CN1052148A - High-purity zirconium and Hf metals and method for making thereof - Google Patents
High-purity zirconium and Hf metals and method for making thereof Download PDFInfo
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- CN1052148A CN1052148A CN 89108871 CN89108871A CN1052148A CN 1052148 A CN1052148 A CN 1052148A CN 89108871 CN89108871 CN 89108871 CN 89108871 A CN89108871 A CN 89108871A CN 1052148 A CN1052148 A CN 1052148A
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- 238000000034 method Methods 0.000 title claims abstract description 45
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 title claims abstract description 15
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 14
- 150000002739 metals Chemical class 0.000 title description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 38
- 230000009467 reduction Effects 0.000 claims abstract description 32
- 230000005496 eutectics Effects 0.000 claims abstract description 13
- 230000004927 fusion Effects 0.000 claims abstract description 11
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 229910001508 alkali metal halide Inorganic materials 0.000 claims abstract description 3
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 150000002496 iodine Chemical class 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 239000010955 niobium Substances 0.000 claims abstract description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000009834 vaporization Methods 0.000 claims abstract description 3
- 230000008016 vaporization Effects 0.000 claims abstract description 3
- 229910007926 ZrCl Inorganic materials 0.000 claims description 49
- 239000011777 magnesium Substances 0.000 claims description 25
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 21
- 229910052749 magnesium Inorganic materials 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 18
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 4
- 230000036760 body temperature Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000009423 ventilation Methods 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000001816 cooling Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000006200 vaporizer Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010963 304 stainless steel Substances 0.000 description 2
- 239000010965 430 stainless steel Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 2
- 230000009102 absorption Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 235000012489 doughnuts Nutrition 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- -1 vanadium Chemical compound 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 208000031481 Pathologic Constriction Diseases 0.000 description 1
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001055 inconels 600 Inorganic materials 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- BUKHSQBUKZIMLB-UHFFFAOYSA-L potassium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[K+] BUKHSQBUKZIMLB-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000005144 thermotropism Effects 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
Produce selected among zirconium, hafnium, tantalum, the method of the metal of vanadium and niobium, comprising chloride with selected metal under the non-vaporization temperature in first container, bromine or iodine salt is made low eutectic solutions in the fusion hot body of one or more alkali or alkaline earth metal halide, this low eutectic solutions is changed in second container, second container remained on to be enough to evaporate under the temperature of this salt, salt steam is sent into one group respectively respectively in the reduction mould of feed, low eutectic solutions to the feeding speed of second container should guarantee salt steam can be by the container operation situation selectivity and sending in the crucible continuously basically.
Description
The present invention relates to high-purity zirconium, hafnium and other metal such as vanadium, the method for making of tantalum and niobium and device, particularly operate continuously and improve the operation total efficiency and make the method and apparatus of high purity product basically.
Past has proposed many production zirconiums, the method for hafnium and other metal, and referring to for example US3114611,4668287,4637831,4613366,4511399,4242136,3966460 and 3175205, its disclosure is for referencial use at this.Generally speaking, these patents all disclose the concrete device that can be used for flow process of the present invention and technology.But these existing methods efficient are very limited, and this is as following detailed description, and its complicated operation, therefore are unsuitable for doing operate continuously and don't generation problem.
For example, carry out ZrCl
4The existing batch process of reductive will be to ZrCl
4Repeatedly handle and must accurately be controlled and to guarantee the optimized running scale operational condition.This processing requirements is difficult for carrying out automatization, so the labor force consumes greatly.This processing also can reduce uses ZrCl
4Produce the output of Zr sponge, because ZrCl
4Treating processes is carried out and ZrCl in wet air
4Collect or tell through absorption.The typical restoring operation of carrying out in conventional equipment can make ZrCl
4Combine in same stove with reduction vessel, in the melting process of magnesium and at reduction round-robin in for some time, excessive ZrCl
4Can distil and can not in reaction, be applied.This excessive ZrCl
4Must from reaction vessel, blow out to avoid the container overvoltage." muriate of taking-up " like this, as alleged in the prior art, follow-up must in wet air, the processing.Output in this case also greatly reduces because of the muriate loss.And existing conventional stove size has limited the batch of material amount of operation each time again.When with rice steamer, ZrCl
4When charging and reduction mould placed same stove, working scale can be restricted because of conventional oven each time.Therefore, if ZrCl
4Do not send into same stove, then the have living space of existing stove all can be used to settle reduction mould within the treatment facility boundary.And, with MgCl
2In the time of can from Zr reduce flow process, removing or emit, just can enlarge working scale widely.For example, existing working scale is typically and can produces about 1800 pounds Zr sponge.
Other method is with ZrCl
4After being dissolved in the melting salt salt is pumped in another container with ZrCl
4Evaporation.This flow process will be removed vacuum requirement to a certain degree and have good heat transfer.Keep the low pressure that is suitable for reduction mould consistently and be more suitable for this flow process, admittedly be that thermal conduction is better.In addition, the melting salt system is inclined to and is removed metal and other impurity, and this preferably retains in the salt bath.
Although there is some satisfactory aspect in the existing method, up to the present also there not be the proposition can be continuously or intact device that puts into practice to continuous effective basically and method with known satisfactory process characteristic.
Gu this present invention proposes continuous high-efficient method of operating basically, this method can be adopted the most satisfactory characteristics of prior art processes effectively in the mode of being associated, and this method can be broadly defined as the method for making of zirconium or Hf metals, comprising chloride with zirconium or hafnium under the non-vaporization temperature in first container, bromine or iodine salt is made low eutectic solutions in the fusion hot body of one or more alkali or alkaline earth metal halide, this low eutectic solutions is changed in second container, to remain in second container under the temperature that is enough to by the pre-selection pressure evaporation salt, then salt steam is changed over to each reduction Rong Dizhong separately respectively, be all to infeed salt steam in each container, still keep in second container, infeeding low eutectic solutions so that salt steam is optionally sent in each reduction mould basically continuously and by the container operation situation by pre-selection pressure.
In the methods of the invention, whole system is that design is with ZrCl
4Rice steamer separates with the Mg reduction mould, can significantly reduce like this to extract muriate out and avoid occurring relevant with it other problem.Because the new constituent in this system can need not the muriate consecutive evaporation accurately to weigh so the magnesium charging can be determined working scale and muriate, handle and other loss thereby reduced.Gu this single ZrCl
4Vaporizer can be expected and operate continuously rather than in batches to the reduction mould feed altogether to several stoves.
By contrast, existing flow process in batches adopts the ZrCl that purifies
4And make the Zr metal, comprising behind the rice steamer filler, crucible being vacuumized and remove all oxygen, nitrogen and water vapour.In ordinary method, typical feed amount deviation about 91% can be reduced in the charging.Remaining 9% has lost, and wherein about 5.5% becomes the extraction muriate, and about 1.7% is remaining, and has an appointment and 1.8% do not count (loss).The extraction chloride material consists of about 20% ZrCl
4, this can circulate, but also can be as residuum in subsequent operations.Gu this is typically the muriatic total amount of the residue of sending into separating step and is actually about 2.8%.
In the methods of the invention, comprise ZrCl from melting salt or the next steam feed step of hot body
4Be dissolved in the molten salt bath.Molten salt bath is pumped in another jar heating therein and from molten salt bath, evaporate ZrCl
4With to several reduction furnace feed.Gu this dissolving vessel has replaced independent step to the rice steamer feed, has wherein more simplified muriate feed task, be about to it and directly send into the fusion bath.
Be published in " Journal of Mefals, Vol 9,1957, and the suitable salt mixture that can be used for system and method for the present invention is understood in the article states of pp193-200, comprising the NaCl-KCl and the ZrCl that wait mol
4Shared.This eutectic mixture is being lower than under about 300 ℃ of temperature and about 61mol%ZrCl
4(85wt%ZrCl
4) fusion together.At about 300 ℃, the ZrCl that from this eutectic composition, comes out
4The very low and steam that produce at the dissolving vessel of 300 ℃ of operations of vapour pressure seldom or can produce smog.The relation of this composition vapour pressure and temperature can make the vapour pressure on the salt bath (dissolver) control quite easily.The preferred vapour pressure that keeps about 2Psig thermotropism reduction mould feed effectively in the vaporizer.Keep 61mol%(85wt% when this system design makes dissolver) and vaporizer remained 61-55mol%(85-81wt%) time, then the evaporator operation temperature is about 375-450 ℃.For example, with 2000 pounds of ZrCl
4Batch of material is dissolved in the crucible with waiting mol Na Cl-KCl.Respectively contain about 6.5wt%NaCl and KCl in the bath, residue 87% is ZrCl
4These ratios are compared with above-mentioned ideal value with reference to the magazine suggestion discrepancy slightly, but this bath can be fusible at 290-300 ℃.Few this cigarette of this bath and be easy to draw control.Liquid-transparent, viscosity are similar to water and proportion is 2.2.Using ZrCl
4, when NaCl and KCl solid mixture began to operate, the original liquid forming process had certain difficulty, in case but initial " puddling " of liquid the beginning, then add the solid mixture and promptly be easy to increase liquid volume.With ZrCl
4The operation that adds balneation quite simply and not can " be fuming " especially.This bath is applicable to the inventive method and flow process.
Fig. 1 is two Zr reduction furnace operation required equipment schemas.
With reference to accompanying drawing, dissolving vessel 10 maintains 300 ℃ with bath.This jar should be as far as possible greatly to reduce ZrCl to greatest extent
4Flocculation.If ZrCl
4Dilution gets too severe, then bathes to solidify.Jar will be hindered, thereby makes the surface contact of wet air reach bottom line.Agitator 12 makes dissolving vessel keep good whipped state, so that the dissolving of chlorination group.The whole absorptions that are provided with on condenser 14 and the dissolver all should be passed through condenser, this again before entering the stripper (not shown) with ZrCl
4The recycled back dissolver.Do not have condenser, excessive muriate loss just may occur.Speed change hot body pump is set, wherein should reaches two kinds of speed, fast when variable.The operational circumstances of pump 16 is that the pumping material slows to low speed to evaporating pot 18, as 20rpm, so bathe the pump that just can reflux.This current downflow that goes up can guarantee that pipeline is unlikely obstruction.With dissolving vessel by comparison, evaporating pot should be enough little.For the dissolving pan furnace, conventional thermal load should only be enough to make ZrCl
4The dissolving, about 50kw and can with the bath in ZrCl
4Dissolution rate and changing.But thermal load was with regard to element very high and the about 200kw of requirement when preparation was newly bathed.For the evaporation pan furnace, with regard to two Zr reduction furnaces of quick operation easily with regard to, need 100kw approximately.ZrCl has just been determined in the heat input
4The largest production speed of steam.But, begin operation in order to impel the Zr reduction furnace, then vaporizer stove size can be littler.
In the methods of the invention, reduction mould can adopt conventional stainless steel lining, in the crucible of making by 304 stainless steels, and also available lining.Adopt NaCl, KCl and ZrCl
4The eutectic salt bath can make ZrCl
4Purifying is also evenly supplied with ZrCl
4Steam.
The main components and parts of system of the present invention comprise:
1. dissolve ZrCl
4The salt bath jar and change salt bath over to second jar pump, in for example 310-350 ℃ of operation down.
2. for example second jar or vaporizer are heated to 390-450 ℃ so that the ZrCl of 1-3psig to be provided
4Steam.
3. with ZrCl
4Steam changes the heating tube of stove and condenser over to, and condenser can be removed all air and produce to guarantee high quality zirconium sponge from vaporizer and heating tube.
4. She Ji reduction furnace can guarantee to control independently:
A. cool off crucible cover,
B. heat or cooling crucible middle part or reduction zone,
C. heat and/or cool off at the bottom of the crucible.
5. crucible can add 430 stainless steel linings or the not lining with 304 Stainless Steel Crucibles with mild steel.
6. regulate the heating and cooling circulation so that:
A. be heated to 825 ℃ and make magnesium fusion,
B. begin to feed ZrCl
4Steam,
C. in face when beginning reaction,, with being cooled to below 725 ℃ outside the crucible of air under carrying out reaction conditions, this can reduce the metal that metal formation amount on the wall and protection are made to greatest extent, makes it not by the iron in the crucible, chromium, nickel contamination.
7. for lined mild steel crucible, from the lining of crucible, discharge reactant, peel lining, from byproduct, tell reaction zirconium metal product and steam below 1050 ℃ stay and the zirconium metal.
8. for 304 Stainless Steel Crucibles:
A. during EO, from reduction mould, emit a part of MgCl, stay MgCl
2Layer is covered with the zirconium metal,
B. under argon or nitrogen atmosphere, cool off reaction mass,
C. from crucible, take lid and bottom off,
D. from crucible, release reaction mass and zirconium is sent into standard steam and stay stove so that with zirconium and the MgCl that catches
2And Mg,
E. the base plate with cleaning is welded on the crucible body that does not clean, and Mg is added crucible, and the lid that will not clean is welded on the crucible again, and removal also replaces argon or nitrogen also to be stored in this inert atmosphere.
9. regularly the discharge section salt bath is enough low at impurity to keep bathing from first jar, thereby guarantees to make high quality zirconium sponge, pumping or connect vacuum vessel and salt bath delivered to container and realize discharging.
The processing parameter of the main aspect of the inventive method comprises:
1. in jar, infeed NaCl, KCl and ZrCl
4310-350 ℃ eutectic salt bath with the dissolving ZrCl
4And pumping and change second jar over to.
2. second jar of air proof is provided and is heated 390-450 ℃ so that the ZrCl of 1-3psig to be provided
4Steam.
3. provide water back to transmit air.
Pipe end provide condenser with air from second jar of feeding pipeline.
5. provide with the reduction furnace of 3 reduction zones so that the cooling lid, at the bottom of heating or process furnace middle part and heating or the cool furnace.
6. provide that not lined or mild steel adds the crucible that 430 stainless steel linings are made with 304 stainless steels.
7. salt bath jar and component are provided, and soak into so that reduce the iron pollution salt bath to greatest extent with the salt bath that 330 stainless steels or Inconel600 make.
8. with solid-state ZrCl
4Send into first dissolving vessel, replace open and close so that at least one valve cuts out all the time by brill or two valves.
9. the metal zirconium powder is sent into salt bath with the jar of minimizing salt bath infiltration and the corrosion of component, iron and other dirt are unlikely enter salt bath.
With argon gas or nitrogen towards inswept gland, or use liquid metal lead, antimony, zinc-tin, the alloy of bismuth or these metals gets up the stirring streams closed in two jars, makes its air proof.
11. between two jars, transmit salt bath, the pipeline that the overflow pumping is too opened or be pumped to jar and regularly slowly get off and flow backwards realizing wherein, thus make second jar of part discharge and accelerate pumping again and it fills up jar.
12. gas is sent into reduction mould according to speed of response limitedly with in assorted in the reduction zirconium:
A. oxygen to be increasing oxygen,
B. add carbonic acid gas or carbon monoxide with increase carbon and oxygen,
C. add organic compound, as acetylene, tetracol phenixin, vinyl trichloride and toluene are with increase carbon, and don't increase oxygen,
D. silicon tetrachloride to be increasing silicon,
E. tin chloride is to increase tin.
13. in pressing the letter pipeline, dash the pressure of monitoring when sweeping in the reduction mould at no argon gas or nitrogen.(conventional reduction system and other salt bath jar must have argon gas or nitrogen towards sweeping).
14. control the ZrCl that in condenser or reduction furnace, flows into following gate sealing valve
4Steam.
15. reduction furnace is weighed to measure reduction rate.
16. turn off hot-zone heating facility on the duct section with the ZrCl that stops doing business
4Vapour stream also blocks to form with the airflow cooling duct, and then with the pipeline heating and evaporate, so just begins to flow again.
Others or the important consideration of implementing the inventive method are as follows:
Temperature control and speed of response
Reduction reaction is thermopositive reaction, temperature of superheat will occur if be not precluded within the crucible.When carrying out restoring operation with rice steamer, the big calorimetric of generation is used for making ZrCl
4Rise and send out.And, do not design inner heat sink, so must remove heat with air cooling for used steam feed design here.
Reduction furnace is to have designed to insert the gas blow pipe at furnace bottom center and place near the exhaust outlet of crucible and lid weld at first.Cool off the transition cooling that can not realize enough control and bottom with this system and caught magnesium (being donut shape), thus reduction operation scale and improve magnesium and the ratio of gained zirconium.For improving the controllability of this method, install second scavenger system again additional, about with three from the inlet tube of crucible stage casing to the stove feed.This can make cooling air enter in the stove between the heating zone.The following low Qu Keyi of cooling air intake pipe is heading straight for keeping donwt heat in crucible bottom, and the top district can heat or cool off and carry out reductive magnesium surface attemperation.
Reduction phase
The purpose of described improvement restoring operation is:
1. make zirconium as quickly as possible,
2. do not allow lining overheated, because this can cause iron and pollution of chromium and be difficult to peel lining,
3. do not allow crucible or lid too hot, otherwise can be out of shape,
4. make magnesium as much as possible participate in reaction.
Requirement order with regard to entire operation must be regulated with operation progress.Several stages that are rich in characteristics are arranged in this operation:
1. make the magnesium fusion,
2. begin reaction
3. crucible is cooled down with the protection crucible, lid and lining,
4. during EO, must heat and discharge last magnesium.
5. operate when complete, require at high temperature placement for some time with from MgCl
2In tell Zr and unreacted Mg moved to MgCl
2The top,
6. the entire operation system cools is got off so that separate with stove.
Make the magnesium fusion
Stove is heated to 825 ℃ as quickly as possible.Reaction heat needn't make all magnesium fusions, because can make fusion finish.
Begin reaction
If valve is waited when appropriate and opened, reaction just began immediately and reached proper speed in 1 hour.During this period of time, container pressure release and use ZrCl
4Replace argon and the magnesium melting operation is finished.When this stage finished, reactor pressure should be stablized, and can not blow or use argon gas again.If at this moment do not cooled off, then furnace temperature can begin to rise.Do not know that weld is that what reason makes lining subside or leak, but net result is a secondary stricture or unsuccessful operation.As if flow process is cooled down and to dwindle this two problems to greatest extent.Can avoid the high thermal shocking that causes because of extremely fast initial reaction speed like this.But, begin to cool down and can make the total reaction time prolongation too soon again, because need the oversize time just can make the reaction beginning.
The air cooling crucible
Tested the cooling differing temps, but, cooled off this reaction that stops doing business below 700 ℃ for used design.For reaction is restarted, then need close cooling system and these elements of opening an account.As if the appropriate balance in this stage can reach high speed of response, and simultaneously few etch lining.
If cooling is not enough, then lining can become fragile and can not peel.The 430SS lining breaks and the content of the iron that causes and chromium is also very high in the sponge.Too hotly during operation can or make lining trickling interrupt operation because of the lining seepage again.
It is very thin to carry out the favourable one side of refrigerative and be the sidewall that forms on the lining above the donut.It is believed that cooling can stop magnesium to soak lining and along sideways expansion.And, can make the center hotter, so that take place near being reflected at the center, rather than in cold side.
Heating when operation draws to an end
If cooling continues too for a long time, even then staying excessive magnesium, operation also can stop doing business.As if magnesium is at MgCl
2In be hunted down and if MgCl
2Be heated, only can float.The time that beginning is heated once more is not quite similar in each time operation, can be indicated by excessive air blowing, and this expression reaction slows down.In case need earlier to heat in some operation and speed of response quickening sometimes, need again to cool off.
An evenly heating is finished in operation
When reaction finishes, importantly in reaction stop doing business and shut-off valve after 900 ℃ of maintenances 2 hours.This evenly heating can guarantee that magnesium all is captured in donwt or salt floats to top layer.If there is not this evenly heating, the magnesium ball will appear in the salt, and this is difficult for removing.If all the other operations follow regular circulation, then should be that the magnesium that is left is few.The operation that goes wrong in the reaction is to have a large amount of magnesium to stay.For this generic operation, evenly heating is just extremely outer important, could reclaim unreacted magnesium like this.
Operating process cools down
After the evenly heating, operating process must enough be cooled off to make under the salt curing before transforming the pipeline removal.Immediately container is opened and placed air, this can make the material combustion on the crucible wall above the salt, occurs the hole in the lining thereby make.If salt still for the fusion attitude, will flow out and make the lining adhesion from the hole.For avoiding these problems, container open close put into air before with operating process cooling 12 hours, dry with two desk fans simultaneously.
Claims (7)
1, produce selected among zirconium, hafnium, tantalum, the method of the metal of vanadium and niobium, comprising chloride with selected metal under the non-vaporization temperature in first container, bromine or iodine salt is made low eutectic solutions in the fusion hot body of one or more alkali or alkaline earth metal halide, this low eutectic solutions is changed in second container, second container remained on to be enough to evaporate under the temperature of this salt, salt steam is sent into one group respectively respectively in the reduction mould of feed, low eutectic solutions to the feeding speed of second container should guarantee salt steam can be by the container operation situation selectivity and sending in the crucible continuously basically.
2, the process of claim 1 wherein that salt is ZrCl
4, the hot body temperature is maintained at about 310-350 ℃, and temperature of charge is maintained at about 390-450 ℃ and ZrCl in second container
4Vapour pressure is the about 3psig of about 1-.
3, the method for claim 2, wherein crucible contains molten magnesium as reductive agent.
4, the method for claim 3, wherein the main service temperature of sidewall of crucible is maintained at about below 725 ℃.
5, the process of claim 1 wherein salt steam that at least a portion sends into crucible under near one section condensation its inlet tube, and incoming flow and crucible pressure are kept preset value by ventilation in this section.
6, the method for claim 1, wherein low eutectic solutions is sent into second container by water back from first container, wherein regularly slow down rate of pumping and realize flowing backwards and making second container guarantee that to the first container portions earial drainage this pipeline is unlikely obstruction, and then accelerate pump speed and fill second container once more.
7, the process of claim 1 wherein that second container comprises a plurality of evaporating pots.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89108871 CN1052148A (en) | 1989-11-29 | 1989-11-29 | High-purity zirconium and Hf metals and method for making thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89108871 CN1052148A (en) | 1989-11-29 | 1989-11-29 | High-purity zirconium and Hf metals and method for making thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1052148A true CN1052148A (en) | 1991-06-12 |
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ID=4857779
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89108871 Pending CN1052148A (en) | 1989-11-29 | 1989-11-29 | High-purity zirconium and Hf metals and method for making thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638249B (en) * | 2009-09-04 | 2010-10-27 | 石政君 | Zirconium tetrachloride purification method |
| CN102206762A (en) * | 2011-05-18 | 2011-10-05 | 南京佑天金属科技有限公司 | Crystal zirconium growth system with iodine doser |
| CN102459665A (en) * | 2009-05-15 | 2012-05-16 | 代尔夫特科技大学 | Process for separating hafnium and zirconium |
| CN101594953B (en) * | 2007-04-25 | 2012-12-05 | 国际钛粉有限责任公司 | Inject VCl4 liquid into superheated TiCl4 for production of Ti-V alloy powder |
| CN104439262A (en) * | 2013-09-22 | 2015-03-25 | 北京有色金属研究总院 | Large-sized metal zirconium powder low in oxygen content and preparation method of zirconium powder |
| CN110453084A (en) * | 2019-08-06 | 2019-11-15 | 辽宁华祥新材料有限公司 | A kind of preparation method of atomic energy level sponge zirconium |
-
1989
- 1989-11-29 CN CN 89108871 patent/CN1052148A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101594953B (en) * | 2007-04-25 | 2012-12-05 | 国际钛粉有限责任公司 | Inject VCl4 liquid into superheated TiCl4 for production of Ti-V alloy powder |
| CN102459665A (en) * | 2009-05-15 | 2012-05-16 | 代尔夫特科技大学 | Process for separating hafnium and zirconium |
| CN102459665B (en) * | 2009-05-15 | 2013-08-28 | 锆铪钛冶金有限公司 | Process for separating hafnium and zirconium |
| CN101638249B (en) * | 2009-09-04 | 2010-10-27 | 石政君 | Zirconium tetrachloride purification method |
| CN102206762A (en) * | 2011-05-18 | 2011-10-05 | 南京佑天金属科技有限公司 | Crystal zirconium growth system with iodine doser |
| CN102206762B (en) * | 2011-05-18 | 2013-09-04 | 南京佑天金属科技有限公司 | Crystal zirconium growth system with iodine doser |
| CN104439262A (en) * | 2013-09-22 | 2015-03-25 | 北京有色金属研究总院 | Large-sized metal zirconium powder low in oxygen content and preparation method of zirconium powder |
| CN110453084A (en) * | 2019-08-06 | 2019-11-15 | 辽宁华祥新材料有限公司 | A kind of preparation method of atomic energy level sponge zirconium |
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