor and contents were allowed to cool under nitrogen, followed by water leaching and chemical analysis of the reaction products.
- the results of a batch oxidation run performed in the apparatus shown in Fig. 4 using a melt of molar composition 0.5 FeCl-, 0.52 NaCl, 0.48 N 2 S0. are shown in the following Table 1.
- the results show the excellent chlorine recovery (91%) attained.
- the melt composition selected for this run is particularly suitable for batch operation in a simple sparged fused salt-bath reactor, since the added alkali-metal salts (NaCl and Na-SO d ) are present in the ratio corresponding to the NaCl-Na-SO, eutectic composition (eutectic temperature 625°C) .
- the iron oxide co-product of the oxidation reaction was separated off by a simple water-leaching procedure, followed by filtration, water-washing and drying. If desired, the soluble salts can be recovered for re-cycling. Further water-washing of the iron oxide is needed to remove traces of absorbed chloride-. This can be achieved by elutriation with water which can be used to classify the product into fractions varying in particle size and suitable for different pigmentary applications or, for example, for use as a filler.
- the present invention not only provides a method of recovering chlorine from iron chloride which chlorine can be recycled to the bauxite chlorination Stage (A) , but also provides a method of producing a potentially industrially useful iron oxide.
- a by-product which has to date caused considerable problems of disposal is transformed into a readily available starting material for two valuable industrial products.
- the optimum reaction conditions for Stage (D) of the process depend, among other things on the particular salt which is employed.
- the oxidation reaction may be effected in the melt or on the particul ⁇ ate solids.
- a suitable source of carbon is coke or coal char.
- the carbon monoxide-forming reaction as represented by equation (8) is endothermic.
- Various methods are availalbe for supplying the necessary heat, for example the coke or coal char bed, which may be either a fixed-bed or a fluidised-bed, may be heated directly by inserting electrodes into the charge and passing on electric current through the charge, as has been described, for example, for a fluidised-bed reactor in U.S. Patent No. 2,921,840, and for a fixed-bed reactor in U.K. Patent No. 001,657.
- An alternative method of supplying process heat is to admit a mixture of oxygen and carbon dioxide to the carbon monoxide generator, the oxygen reacting exothermically with the coke or coal char according to the equations:
- Stages (A) chlorination of bauxite), B (condensation of titanium and silicon tetracr.lorides) , D (dechlorination of ferrous chloride) and ⁇ (generation of carbon monoxide from carbon dioxide and carbon) are as described in the first embodiment of the invention described with reference to Figure 1.
- Stage (C) is affected using metallic iron to separate hs aluminium and iron chlorides and an additional stage (Stage F) is employed in which ferric oxide is reduced with carbon monoxide to give metallic iron.
- Stage F Stage F
- 5zis embodiment may advantageously be employed whe for any reason it is preferred not to recycle phosgene
- Stage (C) of this embodiment and the addition Stage (F) are as described below.
- Stage F
- ferric oxide is reduced with carbon monoxide to give metallic iron.
- the underlying chemical principle of this stage is the well-known ability of carbon monoxide to reduce ferric oxide to metallic iron according to the chemical equation:
- Equation (11) which forms the basis of the production of iron from iron ore in a blast furnace, is given in Mellor's Comprehensive Treatise on Inorganic and Theoretical Chemistry, Volume XIII (Part 2) r p. 813.
- a reaction temperature of ca. 905°C essentially complete reduction of ferric oxide to metallic iron occurs.
- part of the ferric oxide from Stage (D) (dechlorination of ferrous chloride) is fed to a reduction reactor which may take any suitable form e.g. a fixed- or fluidised-bed, where reaction occurs according to Equation (11) with carbon monoxide provided from Stage (E) (generation of carbon monoxide from carbon dioxide and carbon) .
- a fluidised-bed reactor it is possible to provide for a continuous feed of ferric oxide and a continuous bed overflow of metallic iron.
- the metallic iron which is produced in extremely reactive form, is fed to Stage (C) in which FeCl, and AlCl 3 are separated using metallic iron as described hereinafter.
- the by-product carbon dioxide may be recycled to Stage (E) but is preferably put to stack .
- Stage G is preferably put to stack .
- the reducing agent used is metallic iron from Stage (F) (reduction of ferric oxide with CO to give metallic iron) .
- the reduction step is represented by the following chemical equation:
- the reaction is advantageously carried out at a temperature above the boiling-point of eCl 3 (315°C) but below the melting-point of FeCl- (673°C) .
- eCl 3 315°C
- FeCl- 673°C
- Equation (12) reduction of FeCl, to FeCl- according to Equation (12) results in the deposition of FeCl- in solid form from the vapour-phase, leaving a substantially iron-free AlCl, vapour which is fed to the electrolytic cell for the production of aluminium metal.
- the required feed of gaseous FeCl, andAlCl, for the reaction represented by Equation (12) may be obtained by the vaporisation of the mixed condensed FeCl 3 - AlCl, solids from Stage (B) , and feeding the resulting vapour stream into a suitable reactor where the vapour comes into contact with, and is reduced by, the metallic iron from Stage (F) .
- the desired reactor configuration may again take several possible forms, e.g. a fixed- or fluidised-bed. De- position of ferrous chloride in solid form may occur
- this invention comprises a most skilful synthesis from several process stages to give an overall process particularly applicable to the production of electrolytic cell-feed aluminium chloride from the c.hlorination of bauxite.
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GB8132456 | 1981-10-28 | ||
GB8132456 | 1981-10-28 |
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US9896775B2 (en) | 2012-01-04 | 2018-02-20 | Keki Hormusji Gharda | Process for manufacturing aluminum from bauxite or its residue |
NO20190144A1 (en) * | 2019-01-31 | 2020-08-03 | Norsk Hydro As | A process for production of aluminium |
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US1875105A (en) * | 1926-08-07 | 1932-08-30 | Niagara Smelting Corp | Method of and apparatus for mineral chlorination |
GB2020643A (en) * | 1978-05-10 | 1979-11-21 | Mineral Process Licennsing Cor | Recovery of chlorine |
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1982
- 1982-10-22 ZA ZA827753A patent/ZA827753B/xx unknown
- 1982-10-27 IT IT49375/82A patent/IT1158027B/it active
- 1982-10-27 EP EP82903251A patent/EP0092562A1/en not_active Withdrawn
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