CN100557044C - Produce the method and apparatus of metal by corresponding metal halogenide by metal halide and reductive agent reaction - Google Patents
Produce the method and apparatus of metal by corresponding metal halogenide by metal halide and reductive agent reaction Download PDFInfo
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- CN100557044C CN100557044C CNB2005800299722A CN200580029972A CN100557044C CN 100557044 C CN100557044 C CN 100557044C CN B2005800299722 A CNB2005800299722 A CN B2005800299722A CN 200580029972 A CN200580029972 A CN 200580029972A CN 100557044 C CN100557044 C CN 100557044C
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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
- C22B34/1263—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 obtaining metallic titanium from titanium compounds, e.g. by reduction
- C22B34/1268—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 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
- C22B34/1272—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 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams reduction of titanium halides, e.g. Kroll process
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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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
- C22B5/14—Dry methods smelting of sulfides or formation of mattes by gases fluidised material
Abstract
A kind of method of producing metal by corresponding metal halogenide, this method forms the halogenide of described metal and described reductive agent by the reaction of metal halide and reductive agent, this is reflected in the reactor of the fluidized-bed that contains the metal seed particles and carries out under high temperature and normal atmosphere, described method comprises: in reactor, effectively forms the seed particles fluidized-bed and guarantees that the halogenide of unreacted reductive agent and reductive agent is accounting under the main temperature and pressure condition with certain speed and amount injecting inert gas, and can enrichment in reactor; The temperature that keeps mixture in the reactor is below the fusing point of metal; And with and form metallographic phase than the mode that more helps on seed particles, forming metal, transferring metal halogenide and reductive agent in fluidized-bed by the homogeneous gas phase between metal halide and the reductive agent.
Description
The invention provides a kind of method of producing metal or alloy by reduction corresponding metal halogenide.The invention still further relates to the equipment that is fit to implement this method.
The present invention will describe in detail with reference to producing titanium with the magnesium reduction titanium tetrachloride.But, it is to be noted that the present invention has more generalized suitability on principle, so the present invention can be used to use similar reduction reaction to prepare other metal.
Worldwide be used for producing titanium by the Kroll technology of magnesium reduction titanium tetrachloride.This is reflected in the stainless steel reactor and carries out, and fused magnesium contacts with gaseous titanium tetrachloride in this reactor, and the titanium of generation is " sponge " shape.Though this production technique was used about 50 years, the formation mechanism of related reaction mechanism and titanium sponge clearly is not familiar with.This reaction is considered to represent with following equation:
TiCl
4(g)+2Mg(l)＝Ti(s)+2MgCl
2(l)
Regrettably, because sponge adheres to when it forms on the reactor by the iron pollution of reactor, Kroll technology is the low intermittent production method of a kind of poor efficiency and titanium productive rate.And magnesium chloride product and unreacted magnesium can remain in the titanium sponge, and these impurity must be removed subsequently by the vacuum distilling step.This step equally also is an intermittent operation.Consider pollution problem, described cavernous body must be produced the titanium that meets quality by a step or the refining of multistep vacuum arc melting.
The various different process of producing titanium also are proposed.Yet also there is relevant shortcoming in these technologies.Therefore, US 2,827, and 371 describe a kind of method of producing titanium, wherein in the sodium-chlor particulated bed titanium tetrachloride and sodium are reacted under inert atmosphere.But the titanium valve of gained must make it the reactive aftertreatment that reduces through be heated to 850 ℃ under inert atmosphere.
US 4,877, and 445 disclose a kind of fluidized-bed process, and wherein titanium tetrachloride vapors and magnesium vapor react under 1000-1200 ℃ temperature.This is reflected under the low absolute pressure (in the scope of 20-50 holder) and carries out to stop the condensation of unreacted magnesium and reaction product magnesium chloride.The condensation meeting of these materials causes product pollution and/or reactor fouling.In practice, under technical scale, be difficult to keep the required low operating pressure of this class technology.
JP 3-150326 has instructed a kind of alternative method that can under atmospheric pressure carry out.Wherein gaseous titanium tetrachloride and gaseous magnesium are blown in the fluidized-bed of titanium seed particles by hot inert gas stream.Control is sent into the amount of the rare gas element in the bed to guarantee that under the temperature in reactor, the dividing potential drop of unreacted magnesium and magnesium chloride is lower than equilibrium vapor pressure separately in reactor.Use rare gas element to make reaction can under atmospheric pressure carry out and avoid the condensation of unreacted magnesium and/or magnesium chloride in this mode.In described method, the rare gas element of reactant and heat is sent into fluidized-bed by dispersion impeller from the bottom.Its objective is that the result's product titanium in reaction as inhomogeneous reaction is formed at the seed particles surface, and when these particles grow to specific particle diameter, they are shifted out from reactor.
Though, can think from the disclosure of JP3-150326 and unclear, mix uncontrolledly owing to introduce reactant in the fluidized-bed, a large amount of gas-phase reactions can take place in reactor.That such homogeneous phase (gas phase) reaction can cause is tiny, submicron order titanium particulate forms rather than the growth of seed particles.This itself can cause problem, because the fine titanium particles that generates is difficult to handle, and is easier to sintering and oxidation than bigger particle.And tiny particle can cause oxidizing fire in aftertreatment technology.
These problems relevant with disclosed method among the JP 3-150326 also have related at same applicant's JP 3-150327.JP 3-150327 uses as the main fluidized-bed reactor of describing among the JP 3-150326 and handle titanium particulate second fluidized-bed that shifts out continuously from main reactor.One of function of second fluidized-bed is to isolate the titanium particle of required particle diameter in the titanium particle that generates from main reactor.Its objective is that tiny particle is turned back in the reactor deposition by titanium carries out further growth.Can think that those skilled in the art can admit, in JP 3-150327, in the technology of carrying out in this kind mode, it is known that the fine titanium particles that has significant proportion in main reactor generates.
The present invention seeks a kind of method that overcomes the shortcoming relevant with these currently known methodss.Therefore, the present invention seeks to provide a kind of and prepares the method for metal by reduction corresponding metal halogenide, and this method can production high yield and highly purified metal.The present invention also seeks to provide a kind of method of producing metal, and this method can under atmospheric pressure be operated and can not caused a large amount of tiny metallic particles to produce.In a preferred embodiment, technology of the present invention can operate continuously.
In view of the above, the invention provides a kind of method of producing metal by corresponding metal halogenide, this method forms the halogenide of described metal and described reductive agent by the reaction of metal halide and reductive agent, this is reflected in the reactor of the fluidized-bed that contains the metal seed particles and carries out under high temperature and normal atmosphere, and described method comprises:
The halogenide that effectively forms the seed particles fluidized-bed and guarantee unreacted reductive agent and reductive agent with certain speed and amount injecting inert gas in reactor can condensation in reactor under the temperature and pressure condition of using always;
Top temperature is below the fusing point of metal in the maintenance reactor; And
With and form metallographic phase than the mode that more helps on seed particles, forming metal, transferring metal halogenide and reductive agent in fluidized-bed by the homogeneous gas phase between metal halide and the reductive agent.
In content of the present invention, prepared metal can be single alloy of planting metal simple-substance or two kinds or above metal.Unless otherwise indicated, term " metal " refers to single metal or alloy of planting.
Key of the present invention is to consider to promote the contact of reactant on the seed particles surface that constitutes fluidized-bed, thus the inhomogeneous reaction of assurance and make the surface of metal deposition in seed particles.Can think that also this effect can reduce or eliminates the interaction between the reactant in the gas phase fully, this interaction may cause forming tiny metallic particles.In order to promote metal to form on the surface of the seed particles of forming fluidized-bed, the control reactant be transported in the fluidized-bed and the method that makes it to be in contact with one another in the prior art without any open.By adopting concrete step control reactant how to be in contact with one another, technology of the present invention more helps deposit on the seed particles surface by metal makes seed particles roughening rather than reactant by the new tiny metallic particles of homogeneous gas phase generation.
Be not wishing to be bound by theory, it is believed that with one of reactant not with exist on the seed particles surface before co-reactant has any contact and can not carry reactant to fluidized-bed for the mode that reaction obtains, might promote heterogeneous gas-phase reaction on the seed particles surface of formation fluidized-bed.Therefore the mode of implementing method of the present invention depends under the operation condition of fluidized-bed, is present in the type of the surface interaction between used reactant and the seed particles.For example, be adsorbed or be impregnated on the surface of the seed particles that is in contact with it, before needs guarantee that this absorption or dipping occur in this reactant and co-reactant contacts according to the present invention if recognize gaseous reactant.Being familiar with these interactions is crucial for the design of implementing the present invention and equipment.
Successful implementation the present invention also will comprise understanding and/or control carrying out seed particles and how to flow along with technology of the present invention in fluidized-bed.It should be noted that and to think that one of reactant is being important with " combining (associated) " with seed particles before co-reactant contacts.Seed particles can influence this combination in the flow pattern of relevant reactant conveyor zones.And, after this reactant suitably has been attached on the seed particles, the contact of the mobile common dependent reaction thing of the particle in the fluidized-bed.By adopting this method, thereby avoid uncontrollable contact of reactant to avoid the uncontrollable homogeneous gas phase of reactant to become possibility when realizing in fluidized-bed, introducing reactant.In order to obtain the growth of desirable seed particles by metal deposition, must repeat reaction on the seed particles surface.Therefore, after seed particles was by the metal parcel, it also was important that these seed particles that are wrapped of recirculation make it to combine with corresponding reactant once more.After such combination, seed particles is " initialize " for reactant reaction together, and these seed particles flow into the zone that co-reactant exists in the bed.Seed particles constantly cycles through the respective regions that reactant occupies in this way, circulates in particle surface at every turn and forms metal.
In practice, various factors can influence the flow pattern of seed particles in fluidized-bed.The factor of this class can comprise shape, the seed particles of reactor initial particle, how to carry rare gas element and/or temperature condition and variation thereof in reactor.Be necessary to adjust some or all of these variable factors and optimize technology of the present invention.And reactant is conveyed into the mode in the fluidized-bed, and reactant and seed particles to carry out the necessary required residence time that combines also be successfully to operate correlative factor of the present invention.Be admitted to moment of fluidized-bed at reactant, reactant combines with seed particles, and if not so, this situation must be considered.If reactant just should be considered this factor combine the preceding phase transformation that can take place to a certain degree with seed particles.Any or all of these factors taken together can be estimated by computer model and/or test, thereby can design suitable reactor and corresponding operational condition.
In one embodiment of the invention, two kinds of reactants all are transported in the fluidized-bed with the form of gases/vapors, and wherein one of reactant is with before co-reactant contacts, and are adsorbed by seed particles or flood seed particles.Typically, in the present embodiment, metal halide combines with seed particles.
The present embodiment can be implemented by the different separately zone that reactant is transported in the fluidized-bed.In this case, the position of carrying reactant and seed particles flow and satisfy seed particles and contact with one of reactant (first reactant), thus combination with it, and these particles flow into the zone of another (second) reactant existence subsequently.Reactant reacts then metal deposition at particle surface on the surface of seed particles.After the site that is used for this reaction had been arranged, the mobile particle that makes of the seed particles in this contacted with first reactant once more.
The present embodiment can realize by independent nozzle of each reactant.The flow pattern that the consideration seed particles is confirmed in fluidized-bed is arranged the locus of nozzle in reactor on demand.In addition, reactant flow can get a desired effect to use single nozzle to carry independently.Can realize by the nozzle that use has a concentric outlet in this present invention.For example, this nozzle contains the central duct of an a kind of reactant of spray, is surrounded by the circulating line of another reactant on every side.In this case, the seed particles in fluidized-bed fails to be convened for lack of a quorum and passes the reactant flow of carrying from ring pipe usually, enters into the reactant flow of carrying from pipe core, and then circulates this particle flux and so on.In this case, be to be understood that particle flux is suitable for first reactant is carried by ring pipe, and second reactant is carried by pipe core.
Can prevent the too early contact of reactant by injecting inert gas between adjacent reactant flow.Between this indifferent gas physical efficiency prevention reactant of the present invention, react and combine with seed particles up to one of reactant.Yet in this case, rare gas element can not disturb in reactor that seed particles is desirable to flow.In described concentric nozzle design mentioned, rare gas element can be by carrying at the pipe core of carrying reactant and the ring pipe between the ring pipe.
In another embodiment, one of reactant is present in the fluidized-bed with liquid form, this reactant with the surface of co-reactant as wetting before the contacting of particulate stream or parcel seed particles.Although when using liquid reactant, can use other mode of movement, for example by the mode of movement of gravity, the same here suitable gas reactant of above-mentioned same principle.
According to the present invention, use rare gas element to adjust the dividing potential drop of the halogenating reaction thing that forms after unreacted reactant and the reduction reaction.Can be transported to the amount of the rare gas element in the reactor to prevent the condensation under the hope service temperature of reactor of these materials according to the suitable change of required dividing potential drop.Can illustrate how this realizes with reference to the titanium tetrachloride/magnesium reaction system.Wish to stop the magnesium chloride of generation and the condensation of any unreacted magnesium at this.Following table illustrated magnesium chloride under atmospheric pressure when being 1 normal atmosphere (be the dividing potential drop of magnesium chloride) gasification temperature is 1418 ℃, and magnesium is 1100 ℃.Under the absolute pressure that reduces, the dividing potential drop of these materials equals the temperature step-down of absolute pressure, and their gasification temperature is step-down also.
| Partial pressure (atm) | MgCl 2Boiling point (approximation) (℃) | Mg boiling point (approximation) (℃) |
| 1 | 1418 | 1103 |
| 0.5 | 1311 | 1024 |
| (0.065 50 holder) | 1068 | 837 |
For guarantee that preparation technology carries out under the temperature that reduces, avoid the condensation (boiling point of magnesium is lower under uniform pressure) of magnesium chloride simultaneously, finish drilling in the low pressure condition usually and make this technology.Therefore, if this technology was 50 holder (as in US 4,877,445) whens operation in absolute reaction pressure, temperature of reaction will more than 1068 ℃ to avoid the condensation of magnesium chloride.Yet,, can obtain same effect by dividing potential drop that reduces magnesium chloride rather than the absolute pressure that reduces in the reactor according to the present invention.This can realize by the rare gas element that injects appropriate amount in reactor.This makes technology of the present invention under atmospheric pressure to operate under the temperature of the known boiling point that is lower than magnesium chloride.Therefore, if wish at 1320 ℃, normal atmosphere is operation technology of the present invention down, and the branch that must use a certain amount of rare gas element to reduce magnesium chloride is depressed into 0.5atm.The boiling point of magnesium chloride is 1311 ℃ like this, promptly is lower than selected service temperature.
Use more substantial rare gas element can make technology under lower temperature, operate the condensation that (under atmospheric pressure) avoids magnesium chloride simultaneously.But in practice, it is inconvenient and/or uneconomical usually to use too much inert gas dilution to obtain low working pressure.The a large amount of rare gas element of injection also can cause in the undesirable fluctuation of fluidized-bed and be difficult in the particle flow pattern (flow patterns) that liquid bed reaches hope in fluidized-bed.
Those skilled in the art can adjust dividing potential drop in the mode of using rare gas element like a dream, especially under the instruction of JP 3-150326 and JP 3-150327.Usually use argon gas or helium as rare gas element.
Being used to implement seed particles of the present invention is made up of the metal of the desired preparation of reduction reaction.According to related principle, the surface properties by changing seed particles and/or the initial size of seed particles one of can the intensified response things and the binding ability of seed particles.Usually, the initial size of seed particles is 200 to 500 μ m but is not limited only to this scope.Usually wish the particle of roughen is shifted out from reactor.If technology of the present invention is operated with intermittent mode, the particle of roughening is moved out of from reactor, and reinstalls the new seed particles of suitable size in reactor.
In other words, according to embodiment preferred of the present invention, technology of the present invention is operate continuously.In order to reach this purpose, the seed particles that must be wrapped up and grow into predetermined size by metal shifts out and replenishes little seed particles in reactor.These seed particles can be to add to the new seed particles that is used for metal deposition the bed from the autobiography seed particles of the existing seed particles generation of the metal parcel that is worn in the bed and/or from inlet.Particle with expection size can reclaim by suitable outlet from reactor.Basically, the particle of alligatoring shifts out from reactor by the self-regulating method based on particle diameter and fluidization conditions.The particle that is moved out of is cooled subsequently.Importantly, the shifting out of the particle that is wrapped, the generation of autobiography seed particles and the introducing of new seed particles do not have negative impact to forming the desirable flow pattern of fluidized-bed particle in bed.
Typically, reduction reaction is heat release.In this case, according to the preferred embodiments of the invention, at least a reactant is transported in the fluidized-bed with solid-state or liquid form, and at least a subsequently reactant is owing to the temperature in the bed undergoes phase transition.Phase transformation is absorbed heat, and this can help to relax the temperature in the reactor in the reduction reaction process.If utilize the phase change of one or both reactants, still need to guarantee the enforcement of total principle of the present invention and keep.
Here the zone that reactant reacts in fluidized-bed is called " reaction zone ".In a preferred embodiment, behind the surface of metal deposition in seed particles, the particle that is wrapped with new system shifts out (by means of the flow pattern of setting up in the fluidized-bed) and the cold zone quenching promptly beyond reaction zone from reaction zone rapidly.Because normally heat release of reduction reaction, the temperature of reaction zone is higher than the fluidized-bed other parts that reduction reaction does not take place.
Wish temperature in the control fluidized-bed guaranteeing any tiny metallic particles sintering that may form, and bigger metallic particles sintering does not take place.If reaction is heat release, in fact need concrete steps to reduce medial temperature in the fluidized-bed.According to being applicable to total principle of the present invention, in any case the temperature that relaxes in the reactor is to need to consider.Temperature can be by changing reactant temperature and/or, and the amount of the rare gas element of carrying and temperature and/or the transformation mutually that depends on aforesaid reactant are regulated.The energy that reaction is caused discharges and can be used for by suitable heat exchange systems reactant is transformed into gas.If the energy that obtains from reactor itself is not enough, can pass through fuel burning, for example combustion of methane is added energy in air.
The present invention is preferred for by appropriate reductant, and for example magnesium or zinc reduction titanium tetrachloride is produced titanium.That is to say that the present invention can be used for producing alloy and other metal by appropriate reductant with similar reduction reaction.Therefore, the present invention can be used for producing zirconium, silicon, tantalum or niobium from the corresponding chlorinated thing.The suitable reductive agent that adopts under the familiar every kind of situation of those skilled in the art.
For the titanium tetrachloride/magnesium reaction system, in one embodiment, two kinds of reactants all are transported in the fluidized-bed with gaseous form.Be on the surface that the gasiform titanium tetrachloride could be adsorbed or be impregnated into the titanium seed particles that forms fluidized-bed.Thereby guaranteeing that titanium tetrachloride contacts with seed particles occurs in before magnesium contacts.
Scheme as an alternative, magnesium can fused solution form be provided in the fluidized-bed.Magnesium can be moistening/be wrapped in the surface of seed particles, thus contact to form the combination of necessary reactant/seed particles with seed particles.In the fluidized-bed conveying of the flow pattern of seed particles and gaseous titanium tetrachloride adopt should make contact with titanium tetrachloride before magnesium moistening/wrap up seed particles.In a preferred embodiment, magnesium is transported in the reactor with the temperature that is enough to make immediately the magnesium fusing with solid-state form.Describe this phase transformation before this and can be used for relaxing temperature of reactor.
Embodiment of the present invention further specify by accompanying drawing, but are not limitation of the present invention.These accompanying drawings are:
Fig. 1 is the synoptic diagram of a kind of operator scheme of the present invention;
Fig. 2 is the operating concept of the concentric nozzles used in one embodiment of the invention;
And Fig. 3 is the synoptic diagram of another kind of operator scheme of the present invention.
Be that reaction system is discussed with the titanium tetrachloride/magnesium in the accompanying drawing below.But for this reaction system, its purpose is only used for illustrating and is not limited to the embodiment shown in the figure.
In the embodiment of Fig. 1 signal, Mg and TiCl
4Be transported in the fluidized-bed with gaseous form.TiCl
4Carry from the bed bottom by concentric nozzles with Mg, Mg carries by pipe core, TiCl
4By around ring pipe carry.In the embodiment depicted in fig. 1, two such nozzles are arranged, each all is contained between the argon gas transfer lime that argon gas is provided in the subtend fluidized-bed.
As mentioned above, adopt appropriate operational parameters, can believe near each concentric nozzles the seed particles flow pattern as shown in Figure 2.The seed particles here is recycled to Mg from outer peripheral areas and injects central zone on the fluidized-bed position.Carry TiCl
4Contact with seed particles when making it flow to the central section.At TiCl
4It is believed that TiCl when contacting with seed particles
4Be attracted to or flood the surface of seed particles.Subsequently in conjunction with TiCl
4Seed particles flow into reaction zone, contact with coreagent Mg therein.In reaction zone, TiCl
4With the surface reaction of Mg in seed particles, thereby Ti is deposited on the growth that particle surface causes seed particles as a result.This reaction be heat release and different according to the argon gas amount of the temperature of reactant and use, reaction zone temperature is usually between 1800-3500 ℃.Argon gas can first preheating before injecting.
By behind the Ti parcel, parcel back seed particles is removed from reaction zone in reaction zone, and enter into fluidized-bed than cooling segment, in this and rapid quenching after other particle in the bed contact.
Typically, for using the magnesium reduction titanium tetrachloride, fluidized-bed is 1200 ℃ of temperature, and normal atmosphere is operation down.The temperature of corresponding reaction zone is about 1880 ℃.
The MgCl that reduction reaction generates
2Under the underlying condition of reactor, still remain gaseous state.If operation under lower temperature then need to use more argon gas makes MgCl
2Have lower partial vapor pressure, thus the MgCl that has discussed before avoiding according to the reaction generation
2Condensation.
MgCl
2Gas and argon gas leave and enter chilling apparatus from the top of fluidized-bed reactor, and this device can be particle MgCl
2The circulating fluidized bed expander that forms.Argon gas is cooled off rapidly and MgCl in described bed
2MgCl in bed
2The particle surface condensation.Can use various expander design.Described MgCl
2Particle can be used for generating magnesium in a usual manner at electrolyzer.
Titanium particle with suitable size can reclaim and replenish new seed particles from fluidized-bed reactor.The present invention can continuous operations in this way.
As a kind of alternate embodiment of operating procedure of the present invention as shown in Figure 3.This embodiment adopts the spouted bed bioreactor that comprises titanium seed particles fluidized-bed.The rare gas element and the gaseous state TiCl of heat
4Send into from this bottom.Argon gas is sent into by the central nozzle of jet pipe end.TiCl
4Argon gas injects the jet pipe outside surface of nozzle and the annular space between the reactor internal surface is transported to fluidized-bed through having.Solid-state Mg is by being positioned at TiCl on the reactor wall
4Independent inlet on the inlet is sent into.Cause the fusing immediately of Mg and can believe in the temperature of inside reactor and cause seed particles to be wrapped up by the Mg of skim thus in the magnesium ingress.
The flow pattern of the seed particles that is wrapped should make these seed particles flow into TiCl subsequently
4The fluidized bed region that exists.MgCl takes place to form on the surface of the seed particles of Mg parcel in reduction reaction then
2(under main condition, being gaseous state) and the new Ti integument on seed particles.As above-mentioned other embodiment, the flow pattern of particle in the bed is such, the particle of titanium parcel cycle through take place in the reaction system quenching than the cooling zone.This can carry out in same container or different container.Particle after the quenching can be wrapped up by Mg by follow-up reaction at them, or emit from reactor near the recirculation Mg inlet, and suitable additional described particle.MgCl
2Can handle by the method that above-mentioned Fig. 1 relates to.
Because effective heat transfer surface area of unit volume is big in the fluidized-bed, can realize exchange rate efficiently.The temperature fluctuation that the input of reactant and/or rare gas element and/or the reaction in fluidized-bed are caused reaches rapid balance.
In these two embodiments, importantly seed particles with suitably combine with one of reactant before co-reactant contacts.This can realize by changing above-mentioned processing parameter.
In this specification sheets and claim thereafter, unless do regulation in the text in addition, word " comprises " and various variation for example " comprises " and " comprising " should be understood to expression and comprise certain integral body or step or one group of integral body or step, does not also comprise other integral body or step or whole group or step group but do not get rid of.
Any prior art of quoting in this manual partly belongs to common practise in Australia, can not be considered to common practise or any type of hint.
Claims (22)
1. method of producing metal by corresponding metal halogenide, this method forms the halogenide of described metal and described reductive agent by the reaction of metal halide and reductive agent, this is reflected in the reactor of the fluidized-bed that contains the metal seed particles and carries out under high temperature and normal atmosphere, and described method comprises:
The halogenide that forms the seed particles fluidized-bed with certain speed and significant quantity injecting inert gas and guarantee unreacted reductive agent and reductive agent in reactor can condensation in reactor under temperature and pressure condition commonly used;
Top temperature is below the fusing point of metal in the maintenance reactor;
With and form metallographic phase than the mode that more helps on seed particles, forming metal, transferring metal halogenide and reductive agent in fluidized-bed by the homogeneous gas phase between metal halide and the reductive agent; And
By carry reactant make in the fluidized-bed one of reactant with exist on the surface of seed particles before co-reactant contact and can be the reaction acquisition, promote lip-deep inhomogeneous reaction in the seed particles of formation fluidized-bed.
According to the process of claim 1 wherein reactant be transported in the fluidized-bed with the gases/vapors form and one of reactant with adsorbed by seed particles before co-reactant contacts or flood seed particles.
3. according to the method for claim 2, wherein the metal halide of Sheng Chenging combines with seed particles.
4. according to the method for claim 2, wherein reactant is transported to the different zones in the fluidized-bed respectively.
5. according to the method for claim 4, wherein carry the position and the flowing of seed particles of reactant should make seed particles contact with one of reactant, thereby combination with it, these particles flow into the zone that another reactant exists subsequently, and reactant reacts then metal deposition at particle surface on the surface of seed particles.
6. according to the method for claim 2, wherein every kind of reactant uses injection nozzle separately to carry.
7. according to the method for claim 2, wherein use injection nozzle to carry reactant with concentric reactant outlet.
8. according to the method for claim 7, wherein stop the too early contact of reactant by injecting inert gas between adjacent reactant flow.
9. method according to Claim 8, wherein rare gas element is carried by being contained in pipe core and the ring pipe between the ring pipe of carrying reactant.
10. according to the process of claim 1 wherein that one of reactant is present in the fluidized-bed with liquid form, this reactant because particulate flows with the surface of wetting seed particles before co-reactant contacts.
11. according to the process of claim 1 wherein that seed particles is by forming with the metallographic phase that will generate by reduction reaction metal together.
12. according to the process of claim 1 wherein that the particle of roughening shifts out from reactor by the self-adjusting method based on size of particles and fluidization conditions.
13. method according to claim 1, wherein reduction reaction is heat release, and at least a reactant is transported in the fluidized-bed with solid-state or liquid form, this at least a reactant is owing to the temperature in the fluidized-bed undergoes phase transition subsequently, thereby relaxes the temperature in the reactor in the reduction reaction process.
14., be used for preparing titanium by the reduction titanium tetrachloride according to the method for claim 1.
15. according to the method for claim 14, wherein reductive agent is a magnesium.
16. according to the method for claim 15, wherein titanium tetrachloride and magnesium are transported in the fluidized-bed with gaseous form.
17. according to the method for claim 15, wherein magnesium is present in the fluidized-bed with the form of fused solution, wherein titanium tetrachloride is transported in the fluidized-bed with gaseous form, wherein magnesium with wetting seed particles before titanium tetrachloride contacts.
18. according to the method for claim 17, wherein magnesium is transported in the reactor with the temperature that is enough to make immediately the magnesium fusing with solid-state form.
19. implement the device of the method for claim 1, it comprises fluidized-bed reactor, this fluidized-bed reactor be suitable for by metal halide and homogeneous gas phase between the reductive agent form metal more help making the mode transferring metal halogenide that forms on the seed particles of metal in fluidized-bed and reductive agent to this fluidized-bed with by carry reactant make in the fluidized-bed one of reactant with exist on the surface of seed particles before co-reactant contact and can serve as the reaction acquisition, promote lip-deep inhomogeneous reaction in the seed particles of formation fluidized-bed.
20. according to the device of claim 19, comprise that is used for carrying the injection nozzle of gaseous reactant to fluidized-bed, described nozzle comprises concentric reactant outlet.
21. according to the device of claim 20, wherein injection nozzle comprises a ring pipe of carrying rare gas element, this ring pipe is contained between the pipe core and surrounding tube of carrying reactant.
22. according to the device of claim 19, comprise a spouted fluidized bed bioreactor, be suitable for carrying the rare gas element of gaseous metal halogenide and heating from the bottom of this fluidized-bed; Independently enter the mouth in reactor with the conveying solid substance reactant, described inlet is on the reactor wall more than the fluidized-bed bottom.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2004904305 | 2004-07-30 | ||
| AU2004904305A AU2004904305A0 (en) | 2004-07-30 | Industrial Process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101014721A CN101014721A (en) | 2007-08-08 |
| CN100557044C true CN100557044C (en) | 2009-11-04 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800299722A Expired - Fee Related CN100557044C (en) | 2004-07-30 | 2005-07-29 | Produce the method and apparatus of metal by corresponding metal halogenide by metal halide and reductive agent reaction |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20090120239A1 (en) |
| CN (1) | CN100557044C (en) |
| WO (1) | WO2006010223A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108350524A (en) * | 2015-08-14 | 2018-07-31 | 库吉钛私人有限公司 | With the method for excessive oxidant production composite material |
| US10960469B2 (en) | 2015-08-14 | 2021-03-30 | Coogee Titanium Pty Ltd | Methods using high surface area per volume reactive particulate |
| US11162157B2 (en) | 2015-08-14 | 2021-11-02 | Coogee Titanium Pty Ltd | Method for recovery of metal-containing material from a composite material |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7914600B2 (en) * | 2007-01-22 | 2011-03-29 | Materials & Electrochemical Research Corp. | Continuous production of titanium by the metallothermic reduction of TiCl4 |
| AU2010252965B2 (en) * | 2009-05-29 | 2013-05-23 | Hitachi Metals, Ltd. | Method for producing titanium metal |
| JP5571537B2 (en) * | 2010-11-22 | 2014-08-13 | 日立金属株式会社 | Metal titanium manufacturing apparatus and metal titanium manufacturing method |
| CN102816942B (en) * | 2012-09-11 | 2013-11-06 | 朝阳金达钛业有限责任公司 | Process and device for producing high-nitrogen sponge titanium |
| CN106350687B (en) * | 2016-09-05 | 2018-08-14 | 成都先进金属材料产业技术研究院有限公司 | The device and method of separating-purifying titanium sponge |
| CN111283215B (en) * | 2020-02-24 | 2021-06-11 | 北京科技大学 | Method for preparing oxygen-free passivated titanium and titanium alloy powder products by gas-solid fluidization |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4039324A (en) * | 1975-11-14 | 1977-08-02 | Cyprus Metallurgical Processes Corporation | Fluidized hydrogen reduction process for the recovery of copper |
| JPS6415334A (en) * | 1987-07-09 | 1989-01-19 | Toho Titanium Co Ltd | Production of metal from metal halide |
| JPH03150326A (en) * | 1989-11-06 | 1991-06-26 | Osaka Titanium Co Ltd | Production of metal by reduction |
| JPH03150327A (en) * | 1989-11-06 | 1991-06-26 | Osaka Titanium Co Ltd | Manufacture of metallic ti |
| JP3615466B2 (en) * | 2000-06-14 | 2005-02-02 | 東邦チタニウム株式会社 | Sponge titanium manufacturing method and manufacturing apparatus |
| US6902601B2 (en) * | 2002-09-12 | 2005-06-07 | Millennium Inorganic Chemicals, Inc. | Method of making elemental materials and alloys |
| US6955703B2 (en) * | 2002-12-26 | 2005-10-18 | Millennium Inorganic Chemicals, Inc. | Process for the production of elemental material and alloys |
| US7837759B2 (en) * | 2004-10-20 | 2010-11-23 | Commonwealth Scientific And Industrial Research Organisation | Low temperature industrial process |
-
2005
- 2005-07-29 WO PCT/AU2005/001126 patent/WO2006010223A1/en active Application Filing
- 2005-07-29 CN CNB2005800299722A patent/CN100557044C/en not_active Expired - Fee Related
- 2005-07-29 US US11/658,753 patent/US20090120239A1/en not_active Abandoned
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108350524A (en) * | 2015-08-14 | 2018-07-31 | 库吉钛私人有限公司 | With the method for excessive oxidant production composite material |
| US10960469B2 (en) | 2015-08-14 | 2021-03-30 | Coogee Titanium Pty Ltd | Methods using high surface area per volume reactive particulate |
| US11078556B2 (en) | 2015-08-14 | 2021-08-03 | Coogee Titanium Pty Ltd | Method for production of a composite material using excess oxidant |
| US11162157B2 (en) | 2015-08-14 | 2021-11-02 | Coogee Titanium Pty Ltd | Method for recovery of metal-containing material from a composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| US20090120239A1 (en) | 2009-05-14 |
| CN101014721A (en) | 2007-08-08 |
| WO2006010223A1 (en) | 2006-02-02 |
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