NO144297B - PROCEDURE FOR OXYDATION OF TITANIUM ORE - Google Patents
PROCEDURE FOR OXYDATION OF TITANIUM ORE Download PDFInfo
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- NO144297B NO144297B NO763518A NO763518A NO144297B NO 144297 B NO144297 B NO 144297B NO 763518 A NO763518 A NO 763518A NO 763518 A NO763518 A NO 763518A NO 144297 B NO144297 B NO 144297B
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- oxygen
- temperature
- ore
- carbon
- oxidation
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- 238000007254 oxidation reaction Methods 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title description 2
- 239000010936 titanium Substances 0.000 title description 2
- 229910052719 titanium Inorganic materials 0.000 title description 2
- 230000003647 oxidation Effects 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000003570 air Substances 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 7
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002006 petroleum coke Substances 0.000 claims description 3
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000000571 coke Substances 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- -1 hydroxyl ions Chemical class 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
-
- 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
- C22B1/10—Roasting processes in fluidised form
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Ceramic Products (AREA)
Description
Oppfinnelsen angår oxydasjon av titanjernmalmer, som ilmenitt, for å befordre en selektiv fjernelse av jernforbind-elsene i malmene ved høy temperatur ved utluting eller klorer- The invention relates to the oxidation of titanium iron ores, such as ilmenite, to promote a selective removal of the iron compounds in the ores at high temperature by leaching or chlorination.
ing. Eng.
Oxydasjon av ilmenitt er en hurtig og enkel prosess som Oxidation of ilmenite is a fast and simple process which
finner sted ved en temperatur av 600°C og derover i en oxygenholdig atmosfære. Produktet ved oxydasjon av ilmenitt kan variere av-hengig av typen av den anvendte ilmenitt og oxydasjonstemperaturen. Det foreligger en tilbøyelighet til at materialet vil omdannes til pseudobrokitt ved en temperatur av 900°C og derover, som beskrevet i US patentskrifter nr. 3875286 og nr. 3803287. I det sistnevnte patentskrift er det angitt at den oxyderende røsting nedsetter titanets reaktivitet i ilmenitt overfor klor slik at den preferen-sielle klorering av jern påskyndes, og samtidig forbedres separer-ingen av jern under elektrostatisk oppredning. I US patentskrift nr. 3875286 er et foroxydasjonstrinn angitt, fulgt av et reduk-sjonstrinn for å forbedre anrikningen ved utluting under anvendelse f.eks. av saltsyre som inneholder en del toverdig jernklorid for å lette utlutingsprosessen. takes place at a temperature of 600°C and above in an oxygen-containing atmosphere. The product by oxidation of ilmenite can vary depending on the type of ilmenite used and the oxidation temperature. There is a tendency for the material to transform into pseudobrochite at a temperature of 900°C and above, as described in US patents no. 3875286 and no. 3803287. In the latter patent it is stated that the oxidizing roasting reduces the reactivity of titanium in ilmenite against chlorine so that the preferential chlorination of iron is accelerated, and at the same time the separation of iron during electrostatic preparation is improved. In US Patent No. 3875286 a preoxidation step is indicated, followed by a reduction step to improve the enrichment by leaching using e.g. of hydrochloric acid containing some divalent ferric chloride to facilitate the leaching process.
I US patentskrift nr. 38 75286 er ikke oxydasjonsbetingelsene krevet som en del av den deri krevede oppfinnelse. I begge de to US patentskrifter efterfølges oxydasjonen av en reduksjon i en atmosfære som har et underskudd av oxygen. In US Patent No. 38 75286, the oxidation conditions are not claimed as part of the invention claimed therein. In both of the two US patents, the oxidation is followed by a reduction in an atmosphere that has a deficit of oxygen.
Ved anrikning av strandsandilmenitt ved høytemperatur-klorering er det nødvendig å forvarme ilmenitten for å drive av hydrogen som er tilstede ikke bare som vann, men som en del av hydroxylioner som er absorbert på malmens store overflate. Det er nødvendig å fjerne hydrogen for å unngå klortap i form av hydrogenklorid ved de høye temperaturer som anvendes i anriknings-reaktoren. When beneficiating beach sand ilmenite by high-temperature chlorination, it is necessary to preheat the ilmenite to drive off hydrogen which is present not only as water, but as part of hydroxyl ions absorbed on the large surface of the ore. It is necessary to remove hydrogen to avoid chlorine loss in the form of hydrogen chloride at the high temperatures used in the enrichment reactor.
En annen og like viktig grunn til forvarmingen av ilmenitten er for opprettholdelse av varmebalansen for anrikningen ved høy-temneraturklorerinq da høye temperaturer er ønskede for = oppnå Another and equally important reason for the preheating of the ilmenite is to maintain the heat balance for the enrichment during high-temperature chlorination, as high temperatures are desired to = achieve
de ønskede reaksjonshastigheter og fordampningshastigheter. Det er derfor gunstig ved anrikning ved høytemperaturklorering å forvarme ilmenitten til en temperatur av over 600°C. the desired reaction rates and evaporation rates. It is therefore advantageous for enrichment by high-temperature chlorination to preheat the ilmenite to a temperature of over 600°C.
Det har nu vist seg at det er mulig å kombinere både oxydasjon og forvarming av ilmenitt ved å lede luft eller oxygen gjennom en blanding av malm og partikkelformig carbon, idet forbrenningen av carbonet innen et visst temepraturområde gir den nødvendige varme, men overraskende uten at carbonet hindrer oxydasjon av malmen. Den foreliggende fremgangsmåte er spesielt gunstig da naturgass spares ved denne og det kan anvendes rimeligere koks som idag er et lettere tilgjengelig brensel. It has now been shown that it is possible to combine both oxidation and preheating of ilmenite by passing air or oxygen through a mixture of ore and particulate carbon, as the combustion of the carbon within a certain temperature range provides the necessary heat, but surprisingly without the carbon prevents oxidation of the ore. The present method is particularly advantageous as natural gas is saved by this and cheaper coke can be used, which is today a more readily available fuel.
Oppfinnelsen angår en fremgangsmåte ved oxydasjon av en titanjernmalm, hvor malmen bringes i kontakt med luft, oxygen eller oxygenanriket luft ved en temperatur av minst 600°C, og fremgangsmåten er særpreget ved at malmen blandes med 5-35 vekt% partikkelformig carbon og at den erholdte blanding bringes i kontakt med luft, oxygen eller oxygenanriket luft ved en temperatur av 600-1080°C. The invention relates to a method for the oxidation of a titanium iron ore, where the ore is brought into contact with air, oxygen or oxygen-enriched air at a temperature of at least 600°C, and the method is characterized by the fact that the ore is mixed with 5-35% by weight of particulate carbon and that the the resulting mixture is brought into contact with air, oxygen or oxygen-enriched air at a temperature of 600-1080°C.
Blandingen av malm og carbon bringes fortrinnsvis i kontakt med luft, oxygen eller oxygenanriket luft ved den nevnte temperatur av 600-1080°C i 0,1-3 timer. Det kan også anvendes en lengre kontakttid for blandingen av malm og koks med luft, oxygen eller oxygenanriket luft ved den nevnte temperatur av 600-1080 C. Når hård petroleumskoks anvendes som partikkelformig carbon, er en kontakttid av 0,5-1,5 timer ved en temperatur av 650-950°C spesielt gunstig. The mixture of ore and carbon is preferably brought into contact with air, oxygen or oxygen-enriched air at the aforementioned temperature of 600-1080°C for 0.1-3 hours. A longer contact time can also be used for the mixture of ore and coke with air, oxygen or oxygen-enriched air at the aforementioned temperature of 600-1080 C. When hard petroleum coke is used as particulate carbon, a contact time of 0.5-1.5 hours is at a temperature of 650-950°C particularly favorable.
Det oppvarmede, oxyderte produkt er nyttig som råmateriale for fremstilling av titandioxydpigmenter. Det har ifølge oppfinnelsen vist seg at et slikt lag av koks og ilmenitt kan drives under stabile betingelser innen det temperaturområde som er nød-vendig for tørking og dehydroxylering av forvitrede ilmenitter, The heated, oxidized product is useful as a raw material for the production of titanium dioxide pigments. According to the invention, it has been shown that such a layer of coke and ilmenite can be operated under stable conditions within the temperature range necessary for drying and dehydroxylation of weathered ilmenites,
og for tilveiebringelse av en forvarmet malm med en egnet temperatur til å tilfredsstille den nødvendige varmebalanse i anriknings-reaktoren. and for providing a preheated ore of a suitable temperature to satisfy the required heat balance in the enrichment reactor.
En stabil drift av et fluidisert carbonskikt kan lettere oppnås innen det høytemperaturområde hvor carbonforbrenningen er diffusjonsregulert. Den over fire gangers forskjell i aktiver-ingsenergi mellom det kinetiskregulerte og diffusjonsregulerte A stable operation of a fluidized carbon layer can be more easily achieved within the high temperature range where the carbon combustion is diffusion regulated. The over fourfold difference in activation energy between the kinetically regulated and diffusion regulated
område av carbonforbrenning forbedrer stabiliteten. area of carbon combustion improves stability.
Selv om en øket lagtykkelse kan anvendes for å motvirke Although an increased layer thickness can be used to counteract this
en nedsatt reaktivitet, innebærer en øket lagtykkelse den ulempe at den øker oppholdstiden. Det har ifølge oppfinnelsen vist seg at fordelene ved ilmenittoxydasjon kan motvirkes av en lang oppholdstid som tillater krystallforandringer som nedsetter en oxydert malms anrikningsaktivitet. Den foretrukne lagtykkelse er 0,15-0,91 m, men lagtykkelsen kan også være større, dvs. 0,91-1,83 m. a reduced reactivity, an increased layer thickness entails the disadvantage that it increases the residence time. According to the invention, it has been shown that the advantages of ilmenite oxidation can be counteracted by a long residence time which allows crystal changes which reduce the enrichment activity of an oxidized ore. The preferred layer thickness is 0.15-0.91 m, but the layer thickness can also be greater, i.e. 0.91-1.83 m.
Den foreliggende fremgangsmåte utføres innen det høye reak-tivitetsområde slik at lagtykkelsen og oppholdstiden kan holdes så lave som mulig mens det fremdeles oppnås en vesentlig oxydasjon. Ved å regulere forholdet mellom geometriste overflatearealer og ved The present method is carried out within the high reactivity range so that the layer thickness and residence time can be kept as low as possible while substantial oxidation is still achieved. By regulating the relationship between geometric surface areas and wood
å holde temperaturen innen egnede områder kan både forbrenning, malmoxydasjon og forvarmingsstabilitet opprettholdes. by keeping the temperature within suitable ranges, both combustion, ore oxidation and preheating stability can be maintained.
Det ustabile temperaturområde vil avhenge av carbonover-flatens aktivitet. Petroleumskoks med sine inerte egenskaper er vel egnet for anrikningsreaktorer. Forbrenningstemperaturen er høy, og det stabile temperaturområde for behandling av laget med luft ligger over 550°C og overensstemmer godt med de ovennevnte krav til forvarming av en malm til en temperatur av 600°C og derover. Ved å anvende et fluidisert ilmentittlag kan partikler overføres fra sonen over oxygenet og ned i en sone hvor de kan oxyderes i løpet av en del av den tid som tilbringes i laget. Fremstillingen av carbonmonoxyd ved omsetning av carbonoverflaten med oxygen efterfølges av den sekundære omdannelse til carbondioxyd i gassfase, og temperaturer under 1000°C vil føre til at det dannes i det vesentlige bare carbondioxyd og vil således ikke motvirke ilmenittoxydasjonen på grunn av en påfølgende reduksjon med CO. The unstable temperature range will depend on the activity of the carbon over surface. Petroleum coke with its inert properties is well suited for enrichment reactors. The combustion temperature is high, and the stable temperature range for treating the layer with air is above 550°C and corresponds well with the above-mentioned requirements for preheating an ore to a temperature of 600°C and above. By using a fluidized ilmentite layer, particles can be transferred from the zone above the oxygen and down into a zone where they can be oxidized during part of the time spent in the layer. The production of carbon monoxide by reacting the carbon surface with oxygen is followed by the secondary conversion to carbon dioxide in the gas phase, and temperatures below 1000°C will lead to essentially only carbon dioxide being formed and will thus not counteract the ilmenite oxidation due to a subsequent reduction with CO .
Eksempel 1 Example 1
En kvartsreaktor for et fluidisert lag og med en diameter A quartz reactor for a fluidized bed and with a diameter
på 2,54 cm og som ble utvendig oppvarmet, ble fylt med 20 g ilmenitt og 4 g koks. Deres egenskaper er angitt i tabell I. of 2.54 cm and which was externally heated, was filled with 20 g of ilmenite and 4 g of coke. Their characteristics are listed in Table I.
I tabell II er angitt resultater av 10 minutters forsøk ved tre forskjellige temperaturer. Table II shows the results of 10-minute tests at three different temperatures.
x Beregnet ut fra carbontap og oxydasjon av jern. x Calculated from carbon loss and oxidation of iron.
Dette eksempel viser at ilmenitten kan bli i det vesentlige fullstendig oxydert i nærvær av carbon ved temperaturer over det kinetisk begrensende område og at selv om luften ble i det vesentlige fullstendig forbrukt ved forbrenning og oxydasjon, gikk det med en konstant fraksjon, dvs. 23%, for å oxydere ilmenitten ved en temperatur av 750°C og derover. This example shows that the ilmenite can be essentially completely oxidized in the presence of carbon at temperatures above the kinetically limiting range and that even though the air was essentially completely consumed by combustion and oxidation, it proceeded with a constant fraction, i.e. 23% , to oxidize the ilmenite at a temperature of 750°C and above.
Enkelte ilmenittkorn er vanskeligere å oxydere enn andre, og det forekommer sannsynlig at resten av toverdig jern foreligger helt i de korn som det er mer vanskelig å oxydere. Den ilmenitt som lett lar seg oxydere, ble således hurtig omdannet. Certain ilmenite grains are more difficult to oxidize than others, and it seems likely that the rest of the divalent iron is present entirely in the grains that are more difficult to oxidize. The ilmenite, which easily oxidizes, was thus rapidly transformed.
Eksempel 2 Example 2
En reaktor for fluidisert lag og med en innvendig diameter av 1,68 m og innvendig foret og forsynt med en flerpunkts gass-fordelingsanordning ble drevet med en blanding av malm og koks med en statisk lagtykkelse på 25,4 cm. I tabell III er gjengitt en rekke analyser av prøver som ble tatt fra laget som avvekslende ble utsatt for reduserende og oxyderende betingelser, som angitt ved den medgåtte tid. Reduksjonen fant sted mens laget var statisk og oxydasjonen mens laget ble oppvarmet. For hver syklus ble laget oppvarmet til en temperatur av 950°C før det ble av-kjølt. A fluidized bed reactor with an internal diameter of 1.68 m and internally lined and provided with a multi-point gas distribution device was operated with a mixture of ore and coke with a static bed thickness of 25.4 cm. Table III shows a number of analyzes of samples that were taken from the layer that was alternately exposed to reducing and oxidizing conditions, as indicated by the elapsed time. The reduction took place while the layer was static and the oxidation while the layer was heated. For each cycle, the layer was heated to a temperature of 950°C before being cooled.
Laget ble igjen fluidisert med nitrogen, og prøver ble tatt fra laget efter reduksjonsperioder. For oppvarmingssykluser ble oxygen anriket med luft anvendt med et høyeste innhold av 30% oxygen. Koks ble tilsatt efter at den første prøve var blitt tatt. The layer was again fluidized with nitrogen, and samples were taken from the layer after reduction periods. For heating cycles, oxygen enriched with air was used with a maximum content of 30% oxygen. Coke was added after the first sample had been taken.
For å vise den skadelige innvirkning av en for lang oppholdstid presenteres eksempel 3. To show the harmful impact of too long a residence time, example 3 is presented.
Eksempel 3 Example 3
Laboratorieoxydasjon ble utført i et 2,54 cm tykt fluidisert lag med 20 g prøver av Murphy-malm-ilmenitt under anvendelse av luftoxydasjon uten at carbon var tilstede. Det viste seg at en oxydasjon kunne fullføres i løpet av lang tid, f.eks. lenger enn i ca. 1 time, men produktet hadde lave utbytningshastigheter sammen-lignet med naturlig malm eller hurtig oxydert malm. Denne virk-ning fremgår av resultatene angitt i tabell IV. Laboratory oxidation was performed in a 2.54 cm thick fluidized bed of 20 g samples of Murphy ore ilmenite using air oxidation in the absence of carbon. It turned out that an oxidation could be completed over a long period of time, e.g. longer than in approx. 1 hour, but the product had low recovery rates compared to natural ore or rapidly oxidized ore. This effect can be seen from the results shown in Table IV.
De i tabellene III og IV angitte aktiviteter er utbytningshastigheter tatt ut fra helningen til en halv-logkurve for log (gram gjenværende Fe) avsatt i forhold til tiden. Den samme laboratorie-reaktor ble anvendt som i eksempel 1 med TiCl4 og fluidisering med nitrogen av en 10 g charge (uten carbon) ved en hastighet av 0,5/s og ved anvendelse av 26 mmol/min . av hver- Prøver ble tatt med forskjellige tidsmellomrom. The activities indicated in Tables III and IV are recovery rates taken from the slope of a half-log curve for log (grams of Fe remaining) deposited in relation to time. The same laboratory reactor was used as in example 1 with TiCl4 and fluidization with nitrogen of a 10 g charge (without carbon) at a speed of 0.5/s and using 26 mmol/min. of each- Samples were taken at different time intervals.
Det fremgår av de i tabell III angitte aktiviteter at disse It appears from the activities listed in Table III that these
kan variere oppad og nedad ikke bare i avhengighet av oxydasjonstil-standen, men også i avhengighet av oppholdstiden ved høye temperaturer. can vary upwards and downwards not only depending on the oxidation state, but also depending on the residence time at high temperatures.
For utførelse av den foreliggende fremgangsmåte bør derfor det fluidiserte lag hvori malmen og carbonet forvarmes, tørkes og oxyderes, være laget for behandling innen de følgende grenser for de anvendte betingelser: For carrying out the present method, the fluidized bed in which the ore and carbon are preheated, dried and oxidized should therefore be prepared for treatment within the following limits for the conditions used:
Oppholdstid under 1 time Stay under 1 hour
Carbonoverflateareal under 6,14 m 2/kg Carbon surface area below 6.14 m 2/kg
Gasshastighet 0,09-0,46 m/s Gas velocity 0.09-0.46 m/s
Temperatur 650-950°C Temperature 650-950°C
Antennelsestemperatur for carbon-luft over 450°C. Ignition temperature for carbon-air above 450°C.
Det bør tas hensyn til typen av ilmenittpartikler som skal oxyderes. Massive ilmenitter, som Tellnes-malmer, må oxyderes ved høyere temperaturer enn sterkt forvitrede strandsander, selv om det for fullstendig oxydasjon av strandsander som inneholder små mengder uforvitret ilmenitt, kreves høyere temperaturer eller Consideration should be given to the type of ilmenite particles to be oxidized. Massive ilmenites, such as Tellnes ores, must be oxidized at higher temperatures than highly weathered beach sands, although complete oxidation of beach sands containing small amounts of unweathered ilmenite requires higher temperatures or
lengre oxydasjonseksponeringstid. longer oxidation exposure time.
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US62341775A | 1975-10-17 | 1975-10-17 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO763518L NO763518L (en) | 1977-04-19 |
| NO144297B true NO144297B (en) | 1981-04-27 |
| NO144297C NO144297C (en) | 1981-08-05 |
Family
ID=24498010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO763518A NO144297C (en) | 1975-10-17 | 1976-10-15 | PROCEDURE FOR OXYDATION OF TITANIUM ORE |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5249997A (en) |
| AU (1) | AU504225B2 (en) |
| BE (1) | BE847207A (en) |
| CA (1) | CA1077239A (en) |
| DE (1) | DE2644581A1 (en) |
| FR (1) | FR2328048A1 (en) |
| GB (1) | GB1502576A (en) |
| IT (1) | IT1069022B (en) |
| NL (1) | NL7611451A (en) |
| NO (1) | NO144297C (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56149490U (en) * | 1980-04-07 | 1981-11-10 | ||
| JPS56143940A (en) * | 1980-04-09 | 1981-11-10 | Shimadzu Corp | Leakage inspecting system |
| JPS5756929Y2 (en) * | 1980-04-11 | 1982-12-07 | ||
| JPS58147628A (en) * | 1982-02-26 | 1983-09-02 | Toshiba Corp | Device for inspecting gas leakage from cooling unit |
| DE3210729A1 (en) * | 1982-03-24 | 1983-10-06 | Hoechst Ag | METHOD FOR PRODUCING TITANIUM DIOXIDE CONCENTRATES |
| US4791805A (en) * | 1985-06-07 | 1988-12-20 | Expertek, Inc. | Fuel tank leak detection apparatus |
| DE10260739B3 (en) | 2002-12-23 | 2004-09-16 | Outokumpu Oy | Process and plant for producing metal oxide from metal compounds |
| DE10260741A1 (en) | 2002-12-23 | 2004-07-08 | Outokumpu Oyj | Process and plant for the heat treatment of fine-grained solids |
| DE10260737B4 (en) | 2002-12-23 | 2005-06-30 | Outokumpu Oyj | Process and plant for the heat treatment of titanium-containing solids |
| DE10260734B4 (en) | 2002-12-23 | 2005-05-04 | Outokumpu Oyj | Process and plant for the production of carbon coke |
| DE10260731B4 (en) | 2002-12-23 | 2005-04-14 | Outokumpu Oyj | Process and plant for the heat treatment of iron oxide-containing solids |
| DE10260733B4 (en) | 2002-12-23 | 2010-08-12 | Outokumpu Oyj | Process and plant for the heat treatment of iron oxide-containing solids |
| DE10260738A1 (en) | 2002-12-23 | 2004-07-15 | Outokumpu Oyj | Process and plant for conveying fine-grained solids |
| JP2014234548A (en) * | 2013-06-05 | 2014-12-15 | 東邦チタニウム株式会社 | Method for increasing quality of titanium refining raw material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2234844A1 (en) * | 1972-07-15 | 1974-01-31 | Bayer Ag | PROCESS FOR DIGESTION OF TITANIUM ORES |
-
1976
- 1976-09-21 AU AU17972/76A patent/AU504225B2/en not_active Expired
- 1976-09-23 GB GB39569/76A patent/GB1502576A/en not_active Expired
- 1976-10-02 DE DE19762644581 patent/DE2644581A1/en not_active Withdrawn
- 1976-10-13 BE BE171447A patent/BE847207A/en unknown
- 1976-10-14 FR FR7631461A patent/FR2328048A1/en active Granted
- 1976-10-15 NO NO763518A patent/NO144297C/en unknown
- 1976-10-15 JP JP51123044A patent/JPS5249997A/en active Pending
- 1976-10-15 CA CA263,445A patent/CA1077239A/en not_active Expired
- 1976-10-15 IT IT28364/76A patent/IT1069022B/en active
- 1976-10-15 NL NL7611451A patent/NL7611451A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| CA1077239A (en) | 1980-05-13 |
| NL7611451A (en) | 1977-04-19 |
| IT1069022B (en) | 1985-03-21 |
| NO144297C (en) | 1981-08-05 |
| NO763518L (en) | 1977-04-19 |
| FR2328048A1 (en) | 1977-05-13 |
| FR2328048B1 (en) | 1981-01-09 |
| DE2644581A1 (en) | 1977-04-28 |
| BE847207A (en) | 1977-01-31 |
| AU504225B2 (en) | 1979-10-04 |
| GB1502576A (en) | 1978-03-01 |
| AU1797276A (en) | 1978-04-06 |
| JPS5249997A (en) | 1977-04-21 |
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