CA1077239A - Ilmenite oxidation in a carbon-containing fluidized bed - Google Patents
Ilmenite oxidation in a carbon-containing fluidized bedInfo
- Publication number
- CA1077239A CA1077239A CA263,445A CA263445A CA1077239A CA 1077239 A CA1077239 A CA 1077239A CA 263445 A CA263445 A CA 263445A CA 1077239 A CA1077239 A CA 1077239A
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- Prior art keywords
- carbon
- ore
- oxidation
- air
- oxygen
- Prior art date
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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
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- 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)
Abstract
ABSTRACT OF THE INVENTION
Ilmenite, a titanium dioxide containing mineral, mixed with particulate carbon and the mixture subjected to air or oxygen in a gas-solids reactor at temperatures of 600 to 1080°C.
results in the oxidation of the ilmenite which is preferred starting material for beneficiation by the chloride process into synthetic rutile.
Ilmenite, a titanium dioxide containing mineral, mixed with particulate carbon and the mixture subjected to air or oxygen in a gas-solids reactor at temperatures of 600 to 1080°C.
results in the oxidation of the ilmenite which is preferred starting material for beneficiation by the chloride process into synthetic rutile.
Description
~07723~
~ACKGROU~D OF T~E I~VENTION
(a) Field of th~ Invention ~ his invention relat~s to the benef~ciatlon of m~nerals and more particularly to the oxidation of titaniforous ore~ suah a~ ilm~n$te to facilitat~ high tempcrature ~electiv~ re~oval of iron valu~s in said ores by lea~hin~ or chlorination process ~ b) Brief Summarv of the Prior Art Ilmenite oxidation i~ a rapid and ea#y process wh~ch taXes place at temperatura~ from 600C and higher in an oxygen containing atmosphér- The product of an ilm-nite oxidation may vary depending upon the nature of the ilmenito and tho temp-~ratur- of oxldatisn There i8 a t ndenay to tran~form tha mat~rial to p~eudobrookit~ at temperatures of 900C and ovor a~
taught by Robinson et al in U S 3 875 2K and Fuku~hima et al in U S 3 803 287 Fuku~hima ~ay~, 'the oxidation-roasting weak-ns the reactivity of titanium in ilmenite with chlorine ~o a¢c~lerate th~ pr6fer~ntlal chlorination of iron and at the ~ame t~me lmpro~es th~ ~eparatio~ of iron in th~ couE~e of electro-tatic dr~sing' In Robin~o~ a preoxidation ~tep has been taught ~ollow~d by a reduc*ion ~tep to improv- l~aching b n ficiat~on u~ing, for example, hydrochloric acid which ¢ontain ~om~ ferrous chlorid~ to aid the leaehing proces~
Robinson do~ not claim th~ oxidation ~onditions a~ ~
part of his i~vention Both Robinson and Fuku~hima follow the oxidat~on ~y a r0duction in a~ o~yg~n de~icient at~o-phere In high t~mperature chlorlnation boneficlation of beach Jand il~enito, it i- neco-aary to preh at the ll~enite in ord r to drive off hydrog-n pr-s-nt not only a- water but a- part of hydroxyl- absorbed on the x~en ive ore urface The removal of hydrog n la required in ord r to prev nt chlorine lo--o- to hydrogen chloride at the high to~perature of th beneficiation r-actor Another and qually important rea-on for preheating the il~nit- i- to maintain the h-at balanc- for the hlgh t~aperature chlorination ben-flciatlon Jince high t~p-rature~
are de drable for de-ired ratea of reactlon and volatlllzatlon Th r-fore it ia conveni-nt ln b neficiation by high temp r~ture chlorination to preh at the il~ nite to t _peratureJ in XC-8a of 600C
~ have dlacover-d that lt i- po--ibl- to combine both oxidatlon and preheatlng of ilo nite by paaaing air or oxygen through a ~lxtur- of ore and partl~l~t- carbon wh rein th co~bu tlon of carbon ov~r a rang of t~p ratur-a providbJ
the h at r~quir-d y t un-xpect-dly the pre-ence of carbon does not pr-v nt o~idation of the or- our procea- i- p~rticularly d Jirable alnce it aav-a natural ga~ and Jubstitute- ch ap r coke which i- prea-ntly a mor- available fuel SUMMARY OF T~e I~V~TIO~
Thia lnventlon i- direct-d to a procesa for heating and oxidizing a titanif-rou- ore to remove water and hydroxyl group# from the ore and at the sa~e tiDe oxidize the ore to a for~ ~ore am nable to beneficiation by the selectlve removal of iron valuea from said ore by eontacting the ore mixed with particulate carbon, under fluidizing conditions at te~peratures of 600 to 1080C with air, oxygen or oxygen enriched air for a period of time of 0,1 to 3 hour~ or longer The heated oxidized product i8 useful as a raw - , . .
.
material for the production of titanium dioxide plgments. ~e have found that such a coke-ilmenite bod can be operated under ~table conditlon~ ln th- range of t~mperature n~eded for drying and dehydroxylating weathered i}menite~ and provide preheatod ore at a ~uitable temperature to meet the heat balance need~ of the beneficiator reactor.
Stabillty of operatlon of a fluldized carbon bed is mor~ ea8ily achioved in the high tomperaturo region where the carbon combustion reaction i~ diffu~ion controlled~ The more than four fold differenco in nergy of activation between the kinetic and diffusion controlled regime of carbon coobu~tion improve~ ~tabillty.
Although ln¢rea~ed bed depth can be u~ed to counter docrea-od reactivity there i8 a di~advantaqe to bed depth in that it incrçase~ holding time. ~e have found th~t th-ben-flt~ of ilmenite oxidation can be counter-d by long holding ti~o wh~ch allow~ cry-tal changes that reduc- the b neficiation activity of an oxidized oro. Th- preferred bed depth i8 0,5 to 3 ft.; however the ~ed depth can be deeper, i.e. 3 to 6 ft.
Our invention operates in the high reactivity rogion to allow bed depth and holding time to be minimized while still yielding ~ubstantial oxidation. ~y controlling the ratio of geo~ tric Jurfaco ar-as and by keoping temperature within suit-abl- ranges, both combu~tion, ore oxidation and preheater sta~llity can be maintained. ', The unstable region of temperature will depend upon the activity of the carbon ~urfa~e. Petroleu~ coke with it~
inert gualities i8 well sulted to beneficiation reactors.
Ignition temperature i8 hlgh and the stable region of the bed operation with air lie8 above 550C. and coincides nicely with the above ~entioned requirement~ for ore preheatlng to temper-atures of 600C. and above.
By u-ing a fluidized il~enite bed, particle~ can travel from the zone abov~ the oxygen down into a zon where they can be oxidized for a portion of th- ti~e pent in th b d The production of carbon monoxlde by carbon urfac-reaction with oxygen i~ followed by the ~econdary conver~ion to carbon dioxid~ in th- ga~ pha~- and t~Jp-ratur-~ below 1000C
will yield ubstantially all carbon diox~de and thu~ will not hlnder the ll~ nlte oxidation by ub-egu nt r-duction by CO
~XAMPLF 1 A 1~ diametor quartz fluid~z-d bed r~actor ext-rnally h-ated waz charg d with 20g of iL~ ~ite and 4g of coke Th d r prop rti-z are glven in Table I
Table II giv-~ data fro~ 10 minute runr for three t~p ratur-- -TA~LE I
SO~ID R~ACTA~T PROPBRTIF8 Iln nit-s Murphyor-z ~a~t Coa-t Au~tralian), 20g ~atural 8tate Tio2 - 54,5X, by welght F O - 20,9X, by weight F 2O3 - 20,8X, by weight Coke Great L~ke~ carbon Co calcined p trol-u~ coke 4g -~
S~lected fraction 30 x 44 m-zh contalning lX S
Air 52 ~oolr hin for 10 minute~
TABLF II
Labor~tory Fluidlz-d Bed Air Oxidation of an Il~enite-Coke ~ixture TEMP~RATUR~ ~A~YSIS COK~ OUT MMOLS ArR*
C %FeXFe gramsCoke Il~enite TDtal 650 30,80 3,28 3,1381 342 11,0 453 750 30,71 3,06 3,017 390 112,8 502,8 850 30,93 2,51 3,007 394 117,5 511,5 * Calculated from carbon 101!~8 and iron oxidation.
; - :
~ 0 7~Z3 9 Thi~ x~mple ~how- that th~ enit- can be ubJtan-tially o~idiz-d in th- pre~-nc- of carbon at t-~p rature~ abov-th- kinetic limiting range and that although the air wa- n arly all con~umed in combu~tion and oxidation, a con-tant fraction, i e 23X, went to oxidiz- th ilmenit- at 750C and abov-9O~ ilm nit- grain~ ar- mor- dlfficult to oxidiz~
than oth-r~ and it -em~ likely that the r-~idual f-rrou- iJ
all in th moro difficultly oxidized grain- Thu- th- aJily oxidlz-d il~ nite waz quickly convert-d DWSPL~ II
A fluidLz-d b d r-actor 5,5' ID, r-fractory lin d wlth a multipoint gaJ diJtributor wa- op~rat-d with n or--coke mlxture of 10~ ~tatic b d d pth Tabl- III gi~e~ a ~eri-~ of analy e- of ~ampl-~ taken fro~ th b d which wa~ cycled b~tw en r-auc-d and oxidized condition~ a~ indicat-d by the time elap-ed R du~tion took place whll- the bed wa- tatic, oxidation whil-th- b~ d wa- b ing h at-d up On each ¢ycl- th~ bed wa- brought to 9S0C b-for- being ~et down TABL~ III T-~D.
T _ p $~ple Tim X Cok- Cycl- %Fe Activity X~hin 9S0 1 6,23 Initial 72,88 83,6 865 2 64 min 9,90 R d 84,31 84,31 9S0 3 36 ~ 9,84 Oxid 75,25 97,8 890 4 54 ~ 8,09 Red 78,53 98 ; ~ 950 5 26 ~ 7,72 Oxid 50,66 139,4 835 6 137 N 7,01 Red 86,71 57,5 9S0 7 50 H 6,40 Oxid 42,48 92 710 8 609 N 5,15 Red ge,27 59,8 950 9 65 N 2,91 Oxld 22,93 128 The bed wa~ r-fluidized with nitrog n and 2mpled after reduction period- On h at up ¢y¢les o~ygen nri¢hed air wa~ u~ed with a ~aximu~ of 30X oxyg-n Coke was added after -:, . , - . .
:: .
: .
the initlal Jample To illu-trate the delet-rious effect of xceb-ive holding time xa~ple III iJ presented W~L~ I I I
~ aboratory oxidation by r-action of the oxidlzed llmenite with TiC14 wa~ accompli-hed in a 1" fluidlz-d bed on 20g aample- of Mhrphyore~ ilmenit- u-ing air oxidation without carbon being pr--ont It wa~ found that oxidation for long p riod- of tlme could be complet-d but th product po~s-~-ed low repla¢-~ent rate~ when aompared to natural or rapidly oxldiz-d ore Table rv give- r-~ult~ of 810w oxidations and th or- actlvitie- co~parod with rapid oxidation rate-TABL~ rv ~ff ct of Time at T mperatur- on Beneficiation Aativit~e- of Oxidlz-d Beach Sand Ilm nlte Tim Oxidation Iron OxideActivity*
T mp rature X F-rria Xvmin O hra ~atural Mhrphyore~ 50X 140,0 16 hr~ 650C 100X 36,5 205 hr~ 900C 100X 57,5 30 min 900C 100X 140,0 Iron oxide replacement with TiC14 to form internal Tio2 and volatiliz- iron chlorid-a at 1000C
Act~viti-s giv-n in Tsblea II~ and IV are replacem-nt rat-~ taken from the alope of a aomi-log plot of log (grams Fe remaining) v8. time The aame laboratory reactor ia used as in ~xample I with TlC14 and nitrogen fluidizing a 10 gram charge (without carbon) at a 0,5/80C. velocity using 26 mmols/min each Samples were taken at various time interval~
It i8 apparent from the activitie~ shown in Table III
that the activit~es can vary up and down not only with the oxidation state but with holding time at high temperatures Therefor~, to pract~se our invention, the ~luldized bed whereln the ore and carbon are proheated, dried and oxidized, should be de~igned and operated within th~ following limit~:
Retention time le88 than 1 hour ~arbon surface area les~ than 30 ft /lb.
Ga~ volocity .3-1.5'/~ec Temperature 650-950C.
Carbon - air ignition temperature above 450C.
Consideration ~hould bo given to the type of i~menite particl~ to be oxidizod. Massivo ilmenite~ ~uch a~ Telln-~
oro~ have to be oxidized at higher temperatures than highly weathered beach ~and~, although for complete oxidation beach sand- which contain small amount~ of unweathered ilmonlt- will regulre higher temperatures or longer oxidatlon expo~ure time.
The foregoing d~tailed description has been giv-n for clarity of und~retanding only and no unn-ce~ary limltations aro to b~ understood therefrom. The inrention i~ not limited to the exact details ~hown and de~cribed for obviou~ modific-ations will occur to tho~e skilled in the art.
~ACKGROU~D OF T~E I~VENTION
(a) Field of th~ Invention ~ his invention relat~s to the benef~ciatlon of m~nerals and more particularly to the oxidation of titaniforous ore~ suah a~ ilm~n$te to facilitat~ high tempcrature ~electiv~ re~oval of iron valu~s in said ores by lea~hin~ or chlorination process ~ b) Brief Summarv of the Prior Art Ilmenite oxidation i~ a rapid and ea#y process wh~ch taXes place at temperatura~ from 600C and higher in an oxygen containing atmosphér- The product of an ilm-nite oxidation may vary depending upon the nature of the ilmenito and tho temp-~ratur- of oxldatisn There i8 a t ndenay to tran~form tha mat~rial to p~eudobrookit~ at temperatures of 900C and ovor a~
taught by Robinson et al in U S 3 875 2K and Fuku~hima et al in U S 3 803 287 Fuku~hima ~ay~, 'the oxidation-roasting weak-ns the reactivity of titanium in ilmenite with chlorine ~o a¢c~lerate th~ pr6fer~ntlal chlorination of iron and at the ~ame t~me lmpro~es th~ ~eparatio~ of iron in th~ couE~e of electro-tatic dr~sing' In Robin~o~ a preoxidation ~tep has been taught ~ollow~d by a reduc*ion ~tep to improv- l~aching b n ficiat~on u~ing, for example, hydrochloric acid which ¢ontain ~om~ ferrous chlorid~ to aid the leaehing proces~
Robinson do~ not claim th~ oxidation ~onditions a~ ~
part of his i~vention Both Robinson and Fuku~hima follow the oxidat~on ~y a r0duction in a~ o~yg~n de~icient at~o-phere In high t~mperature chlorlnation boneficlation of beach Jand il~enito, it i- neco-aary to preh at the ll~enite in ord r to drive off hydrog-n pr-s-nt not only a- water but a- part of hydroxyl- absorbed on the x~en ive ore urface The removal of hydrog n la required in ord r to prev nt chlorine lo--o- to hydrogen chloride at the high to~perature of th beneficiation r-actor Another and qually important rea-on for preheating the il~nit- i- to maintain the h-at balanc- for the hlgh t~aperature chlorination ben-flciatlon Jince high t~p-rature~
are de drable for de-ired ratea of reactlon and volatlllzatlon Th r-fore it ia conveni-nt ln b neficiation by high temp r~ture chlorination to preh at the il~ nite to t _peratureJ in XC-8a of 600C
~ have dlacover-d that lt i- po--ibl- to combine both oxidatlon and preheatlng of ilo nite by paaaing air or oxygen through a ~lxtur- of ore and partl~l~t- carbon wh rein th co~bu tlon of carbon ov~r a rang of t~p ratur-a providbJ
the h at r~quir-d y t un-xpect-dly the pre-ence of carbon does not pr-v nt o~idation of the or- our procea- i- p~rticularly d Jirable alnce it aav-a natural ga~ and Jubstitute- ch ap r coke which i- prea-ntly a mor- available fuel SUMMARY OF T~e I~V~TIO~
Thia lnventlon i- direct-d to a procesa for heating and oxidizing a titanif-rou- ore to remove water and hydroxyl group# from the ore and at the sa~e tiDe oxidize the ore to a for~ ~ore am nable to beneficiation by the selectlve removal of iron valuea from said ore by eontacting the ore mixed with particulate carbon, under fluidizing conditions at te~peratures of 600 to 1080C with air, oxygen or oxygen enriched air for a period of time of 0,1 to 3 hour~ or longer The heated oxidized product i8 useful as a raw - , . .
.
material for the production of titanium dioxide plgments. ~e have found that such a coke-ilmenite bod can be operated under ~table conditlon~ ln th- range of t~mperature n~eded for drying and dehydroxylating weathered i}menite~ and provide preheatod ore at a ~uitable temperature to meet the heat balance need~ of the beneficiator reactor.
Stabillty of operatlon of a fluldized carbon bed is mor~ ea8ily achioved in the high tomperaturo region where the carbon combustion reaction i~ diffu~ion controlled~ The more than four fold differenco in nergy of activation between the kinetic and diffusion controlled regime of carbon coobu~tion improve~ ~tabillty.
Although ln¢rea~ed bed depth can be u~ed to counter docrea-od reactivity there i8 a di~advantaqe to bed depth in that it incrçase~ holding time. ~e have found th~t th-ben-flt~ of ilmenite oxidation can be counter-d by long holding ti~o wh~ch allow~ cry-tal changes that reduc- the b neficiation activity of an oxidized oro. Th- preferred bed depth i8 0,5 to 3 ft.; however the ~ed depth can be deeper, i.e. 3 to 6 ft.
Our invention operates in the high reactivity rogion to allow bed depth and holding time to be minimized while still yielding ~ubstantial oxidation. ~y controlling the ratio of geo~ tric Jurfaco ar-as and by keoping temperature within suit-abl- ranges, both combu~tion, ore oxidation and preheater sta~llity can be maintained. ', The unstable region of temperature will depend upon the activity of the carbon ~urfa~e. Petroleu~ coke with it~
inert gualities i8 well sulted to beneficiation reactors.
Ignition temperature i8 hlgh and the stable region of the bed operation with air lie8 above 550C. and coincides nicely with the above ~entioned requirement~ for ore preheatlng to temper-atures of 600C. and above.
By u-ing a fluidized il~enite bed, particle~ can travel from the zone abov~ the oxygen down into a zon where they can be oxidized for a portion of th- ti~e pent in th b d The production of carbon monoxlde by carbon urfac-reaction with oxygen i~ followed by the ~econdary conver~ion to carbon dioxid~ in th- ga~ pha~- and t~Jp-ratur-~ below 1000C
will yield ubstantially all carbon diox~de and thu~ will not hlnder the ll~ nlte oxidation by ub-egu nt r-duction by CO
~XAMPLF 1 A 1~ diametor quartz fluid~z-d bed r~actor ext-rnally h-ated waz charg d with 20g of iL~ ~ite and 4g of coke Th d r prop rti-z are glven in Table I
Table II giv-~ data fro~ 10 minute runr for three t~p ratur-- -TA~LE I
SO~ID R~ACTA~T PROPBRTIF8 Iln nit-s Murphyor-z ~a~t Coa-t Au~tralian), 20g ~atural 8tate Tio2 - 54,5X, by welght F O - 20,9X, by weight F 2O3 - 20,8X, by weight Coke Great L~ke~ carbon Co calcined p trol-u~ coke 4g -~
S~lected fraction 30 x 44 m-zh contalning lX S
Air 52 ~oolr hin for 10 minute~
TABLF II
Labor~tory Fluidlz-d Bed Air Oxidation of an Il~enite-Coke ~ixture TEMP~RATUR~ ~A~YSIS COK~ OUT MMOLS ArR*
C %FeXFe gramsCoke Il~enite TDtal 650 30,80 3,28 3,1381 342 11,0 453 750 30,71 3,06 3,017 390 112,8 502,8 850 30,93 2,51 3,007 394 117,5 511,5 * Calculated from carbon 101!~8 and iron oxidation.
; - :
~ 0 7~Z3 9 Thi~ x~mple ~how- that th~ enit- can be ubJtan-tially o~idiz-d in th- pre~-nc- of carbon at t-~p rature~ abov-th- kinetic limiting range and that although the air wa- n arly all con~umed in combu~tion and oxidation, a con-tant fraction, i e 23X, went to oxidiz- th ilmenit- at 750C and abov-9O~ ilm nit- grain~ ar- mor- dlfficult to oxidiz~
than oth-r~ and it -em~ likely that the r-~idual f-rrou- iJ
all in th moro difficultly oxidized grain- Thu- th- aJily oxidlz-d il~ nite waz quickly convert-d DWSPL~ II
A fluidLz-d b d r-actor 5,5' ID, r-fractory lin d wlth a multipoint gaJ diJtributor wa- op~rat-d with n or--coke mlxture of 10~ ~tatic b d d pth Tabl- III gi~e~ a ~eri-~ of analy e- of ~ampl-~ taken fro~ th b d which wa~ cycled b~tw en r-auc-d and oxidized condition~ a~ indicat-d by the time elap-ed R du~tion took place whll- the bed wa- tatic, oxidation whil-th- b~ d wa- b ing h at-d up On each ¢ycl- th~ bed wa- brought to 9S0C b-for- being ~et down TABL~ III T-~D.
T _ p $~ple Tim X Cok- Cycl- %Fe Activity X~hin 9S0 1 6,23 Initial 72,88 83,6 865 2 64 min 9,90 R d 84,31 84,31 9S0 3 36 ~ 9,84 Oxid 75,25 97,8 890 4 54 ~ 8,09 Red 78,53 98 ; ~ 950 5 26 ~ 7,72 Oxid 50,66 139,4 835 6 137 N 7,01 Red 86,71 57,5 9S0 7 50 H 6,40 Oxid 42,48 92 710 8 609 N 5,15 Red ge,27 59,8 950 9 65 N 2,91 Oxld 22,93 128 The bed wa~ r-fluidized with nitrog n and 2mpled after reduction period- On h at up ¢y¢les o~ygen nri¢hed air wa~ u~ed with a ~aximu~ of 30X oxyg-n Coke was added after -:, . , - . .
:: .
: .
the initlal Jample To illu-trate the delet-rious effect of xceb-ive holding time xa~ple III iJ presented W~L~ I I I
~ aboratory oxidation by r-action of the oxidlzed llmenite with TiC14 wa~ accompli-hed in a 1" fluidlz-d bed on 20g aample- of Mhrphyore~ ilmenit- u-ing air oxidation without carbon being pr--ont It wa~ found that oxidation for long p riod- of tlme could be complet-d but th product po~s-~-ed low repla¢-~ent rate~ when aompared to natural or rapidly oxldiz-d ore Table rv give- r-~ult~ of 810w oxidations and th or- actlvitie- co~parod with rapid oxidation rate-TABL~ rv ~ff ct of Time at T mperatur- on Beneficiation Aativit~e- of Oxidlz-d Beach Sand Ilm nlte Tim Oxidation Iron OxideActivity*
T mp rature X F-rria Xvmin O hra ~atural Mhrphyore~ 50X 140,0 16 hr~ 650C 100X 36,5 205 hr~ 900C 100X 57,5 30 min 900C 100X 140,0 Iron oxide replacement with TiC14 to form internal Tio2 and volatiliz- iron chlorid-a at 1000C
Act~viti-s giv-n in Tsblea II~ and IV are replacem-nt rat-~ taken from the alope of a aomi-log plot of log (grams Fe remaining) v8. time The aame laboratory reactor ia used as in ~xample I with TlC14 and nitrogen fluidizing a 10 gram charge (without carbon) at a 0,5/80C. velocity using 26 mmols/min each Samples were taken at various time interval~
It i8 apparent from the activitie~ shown in Table III
that the activit~es can vary up and down not only with the oxidation state but with holding time at high temperatures Therefor~, to pract~se our invention, the ~luldized bed whereln the ore and carbon are proheated, dried and oxidized, should be de~igned and operated within th~ following limit~:
Retention time le88 than 1 hour ~arbon surface area les~ than 30 ft /lb.
Ga~ volocity .3-1.5'/~ec Temperature 650-950C.
Carbon - air ignition temperature above 450C.
Consideration ~hould bo given to the type of i~menite particl~ to be oxidizod. Massivo ilmenite~ ~uch a~ Telln-~
oro~ have to be oxidized at higher temperatures than highly weathered beach ~and~, although for complete oxidation beach sand- which contain small amount~ of unweathered ilmonlt- will regulre higher temperatures or longer oxidatlon expo~ure time.
The foregoing d~tailed description has been giv-n for clarity of und~retanding only and no unn-ce~ary limltations aro to b~ understood therefrom. The inrention i~ not limited to the exact details ~hown and de~cribed for obviou~ modific-ations will occur to tho~e skilled in the art.
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for oxidizing a titaniferous ore compris-ing contacting the ore mixed with 5 to 35% by weight of a particu-late carbon with air, oxygen or oxygen enriched air at a tempera-ture of 600 to 1080°C for a period of at least 0.1 hours in a gas solids reactor under fluidizing conditions.
2. The process of claim 1 wherein air, oxygen or oxygen enriched air is contacted with the ore for a period of time of 0.1 to 3 hours.
3. The process of claim 2 wherein the carbon is a hard petroleum coke and the time is 0.5 to 1.5 hours and the tempera-ture is 650 to 950°C.
4. The process of claim 1 wherein the temperature is 600 to 1080°C and the air, oxygen or oxygen enriched air is con-tacted with the ore for 0.1 to 3 hours at a velocity of 0.5 ft/
sec.
sec.
5. The process of claim 1 conducted continuously.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US62341775A | 1975-10-17 | 1975-10-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1077239A true CA1077239A (en) | 1980-05-13 |
Family
ID=24498010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA263,445A Expired CA1077239A (en) | 1975-10-17 | 1976-10-15 | Ilmenite oxidation in a carbon-containing fluidized bed |
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 |
| DE10260741A1 (en) | 2002-12-23 | 2004-07-08 | Outokumpu Oyj | Process and plant for the heat treatment of fine-grained solids |
| DE10260739B3 (en) | 2002-12-23 | 2004-09-16 | Outokumpu Oy | Process and plant for producing metal oxide from metal compounds |
| 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 |
| DE10260734B4 (en) | 2002-12-23 | 2005-05-04 | Outokumpu Oyj | Process and plant for the production of carbon coke |
| DE10260738A1 (en) | 2002-12-23 | 2004-07-15 | Outokumpu Oyj | Process and plant for conveying fine-grained solids |
| DE10260737B4 (en) | 2002-12-23 | 2005-06-30 | Outokumpu Oyj | Process and plant for the heat treatment of titanium-containing 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 CA CA263,445A patent/CA1077239A/en not_active Expired
- 1976-10-15 JP JP51123044A patent/JPS5249997A/en active Pending
- 1976-10-15 NL NL7611451A patent/NL7611451A/en not_active Application Discontinuation
- 1976-10-15 IT IT28364/76A patent/IT1069022B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| DE2644581A1 (en) | 1977-04-28 |
| AU1797276A (en) | 1978-04-06 |
| FR2328048B1 (en) | 1981-01-09 |
| IT1069022B (en) | 1985-03-21 |
| NL7611451A (en) | 1977-04-19 |
| NO144297C (en) | 1981-08-05 |
| NO144297B (en) | 1981-04-27 |
| JPS5249997A (en) | 1977-04-21 |
| BE847207A (en) | 1977-01-31 |
| NO763518L (en) | 1977-04-19 |
| AU504225B2 (en) | 1979-10-04 |
| FR2328048A1 (en) | 1977-05-13 |
| GB1502576A (en) | 1978-03-01 |
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