CN101044268A - Metal producing method and producing device by molten salt electrolysis - Google Patents
Metal producing method and producing device by molten salt electrolysis Download PDFInfo
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- CN101044268A CN101044268A CNA2005800349261A CN200580034926A CN101044268A CN 101044268 A CN101044268 A CN 101044268A CN A2005800349261 A CNA2005800349261 A CN A2005800349261A CN 200580034926 A CN200580034926 A CN 200580034926A CN 101044268 A CN101044268 A CN 101044268A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 157
- 239000002184 metal Substances 0.000 title claims abstract description 157
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 66
- 150000003839 salts Chemical class 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 32
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 41
- 239000001110 calcium chloride Substances 0.000 claims abstract description 41
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 41
- 238000004891 communication Methods 0.000 claims abstract description 28
- 229910052791 calcium Inorganic materials 0.000 claims description 91
- 239000011575 calcium Substances 0.000 claims description 91
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 87
- 238000004519 manufacturing process Methods 0.000 claims description 52
- 230000004927 fusion Effects 0.000 claims description 51
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 36
- 239000010936 titanium Substances 0.000 claims description 36
- 229910052719 titanium Inorganic materials 0.000 claims description 35
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 33
- 238000002844 melting Methods 0.000 claims description 30
- 230000008018 melting Effects 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims 2
- CPRPMYXKLMPQOB-UHFFFAOYSA-K [Na+].[Cl-].[Cl-].[Cl-].[Ba+2] Chemical compound [Na+].[Cl-].[Cl-].[Cl-].[Ba+2] CPRPMYXKLMPQOB-UHFFFAOYSA-K 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000460 chlorine Substances 0.000 description 17
- 229910052801 chlorine Inorganic materials 0.000 description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 238000003287 bathing Methods 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 230000032696 parturition Effects 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 150000001669 calcium Chemical class 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000005325 percolation Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- -1 calcium metals Chemical class 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- C22B34/129—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 by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
- C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
- C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention provides a metal producing method by molten salt electrolysis carried out with calcium chloride molten salt filled in an electrolytic bath provided with an anode and a cathode, characterized in that either one electrode of the anode and the cathode is provided so as to surround the other electrode, the cathode is provided with at least one communication port to allow communication between an inner area surrounded by the cathode and an outer area, and molten salt is allowed to flow from one area, out of the inner area and the outer area, on the anode-provided side to the other area via the communication port.
Description
Technical field
The present invention relates to make metal, particularly relate to and comprise by fusion electrolysis and make the method for calcium metal and utilize this calcium metal to make the manufacture method and the manufacturing installation of metal of the method for metal titanium by metal chloride.
Background technology
In the past, the elemental metals titanium was by the Kroll manufactured that titanium tetrachloride is obtained titanium sponge with molten magnesium reduction, and attempted to reduce manufacturing costs by various improvement.But the Kroll method is owing to be with a series of operation multiple batch process discontinuously, so its efficient is restricted.
For above-mentioned condition, proposed in melting salt with calcium metal reduction-oxidation titanium, directly make the method (for example with reference to patent documentation 1,2) of metal titanium, the reductive agent that manufacturing contains calcium isoreactivity metal or active metal alloy, obtain the EMR method (for example with reference to patent documentation 3) of metal titanium by the electron reduction titanium compound of emitting by this reductive agent.In these methods, the secondary calcium oxide of giving birth to of electrolytic reaction is dissolved in calcium chloride after, utilize calcium metal again by the fusion electrolysis manufacturing.But therefore the calcium metal that is generated by electrolytic reaction to the solubleness height of calcium chloride, dissolves dissipation easily owing to be liquid, and openly the overrich contraction is made the technology of the calcium metal of solid state.
In addition, disclose, under than low in the past temperature, carried out the technology (for example with reference to patent documentation 4) that fusion electrolysis makes calcium metal separate out at negative electrode with solid state by using the fusing point composite molten salt lower than calcium metal.But, in the method, need the special composite molten salt of preparing, in addition, problem that also cost must enter into consideration.
In addition, adopt above-mentioned any method, the calcium metal and the secondary chlorine generation reversed reaction that generates of electrolytic reaction of fusion electrolysis generation all arranged, regenerate the trend of calcium chloride, this becomes the reason that efficient reduces.
As mentioned above, in the method in the past, be difficult with metals such as simple substance form recovery or concentrating metals calcium, organic efficiency is low.In addition, even the high problem of cost may also be arranged.As a result, become the cost cause of increased of making titanium.
Patent documentation 1:WO99/064638 number
Patent documentation 2: the spy opens the 2003-129268 communique
Patent documentation 3: the spy opens the 2003-306725 communique
Patent documentation 4:US3226311 number
Summary of the invention
The present invention In view of the foregoing carries out, purpose is to provide a kind of method of making metal by fusion electrolysis, but its Production Example is as being used for reducing metal titanyl compound or muriatic calcium metal, certainly also can utilize this calcium metal to obtain metal titanium, and be the low method of a kind of cost, can implement efficiently.
Method by fusion electrolysis manufacturing metal of the present invention is to contain the method for passing through fusion electrolysis manufacturing metal that the calcium chloride melting salt carries out in the electrolyzer with anode and negative electrode, it is characterized in that, side's electrode in negative electrode or the anode is provided with in the mode of surrounding the opposing party's electrode, negative electrode has at least one and is communicated with the interior region that negative electrode surrounds and the communication port of external region, makes melting salt territory, anodic one lateral areas is set to the opposing party's area cirulating in zone or the external region internally via communication port.
According to the present invention, side's electrodes surrounding the opposing party electrode in anode and the negative electrode, and melting salt is via the communication port that is arranged on the negative electrode, from zone that anodic one side is set to the opposing party's area cirulating, therefore often pushed inflow by fusion electrolysis at the calcium metal of cathode surface generation and do not had the anodic zone, accumulated in this regional electrolytic bath face thereby concentrate.Therefore, the reversed reaction with the chlorine that generates at anode surface can not take place, can make calcium metal expeditiously.
Device by fusion electrolysis manufacturing metal of the present invention is the device that fusion electrolysis is made metal that passes through that has anode and negative electrode in electrolyzer, it is characterized in that, mode with negative electrode or anodic one side's electrodes surrounding the opposing party electrode is provided with, negative electrode has at least one interior region that is communicated with the negative electrode encirclement and the communication port of external region, the calcium chloride melting salt is supplied with in the zone that anodic one side is set in two zones that negative electrode separated, make the calcium chloride melting salt via communication port to the opposing party's area cirulating, take out the calcium chloride melting salt that contains the calcium metal that generates at negative electrode by the opposing party zone.
By this manufacturing installation, as mentioned above, often pushed into there not being the anodic zone by the calcium metal that fusion electrolysis generates at cathode surface, accumulate in this regional electrolytic bath face thereby concentrate.Therefore, the reversed reaction with the chlorine that generates at anode surface can not take place, can make calcium metal expeditiously.
Further, the method by fusion electrolysis manufacturing metal of the present invention is characterised in that, at the interior region that generates calcium metal by fusion electrolysis the titanium tetrachloride supply-pipe is set, and supplies with the gasiform titanium tetrachloride by this titanium tetrachloride supply-pipe, generates metal titanium.
According to this manufacture method, to the calcium metal supply titanium tetrachloride that generates at interior region by fusion electrolysis, so both react the generation metal titanium.Therefore, the unnecessary calcium metal that reclaims in advance is transferred to titanium manufacturing process again, can obtain metal titanium in the manufacturing process of calcium metal.
The invention effect
According to the present invention, suppressed the reversed reaction of calcium metal that the fusion electrolysis by calcium chloride generates and secondary chlorine of giving birth to, but low-cost high-efficiency ground manufacturing calcium metal.In addition, by direct supply titanium tetrachloride, can also obtain metal titanium.
Description of drawings
The schematic cross-section of the manufacturing process that passes through fusion electrolysis manufacturing calcium metal of Fig. 1 embodiments of the present invention.
The schematic cross-section of the manufacturing process that passes through fusion electrolysis manufacturing calcium metal of Fig. 2 other embodiment of the present invention.
The schematic cross-section of the manufacturing process that passes through fusion electrolysis manufacturing calcium metal of Fig. 3 other embodiment of the present invention.
The schematic cross-section of the manufacturing process that passes through fusion electrolysis manufacturing calcium metal of Fig. 4 other embodiment of the present invention.
The schematic cross-section of the manufacturing process that passes through fusion electrolysis manufacturing calcium metal of Fig. 5 other embodiment of the present invention.
The fusion electrolysis that passes through of Fig. 6 other embodiment of the present invention is made the manufacturing process of calcium metal and the schematic cross-section of the operation of making metal titanium.
The fusion electrolysis that passes through of Fig. 7 other embodiment of the present invention is made the manufacturing process of calcium metal and the schematic cross-section of the operation of making metal titanium.
The fusion electrolysis that passes through of Fig. 8 other embodiment of the present invention is made the manufacturing process of calcium metal and the schematic cross-section of the operation of making metal titanium.
The schematic cross-section of the finned cylinder negative electrode that uses among Fig. 9 the present invention.
Nomenclature
1 electrolyzer
2 electrolytic baths
3 anodes
4 negative electrodes
5 calcium metals
6 bathe supply-pipe
7 extract pipe out
8 chlorine
9 rare gas element supply-pipes
10 agitating vanes
11 titanium tetrachloride supply-pipes
12 titanium tetrachlorides
Embodiment
Below by the description of drawings embodiments of the present invention.The figure expression is used to implement preferred device configuration example of the present invention.Fig. 1 is the schematic cross-section of expression the 1st embodiment of the present invention.Symbol 1 is an electrolyzer, and its inside contains the electrolytic bath 2 that contains calcium chloride (780 ℃ of fusing points), is heated to by not shown heating unit more than the fusing point of calcium chloride, keeps molten state.Symbol 3 is an anode.Symbol 4 is the negative electrode of round tube type, disposes in the mode of surrounding anode 3.The bottom of negative electrode 4 is formed with a plurality of communication port, and melting salt can be inside and outside mobile at negative electrode.Because communication port is formed on the negative electrode bottom, so dividing plate also can be played in negative electrode top.
Further, negative electrode 4 inside are provided with bathes supply-pipe 6, and the raw material calcium chloride of fusion electrolysis is supplied with thus continuously.Negative electrode 4 outer upper are provided with the extraction pipe 7 that is used to take out calcium metal.
Molten metal calcium that is transferred to the outside of negative electrode 4 and floats and the spissated calcium chloride of calcium metal are taken out to outside the system continuously by extracting pipe 7 out.Molten metal calcium that takes out and the spissated calcium chloride of calcium metal for example can be used for using the reduction reaction of the titanium oxide or the titanium chloride of melting salt.
On the other hand, generate chlorine on the surface of anode 3, and be discharged into outside the system.It can be used for chlorination reaction or other purposes of titanium ore.
Fig. 2 is the schematic cross-section of expression the 2nd embodiment of the present invention.Symbol 1 is an electrolyzer, and its inside contains the electrolytic bath 2 that contains calcium chloride (780 ℃ of fusing points), is heated to by not shown heating unit more than the fusing point of calcium chloride, keeps molten state.Symbol 3 is and the incorporate anode of electrolyzer.Symbol 4 is the negative electrode of round tube type, disposes in the mode that is immersed in electrolyzer 1 central part.The bottom of negative electrode 4 is formed with a plurality of communication port, and melting salt can be inside and outside mobile at negative electrode.Because communication port is formed on the negative electrode bottom, so dividing plate also can be played in negative electrode top.
Further, negative electrode 4 outsides are provided with bathes supply-pipe 6, and fusion electrolysis raw material calcium chloride is supplied with thus continuously.Negative electrode 4 inside upper part are provided with the extraction pipe 7 that is used to take out calcium metal.
Molten metal calcium that is transferred to the inboard of negative electrode 4 and floats and the spissated calcium chloride of calcium metal are taken out to outside the system continuously by extracting pipe 7 out.Molten metal calcium that takes out and the spissated calcium chloride of calcium metal for example can be used for using the reduction reaction of the titanium oxide or the titanium chloride of melting salt.
On the other hand, generate chlorine on the surface of anode 3, and be discharged into outside the system.It can be used for chlorination reaction or other purposes of titanium ore.
Fig. 3 is the schematic cross-section of the 3rd preferred implementation of the present invention.Symbol 1～8 is identical with Fig. 2, therefore omits explanation.In Fig. 3, different with the situation of Fig. 2, bottom the interior region of negative electrode 4, be blown into rare gas element by rare gas element supply-pipe 9.Play the effect of gas lift by being blown into of rare gas element, produce upwelling at the interior region of negative electrode 4.Accompany therewith, generate by external region flowing to interior region.As a result, can make the calcium metal that generates at the side face of negative electrode 4 move to negative electrode inside, thereby can suppress the loss that reversed reaction caused of the chlorine that generates with external region at negative electrode in the short period of time.
Fig. 4 is the schematic cross-section of the 4th preferred implementation of the present invention.The configuration of symbol 1～8 is identical with Fig. 2, therefore omits explanation.Be that with the difference of the respective embodiments described above as shown in Figure 4, communication port is arranged on the sidewall of negative electrode 4 obliquely in the mode that tilts from vertical direction.In addition, Fig. 9 is a schematic cross-section of observing negative electrode 4 from the top, and as shown in Figure 9, communication port also similarly tilts from the normal direction of cylinder in the horizontal direction.And negative electrode 4 disposes with free rotation mode.By rotating this negative electrode 4, melting salt is moved to interior region by the external region of negative electrode 4.As a result, can make the calcium metal that generates in the outside of negative electrode 4 move to the interior region of negative electrode, therefore can suppress the loss that reversed reaction caused of the chlorine that generates with external region at negative electrode in the short period of time.
Fig. 5 is the schematic cross-section of the 5th preferred implementation of the present invention.Symbol 1～8 is identical with Fig. 2, therefore omits explanation.Be with the difference of the respective embodiments described above, dispose agitating vane 10, can rotate, can form by the melting salt of bottom and flow to the face of bath by drive shaft in the interior region bottom of negative electrode 4.As a result, can make the calcium metal that generates in the outside of negative electrode 4 move to the interior region of negative electrode, therefore can suppress the loss that reversed reaction caused of the chlorine that generates with external region at negative electrode in the short period of time.
Be noted that by appropriate combination Fig. 3～device shown in Figure 5, can be recovered in the calcium metal of the outside generation of negative electrode 4 efficiently.
As mentioned above, according to the present invention, calcium metal is pushed continuously immediately after generation and is flowed to outside the reaction system, therefore can prevent and the reversed reaction of secondary chlorine of giving birth to, and makes efficiently.Particularly, according to the 2nd embodiment of the present invention, because therefore anode and electrolyzer integrated molding can make device constitute and simplify, preferably.In addition, according to the 3rd～the 5th embodiment, can suppress the reversed reaction of calcium metal and chlorine effectively.
When the fusion electrolysis of calcium chloride, produce chlorine by anode.Therefore, anode require to use can anti-chlorine corrosion material, and have electroconductibility, and require to be insoluble to electrolytic bath.As this material, preferred carbon.
On the other hand, negative electrode is not particularly limited so long as conductive material gets final product, and for example, can be made of materials such as carbon steel, stainless steel or copper.Cylindric from negative electrode is processed into, the angle that communication port is set considers that preferably the carbon steel by handling ease constitutes.
The electrolytic bath that requirement is made of calcium chloride remains on more than the fusing point (845 ℃) of calcium metal.If less than the fusing point of calcium metal, then calcium metal becomes solid in negative electrode inside and separates out, the choked flow port, so overslaugh the percolation of melting salt and calcium metal.But, if high more too many, then promoted the evaporation of electrolytic bath than the fusing point of calcium metal, and the solvability increase of calcium metal in calcium chloride, therefore consider not preferred from the angle of productivity.Preferred temperature range is the scope that is no more than 100 ℃ of the fusing points of calcium metal.
The temperature of electrolytic bath can be controlled with the well heater that impregnated in the electrolytic bath.Further,, then can be controlled in the purpose temperature range if make it have refrigerating function, preferred.In addition, also can carry out temperature control by other selectable device.
Can in calcium chloride, add other salt in the electrolytic bath.For example, by adding the fusing point that Repone K can reduce electrolytic bath.By the fusing point of such reduction electrolytic bath, can make the electrolysis procedure temperature have degree of freedom, can reduce the required cost of heating simultaneously.The Repone K that adds in calcium chloride is preferably in the scope of 20 weight %～80 weight %.If add Repone K with this scope, then can make the fusing point of electrolytic bath be reduced to 615 ℃～760 ℃.
Fig. 6 is the schematic cross-section of the 6th preferred implementation of the present invention.Symbol 1 is an electrolyzer, and its inside contains the electrolytic bath 2 that contains calcium chloride, is heated to by not shown heating unit more than the fusing point of calcium chloride, keeps molten state.Symbol 3 is and the incorporate anode of electrolyzer.The negative electrode 4 of round tube type disposes in the mode that is immersed in electrolyzer 1 central part.The upper and lower of negative electrode 4 is open, so melting salt can be cathode external and inner moving.Further, negative electrode 4 interior regions are provided with titanium tetrachloride supply-pipe 11.
The upwelling of the above-mentioned calcium metal that generates at the interior region of negative electrode contacts with the bubble 12 of titanium tetrachloride, and (TiCl reacts
4+ 2Ca → 2CaCl
2+ Ti), generate metal titanium.The metal titanium that generates is transported to electrolytic bath top or bottom along bathing stream, reclaims by not shown retrieving arrangement.
So,, can need not to reclaim calcium metal and be transferred to titanium manufacturing process, after generating calcium metal, almost obtain metal titanium simultaneously according to present embodiment, thus preferred.
Fig. 7 is the schematic cross-section of the 7th preferred implementation of the present invention.Symbol 1 is an electrolyzer, and its inside contains the electrolytic bath 2 that contains calcium chloride, is heated to by not shown heating unit more than the fusing point of calcium chloride, keeps molten state.Symbol 3 is and the incorporate anode of electrolyzer.The negative electrode 4 of round tube type disposes in the mode that is immersed in electrolyzer 1 central part.The bottom of negative electrode 4 is open, and is provided with the communication port that is communicated with cathode external and inside in cathode side, and these communication port tilt to the vertical direction below.Further, as shown in Figure 9, the communication port of negative electrode 4 is also tilted by the normal direction of cylinder in the horizontal direction.Further, but negative electrode 4 install with free rotation mode.The interior region below of negative electrode 4 is provided with titanium tetrachloride supply-pipe 11.
So,, can need not to reclaim calcium metal and be transferred to titanium manufacturing process, after generating calcium metal, almost obtain metal titanium simultaneously according to present embodiment.Therefore and calcium metal accumulates in negative electrode inside, with titanium tetrachloride reaction, can suppress the reversed reaction with secondary chlorine of giving birth to, and is preferred.
Fig. 8 is the schematic cross-section of the 8th preferred implementation of the present invention.Symbol 1 is an electrolyzer, and its inside contains the electrolytic bath 2 that contains calcium chloride, is heated to by not shown heating unit more than the fusing point of calcium chloride, keeps molten state.Symbol 3 is and the incorporate anode of electrolyzer.The negative electrode 4 of round tube type disposes in the mode that is immersed in electrolyzer 1 central part.The bottom of negative electrode 4 is open, and is provided with the communication port that is communicated with cathode external and inside in cathode side.The interior region below of negative electrode 4 is provided with titanium tetrachloride supply-pipe 11.But be provided with agitating vane 10 with free rotation mode at negative electrode 4 interior regions.
So,, need not to reclaim the washing calcium metal and be transferred to titanium manufacturing process, can after generating calcium metal, almost obtain metal titanium simultaneously according to present embodiment.Therefore and calcium metal accumulates in negative electrode inside, with titanium tetrachloride reaction, can suppress the reversed reaction with secondary chlorine of giving birth to, and is preferred.
Embodiment
With electrolyzer shown in Figure 1, carry out the fusion electrolysis of calcium chloride.The temperature of the electrolytic bath that is made of calcium chloride remains on 850 ± 5 ℃, and cyclic negative electrode 4 is cooling especially also, remains on 850 ± 5 ℃.
By bathing supply-pipe 6, to the inboard base feed fused calcium chloride of negative electrode, simultaneously, the calcium metal enriched layer is drawn to outside the system continuously by the extraction pipe that impregnated in cathode external.Be drawn to the reduction reaction that the outer calcium metal of system is supplied to titanium oxide.On the other hand, the chlorine that is produced by anode is supplied to the chlorination reaction of titanium ore.Can make 80% the calcium metal that is equivalent to the theoretical weight of calculating by the energising amount of antianode and negative electrode.
Industrial applicability
According to the present invention, can make efficiently calcium metal by the electrolysis of calcium chloride. In addition, no Can supply with the manufacturing of Titanium with this calcium metal of recovery.
Claims (20)
1. make the method for metal by fusion electrolysis, it is to contain the method for passing through fusion electrolysis manufacturing metal that the calcium chloride melting salt carries out in the electrolyzer with anode and negative electrode, it is characterized in that,
Mode with electrodes surrounding the opposing party's electrode of above-mentioned negative electrode or anodic one side is provided with,
Above-mentioned negative electrode has at least one interior region that is communicated with the negative electrode encirclement and the communication port of external region,
Above-mentioned melting salt via above-mentioned communication port by being provided with the area cirulating of territory, anodic one lateral areas in above-mentioned interior region or the said external zone to the opposing party.
2. the described method by fusion electrolysis manufacturing metal of claim 1 is characterized in that,
Above-mentioned negative electrode is provided with to surround above-mentioned anodic mode,
Above-mentioned negative electrode has at least one interior region that is communicated with above-mentioned negative electrode encirclement and the communication port of external region,
Above-mentioned melting salt is circulated to above-mentioned external region by above-mentioned interior region via above-mentioned communication port.
3. the described method by fusion electrolysis manufacturing metal of claim 2 is characterized in that, supplies with calcium chloride to above-mentioned interior region.
4. the described method by fusion electrolysis manufacturing metal of claim 2 is characterized in that, the melting salt that will contain the calcium metal that generates at above-mentioned negative electrode is extracted out from the said external zone.
5. the described method by fusion electrolysis manufacturing metal of claim 1 is characterized in that,
Above-mentioned electrolyzer is made of carbon, with electrolyzer this as anode, the cylindrical cathode of hollow is configured in the above-mentioned electrolyzer,
Above-mentioned negative electrode has at least one and is communicated with the interior region of above-mentioned negative electrode and the communication port of external region,
Make above-mentioned melting salt via above-mentioned communication port by the said external zone to inner area cirulating.
6. the described method by fusion electrolysis manufacturing metal of claim 5 is characterized in that, supplies with rare gas element by the bottom of above-mentioned negative electrode interior region.
7. the described method of making metal by fusion electrolysis of claim 1, it is characterized in that, as one man tilt the finned cylinder negative electrode of a plurality of communication port of certain angle as the cylindrical cathode of above-mentioned hollow with having normal direction by cylinder sides, make this finned cylinder negative electrode rotation, melting salt is flowed to above-mentioned interior region to above-mentioned external region or by the said external zone by above-mentioned interior region.
8. the described method by fusion electrolysis manufacturing metal of claim 5 is characterized in that, supplies with calcium chloride to above-mentioned external region.
9. the described method by fusion electrolysis manufacturing metal of claim 5 is characterized in that the melting salt that will contain the calcium metal that generates at above-mentioned negative electrode is extracted out from above-mentioned interior region.
10. the described method by fusion electrolysis manufacturing metal of claim 1 is characterized in that, above-mentioned metal is to reclaim with the mixture of melting salt or the form of melts.
11. the described method by fusion electrolysis manufacturing metal of claim 1 is characterized in that above-mentioned melting salt comprises calcium chloride, sodium-chlor, bariumchloride and lithium chloride.
12. the described method of making metal by fusion electrolysis of claim 1, it is characterized in that, at the above-mentioned interior region that generates above-mentioned metal by above-mentioned fusion electrolysis the titanium tetrachloride supply-pipe is set, supplies with the gasiform titanium tetrachloride, generate metal titanium by this titanium tetrachloride supply-pipe.
Make the method for metal 13. claim 12 is described by fusion electrolysis, it is characterized in that, the upwelling by above-mentioned gasiform titanium tetrachloride produces upwelling in the electrolytic bath of above-mentioned interior region, the above-mentioned metal that becomes in electrolytic bath midwifery last time.
14. the described method of making metal by fusion electrolysis of claim 12, it is characterized in that, use above-mentioned finned cylinder electrode as negative electrode, above-mentioned titanium tetrachloride supply-pipe is located at the lower end of above-mentioned interior region, make above-mentioned finned cylinder electrode rotation,, supply with titanium tetrachloride simultaneously at the katabatic drainage that above-mentioned interior region produces electrolysis and bathes, make itself and above-mentioned katabatic drainage subtend, generate metal.
15. the described method of making metal by fusion electrolysis of claim 12, it is characterized in that, above-mentioned titanium tetrachloride supply-pipe is located at the lower end of above-mentioned interior region, at above-mentioned interior region agitating vane is set, make this agitating vane rotation,, supply with titanium tetrachloride simultaneously at the katabatic drainage that above-mentioned interior region produces electrolysis and bathes, make itself and above-mentioned katabatic drainage subtend, generate metal titanium.
16. the described method by fusion electrolysis manufacturing metal of claim 1 is characterized in that above-mentioned metal is calcium metal or metal titanium.
17. by the device of fusion electrolysis manufacturing metal, it is the device that fusion electrolysis is made metal that passes through that electrolyzer has anode and negative electrode, it is characterized in that,
Above-mentioned negative electrode or anodic one side's electrode is provided with in the mode of surrounding the opposing party's electrode,
Above-mentioned negative electrode has at least one interior region that is communicated with the negative electrode encirclement and the communication port of external region,
In two zones that above-mentioned negative electrode separated, be provided with territory, anodic one lateral areas and supply with the calcium chloride melting salt, make above-mentioned calcium chloride melting salt to the opposing party's area cirulating via above-mentioned communication port, the calcium chloride melting salt that will contain the calcium metal that generates at above-mentioned negative electrode is extracted out by above-mentioned the opposing party zone.
18. the described device by fusion electrolysis manufacturing metal of claim 17 is characterized in that above-mentioned negative electrode disposes in rotatable mode.
19. the described device of making metal by fusion electrolysis of claim 17, it is characterized in that, for melting salt is become easily to the mobile of interior region to the external region or by the external region by the interior region of above-mentioned negative electrode, agitating vane is arranged on the lower end of negative electrode inside.
20. the described device by fusion electrolysis manufacturing metal of claim 17 is characterized in that above-mentioned metal is calcium metal or metal titanium.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP297865/2004 | 2004-10-12 | ||
| JP2004297865A JP4247792B2 (en) | 2004-10-12 | 2004-10-12 | Method and apparatus for producing metal by molten salt electrolysis |
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| CN101044268A true CN101044268A (en) | 2007-09-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2005800349261A Pending CN101044268A (en) | 2004-10-12 | 2005-10-05 | Metal producing method and producing device by molten salt electrolysis |
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| Country | Link |
|---|---|
| US (1) | US20080078679A1 (en) |
| EP (1) | EP1811062A4 (en) |
| JP (1) | JP4247792B2 (en) |
| CN (1) | CN101044268A (en) |
| AU (1) | AU2005293038A1 (en) |
| CA (1) | CA2582035A1 (en) |
| EA (1) | EA011903B1 (en) |
| NO (1) | NO20072241L (en) |
| WO (1) | WO2006040978A1 (en) |
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- 2004-10-12 JP JP2004297865A patent/JP4247792B2/en not_active Expired - Fee Related
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- 2005-10-05 EP EP05790573A patent/EP1811062A4/en not_active Withdrawn
- 2005-10-05 CA CA002582035A patent/CA2582035A1/en not_active Abandoned
- 2005-10-05 EA EA200700843A patent/EA011903B1/en not_active IP Right Cessation
- 2005-10-05 WO PCT/JP2005/018449 patent/WO2006040978A1/en active Application Filing
- 2005-10-05 AU AU2005293038A patent/AU2005293038A1/en not_active Abandoned
- 2005-10-05 CN CNA2005800349261A patent/CN101044268A/en active Pending
- 2005-10-05 US US11/576,887 patent/US20080078679A1/en not_active Abandoned
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2007
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Also Published As
| Publication number | Publication date |
|---|---|
| AU2005293038A1 (en) | 2006-04-20 |
| JP2006111895A (en) | 2006-04-27 |
| WO2006040978A1 (en) | 2006-04-20 |
| EP1811062A4 (en) | 2009-04-29 |
| CA2582035A1 (en) | 2006-04-20 |
| EA200700843A1 (en) | 2007-08-31 |
| US20080078679A1 (en) | 2008-04-03 |
| EP1811062A1 (en) | 2007-07-25 |
| NO20072241L (en) | 2007-04-30 |
| JP4247792B2 (en) | 2009-04-02 |
| EA011903B1 (en) | 2009-06-30 |
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