CN104418370B - Method and device for preparing anhydrous magnesium chloride - Google Patents
Method and device for preparing anhydrous magnesium chloride Download PDFInfo
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- CN104418370B CN104418370B CN201310395723.1A CN201310395723A CN104418370B CN 104418370 B CN104418370 B CN 104418370B CN 201310395723 A CN201310395723 A CN 201310395723A CN 104418370 B CN104418370 B CN 104418370B
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- anhydrous magnesium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/26—Magnesium halides
- C01F5/30—Chlorides
- C01F5/34—Dehydrating magnesium chloride containing water of crystallisation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/26—Magnesium halides
- C01F5/30—Chlorides
Abstract
The invention relates to a device for preparing anhydrous magnesium chloride and a preparation method which uses the device. The device is a chlorination dehydration furnace and comprises a storage cabin, wherein the upper part of the storage cabin is a preheating zone; the middle part of the storage cabin is a double salt forming zone; the bottom of the storage cabin is an ammonium removing zone; the storage cabin is connected with an outlet and has certain sealing property. The preparation method comprises the following steps: uniformly mixing magnesium oxide and/or hydrated magnesium chloride and ammonium chloride, adding the mixture into the chlorination dehydration furnace, and heating, thereby preparing anhydrous magnesium chloride; and repeating the above operation steps when the anhydrous magnesium chloride is discharged out, thereby achieving continuous production. A method for preparing anhydrous magnesium chloride by using the rich magnesite and magnesium chloride hexahydrate resources in China is provided by the invention, continuous production of anhydrous magnesium chloride is achieved, the production efficiency is improved, the production cost is lowered, and the cost of environment protection is lowered; the prepared anhydrous magnesium chloride is high in purity, the content of the main impurity magnesium oxide in the anhydrous magnesium chloride can be controlled to be 0.5% or even less than 0.1%, and the anhydrous magnesium chloride can be used for preparing magnesium metal in an electrolysis manner and has very good industrial and commercial prospect.
Description
Technical field
The present invention relates to preparation method and the device of anhydrous magnesium chloride, specifically, relate to a kind of utilization and aoxidize
Magnesium or hydrated magnesium chloride are the method and device that anhydrous magnesium chloride prepared by raw material, use technique and the dress of the present invention
Putting the continuous prodution that can realize anhydrous magnesium chloride, preparing magnesium metal for electrolysis provides raw material.
Background technology
Magnesium belongs to IIA(the second main group on the periodic table of elements) race's alkali earth metal, magnesium metal is silvery white
Metal, matter is hard, and slightly ductility, the density of magnesium is little, and ionization tendency is big.Compared with plastics, magnesium closes
Gold utensil have lightweight, specific strength is high, damping good, thermal fatigue property is good, it is aging to be difficult to, and has again good
Heat conductivity, electromagnetic shielding capability extrusion process performance strong, extraordinary, is particularly susceptible for the advantages such as recovery, is
Substitute iron and steel, aluminium alloy and the high performance structures material of new generation of engineering plastics.For adapting to electronics, communicator
Part Highgrade integration and the development trend of frivolous miniaturization, magnesium alloy is traffic, electronic information, communication, meter
The reason of the product casings such as calculation machine, acoustic image equipment, hand-held tool, motor, forestry, weaving, nuclear power unit
Think material.
The preparation method of magnesium generally has two classes: electrolysis and thermal reduction.The raw material one that wherein electrolysis uses
As be magnesium chloride, thus use generating metal magnesium by electrolyzing magnesium chloride key link be to prepare anhydrous magnesium chloride.
At present, the preparation method of anhydrous magnesium chloride has following several:
(1) low water ammonium carnallite ammonia process prepares anhydrous magnesium chloride
Yuichi Suzukaw specific operation process and principle to the method in patent US3798314 is carried out
Describe: first by low water ammonium carnallite (MgCl2·NH4Cl·nH2O, n=0.5～4) enter at 110 DEG C-160 DEG C
Row preliminary hydro-extraction, the product of preliminary hydro-extraction generates ammino ammonium carnallite at 200～400 DEG C with ammonia haptoreaction
MgCl2·NH4Cl·nNH3(n=0.2～3).By ammino ammonium carnallite when carrying out calcining one section for 712～900 DEG C
Between just obtain anhydrous magnesium chloride.The method is the large usage quantity of ammonia during implementing, and energy consumption is higher, causes
Implementation cost is too high.
(2) gas-solid reaction method prepares anhydrous magnesium chloride
A kind of method is to use ammonium carnallite (MgCl2·NH4Cl·6H2O) be raw material gas-solid reaction method (as
" ammonium carnallite prepares anhydrous magnesium chloride new technology and fundamental research ", Zhou Ningbo, Central South University, 2005
Year thesis for the doctorate): by low for raw material water ammonium carnallite (MgCl2·NH4Cl·nH2O, n=0.5～1.0) and chlorination
Ammonium mix according to mass ratio 1:4 after at 410 DEG C of thermal dehydrations, generate product ammino ammonium carnallite.By ammino ammonium
Carnallite obtains anhydrous magnesium chloride 700 DEG C of calcinings, and wherein the mass fraction of magnesium oxide is less than 0.1%.
Another kind of method is to use bischofite (MgCl2·6H2O) it is the gas-solid reaction method of raw material, such as Zhouning County
Ripple etc. describe in detail in " bischofite gas-solid reaction prepares anhydrous magnesium chloride " the method (Zhou Ningbo etc.,
[J]. chemical research and application, 2010,22(10): 1290-1294): protect at nitrogen by Bischofite in Salt lake
Under in 135 DEG C dehydration 2h make low hydrate water chloromagnesite (MgCl2·nH2O, n=1.6).Low hydrate water chlorine magnesium
Stone mixes according to mass ratio 1:6.5 with solid ammonium chloride, makes the dividing potential drop of ammonia in reaction system reach under high temperature
More than 49.6KPa, makes anhydrous magnesium chloride in 12 minutes in 440 DEG C of dehydrations calcining in 18 minutes and 710 DEG C.System
In the anhydrous magnesium chloride obtained, the mass fraction of magnesium oxide is less than 0.15%.The method is ammonium chloride during implementing
Consumption excessive, ammonium chloride decompose power consumption excessive, the operating cost causing the method is the highest, the most substantial amounts of
Ammonium chloride reclaims difficulty in process of production and easily blocks pipeline.
(3) magnesium oxide chloridising prepares anhydrous magnesium chloride
A kind of method is to use chlorine as chlorinating agent (IG Farben method), and it is by magnesium oxide and reducing agent charcoal
Agglomerate in electrical heating shaft furnace with chlorine reaction (about 800 DEG C) with the melted anhydrous magnesium chloride of preparation, its shortcoming is
Production efficiency is low, chlorine utilization is low and vent gas treatment puts into big, and has chlorinated hydrocarbons in aerofluxus.
Another kind of method is to use ammonium chloride as chlorinating agent, describes this in detail as in CN102491383A
Method: above the mixture that magnesium oxide and ammonium chloride are uniformly mixed to get are added solid covers aluminium oxide or
Quartz sand, heats, and reaction prepares content of magnesia anhydrous magnesium chloride within 0.5wt%.Should
Method there is problems in that a) covering is in heating process, due to the mobile change of the bed of material, it is easy to mixed
Enter in product anhydrous magnesium chloride, had a strong impact on the purity of anhydrous magnesium chloride；B) reactant needs covering stone
Sand or aluminium oxide are persistently protected, and cause the method can only realize batch production, it is impossible to meet continuously
The requirement of automated production.
(4) melted chlorination evaporation prepares anhydrous magnesium chloride melt
A kind of method is that to use chlorine be chlorinating agent, a kind of produces melted anhydrous chlorine as US3953574 discloses
The method changing magnesium, it utilizes containing MgO and H2O is the spray drying MgCl of 5%2Powder and solid carbon
Reducing agent and chlorine react at 800 DEG C.It is complete in the square furnace of two series connection for realizing this process
Become, the MgCl finally given2Fused solution is containing the MgO less than 0.5wt%.US4981674 is by spray dried
Dry MgCl2Powder, magnesite or magnesium oxide add the MgCl of 750-850 DEG C2In fused solution, gas reaction
Agent chlorine and carbon monoxide are by melted MgCl2Gas distributor in pond enters fused solution and forms tiny bubble
React with the magnesium oxide in pond, content of magnesia can be made to be reduced to below 0.1wt%.
Another kind of method is that to use hydrogen chloride gas be chlorinating agent, as Japan Patent 32-9052 describes this in detail
Method: hydrated magnesium chloride is added the electrolyte (MgCl containing 25wt% of magnesium chloride containing2In), simultaneously at 750 DEG C
Lower injection anhydrous hydrogen chloride gas, prepares anhydrous magnesium chloride melt, but the electrolysis of magnesium chloride liquid electrolysis prepared will
Consuming relatively more graphite, produce magnesium metal per ton 13-15kg to be consumed graphite, graphite consumption is big, represents
The content of MgO is high.CN1146757A discloses a kind of directly production from hydrated magnesium chloride feed and contains anhydrous chlorine
Changing magnesium fused solution or the method for electrolyte, it is to be fed containing molten electrolyte from magnesium eletrolysis pond by hydrated magnesium chloride
Stove in produce fused solution, furnace temperature is maintained at 450-650 DEG C, simultaneously by anhydrous hydrogen chloride gas inject melt
In liquid, and stirring fused solution and inject gas with dispersion, keeping magnesium oxide in fused solution is suspended state, makes chlorination
Magnesium dehydration is also reacted with magnesium oxide, obtains being enriched with the fused solution of anhydrous magnesium chloride, and the magnesium oxide in fused solution contains
Amount is not more than 0.2wt% (in terms of the magnesium chloride of 100%).Utilize gas chlorination agent (HCl or Cl2) at fused solution
Middle preparation melt Han anhydrous magnesium chloride is primarily present following point: a) gas chlorination agent utilization rate is the highest, because
Gas is difficult to realize dispersed in fused solution, and needs to keep enough chlorinations in whole fused solution
Gas concentration just can make magnesium oxide be converted into magnesium chloride, gas chlorination when especially content of magnesia is low in fused solution
Agent utilization rate is the lowest；B) recycling of the aqueous hydrogen chloride gas obtained during dehydration needs complicated being dried
System, and this system cost and operating cost the highest.
The key link reducing electrolytic magnesium production cost is exactly with relatively simple process economy, prepares efficiently
The anhydrous magnesium chloride that content of MgO is the lowest.At present, the key issue that restriction anhydrous magnesium chloride produces has: (1) is big
The use sealing to equipment and the corrosion resistance of amount chlorine and hydrogen chloride gas require the highest, and containing water vapor
Tail gas to purify difficulty relatively big (purity need to reach more than 99.5%), add the cost of operation；(2) anhydrous
Magnesium chloride is difficult to continuous prodution, and production efficiency is low；(3) product anhydrous magnesium chloride purity is low, seriously drops
The low current efficiency of follow-up electrolytic process, adds power consumption.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of anhydrous magnesium chloride of preparing
Device, an object of the present invention also resides in provides the method utilizing described device to prepare anhydrous magnesium chloride.Logical
Cross described device and preparation method can realize the serialization of anhydrous magnesium chloride under the conditions of relatively simple process
Produce, the content of MgO anhydrous magnesium chloride less than 0.1% can be prepared in certain preferred circumstances..
The preparation facilities of the anhydrous magnesium chloride that the present invention provides, for chlorination dehydration furnace, described chlorination dehydration furnace bag
Include preheating zone, top 11, middle part double salt is formed and takes off ammonium band 13 with 12 and bottom and pass through what discharging opening 4 connected
There is the storage bin 8 of certain sealing.Wherein, there is the storage bin of certain sealing and refer to ensure anhydrous
Magnesium chloride does not contacts with the oxygen in air and steam, and ensures the inert atmosphere in storehouse, and storage bin is being protected
On the basis of the card smooth and easy circulation of noble gas, there is certain sealing.
Preferably, the heating-up temperature of described preheating zone 11 is 50-200 DEG C, for example, 53 DEG C, 58 DEG C, 66 DEG C,
78℃、85℃、90℃、95℃、100℃、105℃、110℃、115℃、120℃、125℃、130℃、
135 DEG C, 140 DEG C, 145 DEG C, 166 DEG C, 174 DEG C, 180 DEG C, 189 DEG C, 197 DEG C etc., preferably 80-150 DEG C；
The heating-up temperature that described middle part double salt is formed with 12 is 250-400 DEG C, for example, 256 DEG C, 267 DEG C, 276 DEG C,
285℃、290℃、296℃、305℃、315℃、325℃、335℃、345℃、355℃、365℃、
375 DEG C, 385 DEG C, 395 DEG C etc., preferably 300-400 DEG C；Described bottom takes off the heating-up temperature of ammonium band 13
420-750 DEG C, for example, 423 DEG C, 431 DEG C, 440 DEG C, 450 DEG C, 460 DEG C, 480 DEG C, 500 DEG C, 520 DEG C,
540℃、560℃、580℃、600℃、620℃、640℃、660℃、680℃、700℃、720℃、
740 DEG C etc., preferably 450-700 DEG C.
Preferably, the draw ratio >=2:1 of described chlorination dehydration furnace, for example, 2.2:1,2.8:1,3.1:1,3.6:1,
4.1:1,4.6:1,5.1:1,5.6:1,6.1:1,6.6:1,7.1:1,7.6:1,8.1:1,8.6:1 etc., be preferably
≥3.5:1。
Preferably, described storage bin 8 has inert atmosphere.Noble gas is passed through by inert gas entrance 9
In storehouse, gas from gas outlet 10 discharge in storehouse, it is ensured that the inert atmosphere in storehouse.
Preferably, described chlorination dehydration furnace also includes gas overflowing mouth 2 and discharging opening 4.
Preferably, described chlorination dehydration furnace also includes agitating device 3.
An object of the present invention also resides in provides the method utilizing described device to prepare anhydrous magnesium chloride, including
Following steps:
A magnesium oxide is mixed by () with ammonium chloride；
B (), by heating in step (a) gained mixture addition chlorination dehydration furnace, prepares anhydrous magnesium chloride；
C () anhydrous magnesium chloride is discharged while, repeat step (a) and (b), it is achieved continuous prodution.
Preferably, being in terms of 1.00 weight portions by the feeding quantity of magnesium oxide, the feeding quantity of ammonium chloride is 2.6-25.00
Weight portion, for example, 2.8 parts, 4.8 parts, 6.8 parts, 8.8 parts, 10.8 parts, 12.8 parts, 14.8 parts, 16.8
Part, 18.8 parts, 20.0 parts, 22.0 parts, 24.0 parts, preferably 2.70-20.10 weight portion.
The present invention provide utilize described device prepare anhydrous magnesium chloride method two, comprise the steps:
A molecular formula is MgCl by ()2·mH2The hydrated magnesium chloride of O mixes with ammonium chloride；Or by magnesium oxide with point
Minor is MgCl2·mH2The hydrated magnesium chloride of O mixes with ammonium chloride；
Wherein, m ＞ 0, preferably 6 >=m ＞ 0；M represents the knot contained in hydrated magnesium chloride described in per molecule
The number of brilliant water；
B (), by heating in step (a) gained mixture addition chlorination dehydration furnace, prepares anhydrous magnesium chloride；
C () anhydrous magnesium chloride is discharged while, repeat step (a) and (b), it is achieved continuous prodution.
Preferably, with the magnesium chloride without water of crystallization, or the charging of magnesium oxide and the magnesium chloride without water of crystallization
Amount be 1.00 weight portion meters, the i.e. feeding quantity of hydrated magnesium chloride be 1+0.19m weight portion, the charging of ammonium chloride
Amount for 0.28-60.00 weight portion, for example, 0.30 part, 5.30 parts, 10.30 parts, 15.30 parts, 20.30 parts,
25.30 parts, 30.30 parts, 35.30 parts, 40.30 parts, 45.30 parts, 50.30 parts, 55.30 parts, 58.00
Part, preferably 0.28-56.00 weight portion.
Two kinds of described methods, it is preferable that the heating-up temperature of preheating zone 11 in the chlorination dehydration furnace in step (b)
For 50-200 DEG C, for example, 53 DEG C, 58 DEG C, 66 DEG C, 78 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C,
110℃、115℃、120℃、125℃、130℃、135℃、140℃、145℃、166℃、174℃、
180 DEG C, 189 DEG C, 197 DEG C etc., preferably 80-150 DEG C；The heating-up temperature that middle part double salt is formed with 12 is
250-400 DEG C, for example, 256 DEG C, 267 DEG C, 276 DEG C, 285 DEG C, 290 DEG C, 296 DEG C, 305 DEG C, 315 DEG C,
325 DEG C, 335 DEG C, 345 DEG C, 355 DEG C, 365 DEG C, 375 DEG C, 385 DEG C, 395 DEG C etc., preferably 300-400 DEG C；
The heating-up temperature of the de-ammonium band 13 in bottom is 420-750 DEG C, for example, 423 DEG C, 431 DEG C, 440 DEG C, 450 DEG C,
460℃、480℃、500℃、520℃、540℃、560℃、580℃、600℃、620℃、640℃、
660 DEG C, 680 DEG C, 700 DEG C, 720 DEG C, 740 DEG C etc., preferably 450-700 DEG C；
Preferably, the draw ratio >=2:1 of described chlorination dehydration furnace, for example, 2.2:1,2.8:1,3.1:1,3.6:1,
4.1:1,4.6:1,5.1:1,5.6:1,6.1:1,6.6:1,7.1:1,7.6:1,8.1:1,8.6:1 etc., be preferably
≥3.5:1；
Preferably, described storage bin 8 has inert atmosphere；Noble gas is passed through by inert gas entrance 9
In storehouse, gas from gas outlet 10 discharge in storehouse, it is ensured that the inert atmosphere in storehouse.
Preferably, described chlorination dehydration furnace also includes gas overflowing mouth 2 and discharging opening 4.Step (b) can be made
The ammonia and the ammonium chloride that produce are discharged through gas overflowing mouth, and carry out reclaiming to recycle.The nothing prepared
Aqueous magnesium chloride discharging opening 4 bottom superchlorination dehydration furnace is discharged, and the process inert atmosphere of discharge is protected
Protecting, while discharge, a new batch materials is added by the charge door on stove top.
Preferably, described chlorination dehydration furnace also includes agitating device 3.Installing agitating device in chlorination dehydration furnace is
In order to ensure burden direct motion.
Preferably, described mixture is 0.2-5.0h in the heat time heating time of preheating zone, for example, 0.3h, 0.6h,
0.9h、1.2h、1.5h、1.8h、2.1h、2.4h、2.7h、3.0h、3.3h、3.7h、4.1h、4.4h、4.8h
Deng, preferably 0.2-3.5h；Double salt formed band heat time heating time be 0.2-5.0h, for example, 0.3h, 0.5h,
0.7h、0.9h、1.1h、1.3h、1.5h、1.7h、1.9h、2.1h、2.3h、2.5h、2.7h、3.0h、3.3h、
3.7h, 4.1h, 4.4h, 4.8h etc., preferably 0.2-2.5h；It is 0.5-5.0h in the heat time heating time of de-ammonium band,
For example, 0.6h, 0.8h, 1.0h, 1.2h, 1.4h, 1.6h, 1.8h, 2.0h, 2.2h, 2.4h, 2.7h, 3.0h,
3.3h, 3.7h, 4.1h, 4.4h, 4.8h etc., preferably 0.5-2.5h.
Preferably, the thickness in chlorination dehydration furnace of the mixture described in step (b) is not less than 10cm, for example,
12cm、16cm、21cm、26cm、31cm、36cm、41cm、46cm、51cm、56cm、61cm、
66cm, 71cm, 76cm, 81cm etc., preferably not less than 15cm.
Preferably, the ammonia, hydrogen chloride and the ammonium chloride that produce in step (b) are through gas overflowing mouth (2)
Discharge, and carry out reclaiming to recycle.Owing to ammonium chloride has partial sublimation decomposed to be ammonia and chlorination
Hydrogen, so the gas that place overflows includes ammonia, hydrogen chloride and ammonium chloride.
Fig. 1 is the process chart of anhydrous magnesium chloride prepared according to the methods of the invention.Concrete preparation process is: (a)
Magnesium oxide or hydrated magnesium chloride are mixed with ammonium chloride, obtains the mixed of magnesium oxide or hydrated magnesium chloride and ammonium chloride
Compound；B said mixture is added in chlorination dehydration furnace by (), first heat 0.2-5.0h at 50-200 DEG C, so
After 250-400 DEG C heat 0.2-5.0h, finally 420-750 DEG C heat 0.5-5.0h.In heating process,
In order to ensure material can direct motion, material is constantly stirred, and by heating process from gas overflowing mouth
Ammonium chloride and the ammonia discharged recycle；C anhydrous magnesium chloride is discharged by () from discharging opening, repeat step
The operation of (a) and (b), it is achieved continuous prodution.
Inventor is found by numerous studies, and the mechanism of above-mentioned reaction is as follows: magnesium oxide and ammonium chloride exist
50-200 DEG C preheats, and can remove the moisture in material, prevents the generation of hydrolysis in heating process；Water
Close magnesium chloride and ammonium chloride preheats at 50-200 DEG C, hydrated magnesium chloride can be made to carry out preliminary hydro-extraction, weaken
Hydrolysis degree in follow-up intensification heating process.About 300 DEG C, magnesium oxide or hydrated magnesium chloride all can be with chlorinations
Ammonium reaction forms double salt NH4Cl·MgCl2·nH2O (0≤n ＜ 6) (refer to document: Zhang ZM, Lu XC etal,
Preparation of anhydrous magnesium chloride from magnesia, Industrial&
Engineering Chemistry Research, 2012,51 (29): 9713-9718；Zhang ZM, Lu XC etal,
Preparation of Anhydrous Magnesium Chloride from Magnesium Chloride
Hexahydrate.Metallurgical and Materials Transactions B, 2013,44 (2): 354-358), multiple
The structure of salt reduces the combination of water of crystallization and magnesium chloride, is conducive to the carrying out of dehydration, reduces dehydration
Hydrolysis.Even if there occurs hydrolysis, ammonium chloride at a certain temperature can also be with hydrolyzate (hydroxy chloride magnesium
And magnesium oxide) reaction, generate anhydrous magnesium chloride, thus ensure that the purity of product anhydrous magnesium chloride.Temperature
When continuing to raise, water of crystallization gradually sloughed by above-mentioned double salt, and when temperature rises to more than 420 DEG C, chlorine sloughed by double salt
Change ammonium.Ammonium chloride is decomposed into ammonia and hydrogen chloride gas during removing, and these gases have been possible not only to
Steam and the dividing potential drop of oxygen in effect ground diluting reactor, and hydrogen chloride gas can also suppress anti-effectively
Answer the generation of hydrolysis in device, obtain highly purified anhydrous magnesium chloride.
Inventor is also found by numerous studies, and ammonium chloride has following work in the preparation of above-mentioned anhydrous magnesium chloride
With: the double salt of easily dehydration with magnesium oxide or chloride hydrate reactive magnesium, can be generated under (1) low temperature
NH4Cl·MgCl2·nH2O (0≤n ＜ 6), this double salt can effectively suppress the generation of hydrolysis in heating process；
(2) ammonium chloride can react with the hydrolyzate in double salt heating process, is translated into anhydrous chlorination
Magnesium；(3), during ammonium chloride heat resolve, the aerial diffusion coefficient of hydrogen chloride gas is approximately ammonia and expands
(ammonia and hydrogen chloride gas are at air prior to hydrogen chloride gas spilling to dissipate the half of coefficient, ammonia and steam
Middle diffusion coefficient is similar), hydrogen chloride gas be stranded in for a long time material bed in, effectively inhibit hydrolysis anti-
The generation answered；(4) ammonium chloride decompose the hydrogen chloride of release and ammonia can steam and oxygen in diluting reactor
Dividing potential drop, hydrogen chloride gas can suppress the generation of reactant hydrolysis effectively.
Inventor is also found by numerous studies, and the effect of chlorination dehydration furnace preheating zone is as follows: (1) is to oxidation
Magnesium or hydrated magnesium chloride preheat with the mixture of ammonium chloride, thoroughly the moisture in removing material or to material
Carry out predrainage, prevent or weaken the generation of hydrolysis in heating process；(2) can be effective as cover layer
Ground suppression double salt forms volatilization and the decomposition of ammonium chloride in band and de-ammonium band, improves the utilization rate of ammonium chloride；(3)
Connecing of de-ammonium band product anhydrous magnesium chloride and oxygen in air and steam can be effectively completely cut off as cover layer
Touch, it is ensured that hydrolysis does not occur under anhydrous magnesium chloride high temperature.The ammonium chloride discharged from gas overflowing mouth and ammonia
Gas can be recycled, and the ammonium chloride of recovery returns to recycle in step (a), thus reduces and produce into
Originally, production efficiency is improved.
Fig. 2 shows the schematic diagram of the main device-chlorination dehydration furnace realizing this technique.Material is by charge door 1
Adding, chlorination dehydration furnace uses zone heating, preheating zone, stove top 11, middle part double salt to form band 12, the end
Portion takes off the temperature of ammonium band 13 and is formed band heater 6 and de-ammonium band by preheating zone heater 5, double salt respectively
Heater 7 controls, and forms preheating zone, double salt formation in the burner hearth of chlorination dehydration furnace the most respectively
Band and de-ammonium band.In order to ensure material in a furnace can direct motion, in heating process with agitating device 3 right
Material is stirred, and makes material loosening, easy direct motion.The anhydrous magnesium chloride that reaction obtains is via discharging opening 4 row
Enter in storage bin 8, in order to during preventing discharging, anhydrous magnesium chloride occurs with the steam in air and oxygen
Reaction, seals storage bin, and is passed through in storehouse by inert gas entrance 9 by noble gas, gas in storehouse
Body is discharged by gas outlet 10, it is ensured that the inert atmosphere in storehouse, the ammonia of generation, chlorination in heating process
Hydrogen and ammonium chloride are overflowed by the gas overflowing mouth 2 of upper of furnace body.
Raw material (such as, magnesium oxide, magnesium chloride hexahydrate, ammonium chloride etc.) employed in the inventive method is not all had
Having concrete restriction, they all can use common commercial products.Described raw material is preferably in powder type, right
The particle diameter of described powder is not particularly limited.
Compared with the existing method preparing anhydrous magnesium chloride, it is an advantage of the current invention that: (1) technological process
Short, it is possible to achieve continuous prodution, production efficiency is high；(2) technique is simple, it is not necessary to special equipment and
Atmosphere protection, easy operation control；(3) purity of anhydrous magnesium chloride is high, can reach content of MgO less than 0.1
Weight %, can meet the requirement to raw material of the most advanced electrolysis bath；(4) magnesium oxide or hydrated magnesium chloride and chlorine are utilized
Changing ammonium is that anhydrous magnesium chloride prepared by raw material, these cheaper starting materials, is easy to get；(5) ammonium chloride easily reclaims and real
Now recycle, and ammonium chloride is little to the corrosivity of equipment, relatively low to the sealing requirements also ratio of equipment.
Accompanying drawing explanation
Fig. 1 is the process chart that the present invention prepares anhydrous magnesium chloride；
Fig. 2 is present invention chlorination dehydration furnace schematic diagram；
In figure: 1-charge door；2-gas overflowing mouth；3-agitating device；4-discharging opening；5-preheating zone adds hot charging
Put；6-double salt forms band heater；7-takes off ammonium band heater；8-storage bin；9-inert gas entrance；
10-gas outlet；11-preheating zone；12-double salt forms band；13-takes off ammonium band；
Fig. 3 is the XRD figure spectrum of the anhydrous magnesium chloride utilizing magnesium oxide magnesium to prepare in the embodiment of the present invention 1；
Fig. 4 is the XRD figure spectrum of the anhydrous magnesium chloride utilizing magnesium chloride hexahydrate to prepare in the embodiment of the present invention 12.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art it will be clearly understood that
The only help of described embodiment understands the present invention, is not construed as the concrete restriction to the present invention.
In the present invention, anhydrous magnesium chloride meter based on 100%, the content of magnesium oxide is less than 0.5wt% (i.e.,
Contained magnesium oxide in acceptable anhydrous magnesium chloride for the technique that general electrolytic method produces magnesium metal
The upper limit of content), preferably smaller than 0.1wt% (that is, state-of-the-art pluripolarity in current electrolysis method production magnesium metal
The upper limit of the content of contained magnesium oxide in electrolysis bath acceptable anhydrous magnesium chloride).Therefore, according to the present invention
Anhydrous magnesium chloride prepared by method is possible not only to solution production magnesium metal use of directly powering, and can be direct
Magnesium metal is prepared for pluripolarity electrolytic tank electrolysis.
It addition, in the present invention, unless otherwise noted, described containing the magnesium oxide (MgO) in anhydrous magnesium chloride
Content refer to the percetage by weight of the magnesium oxide in terms of the anhydrous magnesium chloride of 100%.
In the present invention, unless otherwise noted, term " hydrated magnesium chloride " refers to the chlorination containing water of crystallization
Magnesium (MgCl2·mH2O, the number of the water of crystallization contained during wherein m represents hydrated magnesium chloride described in per molecule,
m>0)。
Test according to the anhydrous magnesium chloride that the present invention is prepared by following method.
1. titration measuring sample aqueous solution precipitate is to determine magnesium oxide content in anhydrous magnesium chloride
By soluble in water for the anhydrous magnesium chloride sample that obtains, with the quantitative filter paper of four Φ 90mm, (Hangzhou is extraordinary
Paper Co., Ltd) aqueous solution is filtered at least three times repeatedly till filtrate is clarified especially.Filter paper is spent
Ionized water rinses to wash away the magnesium ion adhered to above repeatedly, and after washing, the filter paper containing magnesium oxide particle is put
Enter in beaker, add sulphuric acid (analytical pure, the purity 95.98% of the 1:100 of the preparation of excess；Producer: north
Jing Beiization fine chemicals Co., Ltd), by beaker heated and boiled and stand five minutes and make anti-on electric furnace
Should be complete.Solution in beaker carries out EDTA titrate to determine the content of magnesium ion, thus obtain anhydrous chlorine
Change the content of magnesium oxide in magnesium.
Calculating the precondition of the content of magnesium oxide in anhydrous magnesium chloride according to above method is in anhydrous magnesium chloride
MgOHCl can not be there is.It is 30 minutes that MgOHCl is fully converted to the time of MgO when 500 DEG C,
The time converted when temperature is higher can shorten.Thus judge, MgOHCl under conditions of the embodiment of the present invention
Can be completely converted into MgO, the most sedimentary composition only has magnesium oxide to exist.Data Source is shown in document:
Kashani-Nejad, S., K.Ng, et al. (2005) .MgOHCl kinetics of thermal decomposition (MgOHCl thermal
Decomposition kinetics.), metallurgical and material publication (Metallurgical and Materials Transactions
B)2005。
2. the mensuration of moisture in sample
The sample obtained is processed because being incubated the long period at relatively high temperatures with present invention process, should in sample
Should be without Free water or water of crystallization, even if there being water the most anti-with anhydrous magnesium chloride
Should generate magnesium oxide, the moisture that experiment measures is all sample during measuring and during room temperature preserves
The moisture absorbed.The mensuration of moisture uses karl Fischer titration measuring moisture, and instrument uses Shanghai chemical industry to grind
The KF-1B type moisture test apparatus of Jiu Yuan instrucment and meter plant.Concrete grammar sees: " preparation of basic magnesium chloride and thing thereof
Physicochemical Quality Research ", salt lake S&T resource allocation (1980).
3. use X-ray diffractometer (model: X'Pert PRO MPD；Producer: Philips), penetrated by X
Line diffraction (XRD) determines the existence of anhydrous magnesium chloride.
The raw material used in the present invention is commercially available product, including:
Magnesium oxide: Chemical Reagent Co., Ltd., Sinopharm Group, purity >=98.5%；
Magnesium chloride hexahydrate: magnesium chloride hexahydrate: Xilong Chemical Co., Ltd, purity >=98.0%.
Ammonium chloride: Xilong Chemical Co., Ltd, purity >=99.5%.
Hydrated magnesium chloride: by above-mentioned magnesium chloride hexahydrate 80-160 DEG C of heating, judge according to sample weight loss situation
End product.
The typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
945g ammonium chloride adds after mixing homogeneously with 350g magnesium oxide in the chlorination dehydration furnace that draw ratio is 3.5:1,
Mixture thickness in stove is 15cm, and mixed material heats in different heating tapes: first at 150 DEG C
Heat 0.2 hour, then heat 2.5 hours at 300 DEG C, finally heat 0.5 hour at 700 DEG C, obtain nothing
Aqueous magnesium chloride.Anhydrous magnesium chloride is discharged from furnace bottom discharging opening, and new a collection of mixture material is by stove top
Charge door add.In this embodiment, it is in terms of 1.00 weight portions by the feeding quantity of magnesium oxide, ammonium chloride
Feeding quantity is 2.7 weight portions.Fig. 3 is the XRD figure spectrum of anhydrous magnesium chloride prepared by the present embodiment.
According to above-mentioned measuring method, the anhydrous magnesium chloride obtained is characterized.Its result is as follows:
Sample composition is carried out XRD material phase analysis, and composition is anhydrous MgCl2, as shown in Figure 3；To sample
Precipitate after water-soluble titrates, and the weight recording magnesium oxide is the 0.31% of anhydrous magnesium chloride；To in sample
Moisture is measured, and recording moisture in sample is 0.24%.
Embodiment 2
1404g ammonium chloride adds after mixing homogeneously with 350g magnesium oxide in the chlorination dehydration furnace that draw ratio is 3.5:1,
Mixture thickness in stove is 23cm, and mixed material heats in different heating tapes: first at 80 DEG C
Heat 3.5 hours, then heat 0.2 hour at 400 DEG C, finally heat 2.5 hours at 450 DEG C, obtain nothing
Aqueous magnesium chloride.Anhydrous magnesium chloride is discharged from furnace bottom discharging opening, and new a collection of mixture material is by stove top
Charge door add.In this experiment, it is in terms of 1.00 weight portions by the feeding quantity of magnesium oxide, adding of ammonium chloride
Doses is 4.0 weight portions.
According to above-mentioned measuring method, the anhydrous magnesium chloride obtained is characterized.Its result is as follows:
Sample composition is carried out XRD material phase analysis, and composition is anhydrous MgCl2Show；To sample sinking after water-soluble
Shallow lake thing titrates, and the weight recording magnesium oxide is the 0.11% of anhydrous magnesium chloride；Moisture in sample is entered
Row measures, and recording moisture in sample is 0.09%.
Embodiment 3
1404g ammonium chloride adds after mixing homogeneously with 350g magnesium oxide in the chlorination dehydration furnace that draw ratio is 15:1,
Mixture thickness in stove is 95cm, and mixed material heats in different heating tapes: first at 100 DEG C
Heat 1.0 hours, then heat 1.8 hours at 380 DEG C, finally heat 1.0 hours at 700 DEG C, obtain nothing
Aqueous magnesium chloride.Anhydrous magnesium chloride is discharged from furnace bottom discharging opening, and new a collection of mixture material is by stove top
Charge door add.In this experiment, it is in terms of 1.00 weight portions by the feeding quantity of magnesium oxide, adding of ammonium chloride
Doses is 4.0 weight portions.
According to above-mentioned measuring method, the anhydrous magnesium chloride obtained is characterized.Its result is as follows:
Sample composition is carried out XRD material phase analysis, and composition is anhydrous MgCl2；To sample precipitation after water-soluble
Thing titrates, and the weight recording magnesium oxide is the 0.05% of anhydrous magnesium chloride；Moisture in sample is carried out
Measuring, recording moisture in sample is 0.08%.
Embodiment 4
2340g ammonium chloride adds after mixing homogeneously with 350g magnesium oxide in the chlorination dehydration furnace that draw ratio is 15:1,
Mixture thickness in stove is 134cm, and mixed material heats in different heating tapes: first exist
120 DEG C are heated 0.5 hour, then heat 2.0 hours at 350 DEG C, finally heat 1.2 hours at 680 DEG C,
Obtain anhydrous magnesium chloride.Anhydrous magnesium chloride is discharged from furnace bottom discharging opening, and new a collection of mixture material is by stove
The charge door on sub-top adds.In this experiment, it is in terms of 1.00 weight portions by the feeding quantity of magnesium oxide, chlorination
The feeding quantity of ammonium is 6.7 weight portions.
According to above-mentioned measuring method, the anhydrous magnesium chloride obtained is characterized.Its result is as follows:
Sample composition is carried out XRD material phase analysis, and composition is anhydrous MgCl2；To sample precipitation after water-soluble
Thing titrates, and the weight recording magnesium oxide is the 0.03% of anhydrous magnesium chloride；Moisture in sample is carried out
Measuring, recording moisture in sample is 0.06%.
Embodiment 5
7035g ammonium chloride adds after mixing homogeneously with 350g magnesium oxide in the chlorination dehydration furnace that draw ratio is 3.5:1,
Mixture thickness in stove is 126cm, and mixed material heats in different heating tapes: first exist
120 DEG C are heated 0.5 hour, then heat 2.0 hours at 400 DEG C, finally heat 1.5 hours at 650 DEG C,
Obtain anhydrous magnesium chloride.Anhydrous magnesium chloride is discharged from furnace bottom discharging opening, and new a collection of mixture material is by stove
The charge door on sub-top adds.In this experiment, it is in terms of 1.00 weight portions by the feeding quantity of magnesium oxide, chlorination
The feeding quantity of ammonium is 20.1 weight portions.
According to above-mentioned measuring method, the anhydrous magnesium chloride obtained is characterized.Its result is as follows:
Sample composition is carried out XRD material phase analysis, and composition is anhydrous MgCl2；To sample precipitation after water-soluble
Thing titrates, and the weight recording magnesium oxide is the 0.02% of anhydrous magnesium chloride；Moisture in sample is carried out
Measuring, recording moisture in sample is 0.07%.
Embodiment 6
7035g ammonium chloride adds after mixing homogeneously with 350g magnesium oxide in the chlorination dehydration furnace that draw ratio is 2:1,
Mixture thickness in stove is 56cm, and mixed material heats in different heating tapes: first at 50 DEG C
Heat 5.0 hours, then heat 5.0 hours at 250 DEG C, finally heat 5.0 hours at 420 DEG C, obtain nothing
Aqueous magnesium chloride.Anhydrous magnesium chloride is discharged from furnace bottom discharging opening, and new a collection of mixture material is by stove top
Charge door add.In this experiment, it is in terms of 1.00 weight portions by the feeding quantity of magnesium oxide, adding of ammonium chloride
Doses is 20.1 weight portions.
According to above-mentioned measuring method, the anhydrous magnesium chloride obtained is characterized.Its result is as follows:
Sample composition is carried out XRD material phase analysis, and composition is anhydrous MgCl2；To sample precipitation after water-soluble
Thing titrates, and the weight recording magnesium oxide is the 0.08% of anhydrous magnesium chloride；Moisture in sample is carried out
Measuring, recording moisture in sample is 0.09%.
Embodiment 7
1404g ammonium chloride adds the chlorination dehydration furnace that draw ratio is 3.5:1 with 350g magnesium oxide after mixing homogeneously
In, mixture thickness in stove is 23cm, and mixed material heats in different heating tapes: first exist
200 DEG C are heated 0.2 hour, then heat 0.2 hour at 400 DEG C, finally heat 0.5 hour at 750 DEG C,
Obtain anhydrous magnesium chloride.Anhydrous magnesium chloride is discharged from furnace bottom discharging opening, and new a collection of mixture material is by stove
The charge door on sub-top adds.In this experiment, it is in terms of 1.00 weight portions by the feeding quantity of magnesium oxide, chlorination
The feeding quantity of ammonium is 4.0 weight portions.
According to above-mentioned measuring method, the anhydrous magnesium chloride obtained is characterized.Its result is as follows:
Sample composition is carried out XRD material phase analysis, and composition is anhydrous MgCl2；To sample precipitation after water-soluble
Thing titrates, and the weight recording magnesium oxide is the 0.06% of anhydrous magnesium chloride；Moisture in sample is carried out
Measuring, recording moisture in sample is 0.06%.
Embodiment 8
910g ammonium chloride adds after mixing homogeneously with 350g magnesium oxide in the chlorination dehydration furnace that draw ratio is 2:1,
Mixture thickness in stove is 10cm, and mixed material heats in different heating tapes: first at 150 DEG C
Heat 0.5 hour, then heat 1.0 hours at 350 DEG C, finally heat 3.0 hours at 650 DEG C, obtain nothing
Aqueous magnesium chloride.Anhydrous magnesium chloride is discharged from furnace bottom discharging opening, and new a collection of mixture material is by stove top
Charge door add.In this experiment, it is in terms of 1.00 weight portions by the feeding quantity of magnesium oxide, adding of ammonium chloride
Doses is 2.6 weight portions.
According to above-mentioned measuring method, the anhydrous magnesium chloride obtained is characterized.Its result is as follows:
Sample composition is carried out XRD material phase analysis, and composition is anhydrous MgCl2；To sample precipitation after water-soluble
Thing titrates, and the weight recording magnesium oxide is the 0.09% of anhydrous magnesium chloride；Moisture in sample is carried out
Measuring, recording moisture in sample is 0.07%.
Embodiment 9
8750g ammonium chloride adds the chlorination dehydration furnace that draw ratio is 3.5:1 with 350g magnesium oxide after mixing homogeneously
In, mixture thickness in stove is 72cm, and mixed material heats in different heating tapes: first exist
150 DEG C are heated 0.5 hour, then heat 1.0 hours at 350 DEG C, finally heat 4.5 hours at 750 DEG C,
Obtain anhydrous magnesium chloride.Anhydrous magnesium chloride is discharged from furnace bottom discharging opening, and new a collection of mixture material is by stove
The charge door on sub-top adds.In this experiment, it is in terms of 1.00 weight portions by the feeding quantity of magnesium oxide, chlorination
The feeding quantity of ammonium is 25 weight portions.
According to above-mentioned measuring method, the anhydrous magnesium chloride obtained is characterized.Its result is as follows:
Sample composition is carried out XRD material phase analysis, and composition is anhydrous MgCl2；To sample precipitation after water-soluble
Thing titrates, and the weight recording magnesium oxide is the 0.03% of anhydrous magnesium chloride；Moisture in sample is carried out
Measuring, recording moisture in sample is 0.02%.
Embodiment 10
535g ammonium chloride and 2030g magnesium chloride hexahydrate (MgCl2·6H2O) draw ratio is added after mix homogeneously
For in the chlorination dehydration furnace of 3.5:1, mixture thickness in stove is 38cm, and mixed material adds different
The torrid zone is heated: first heat 0.2 hour at 150 DEG C, then 400 DEG C of heating 2.5 hours, finally
Heat 0.5 hour at 700 DEG C, obtain anhydrous magnesium chloride.Anhydrous magnesium chloride is discharged from furnace bottom discharging opening,
New a collection of mixture material is added by the charge door on stove top.In this experiment, with the chlorine without water of crystallization
The feeding quantity changing magnesium is 1.00 weight portion meters, and the feeding quantity of ammonium chloride is 0.56 weight portion.
According to above-mentioned measuring method, the anhydrous magnesium chloride obtained is characterized.Its result is as follows:
Sample composition is carried out XRD material phase analysis, and composition is anhydrous MgCl2；To sample precipitation after water-soluble
Thing titrates, and the weight recording magnesium oxide is the 0.07% of anhydrous magnesium chloride；Moisture in sample is carried out
Measuring, recording moisture in sample is 0.07%.
Embodiment 11
267.5g ammonium chloride and 2030g magnesium chloride hexahydrate (MgCl2·6H2O) major diameter is added after mix homogeneously
Ratio is in the chlorination dehydration furnace of 3.5:1, and mixture thickness in stove is 21cm, and mixed material is different
Heating tape is heated: first heats 5 hours at 50 DEG C, then heats 5 hours at 250 DEG C, finally exist
750 DEG C are heated 0.5 hour, obtain anhydrous magnesium chloride.Anhydrous magnesium chloride is discharged from furnace bottom discharging opening, newly
A collection of mixture material is added by the charge door on stove top.In this experiment, with the chlorination without water of crystallization
The feeding quantity of magnesium is 1.00 weight portion meters, and the feeding quantity of ammonium chloride is 0.28 weight portion.
According to above-mentioned measuring method, the anhydrous magnesium chloride obtained is characterized.Its result is as follows:
Sample composition is carried out XRD material phase analysis, and composition is anhydrous MgCl2；To sample precipitation after water-soluble
Thing titrates, and the weight recording magnesium oxide is the 0.09% of anhydrous magnesium chloride；Moisture in sample is carried out
Measuring, recording moisture in sample is 0.04%.
Embodiment 12
535g ammonium chloride and 2030g magnesium chloride hexahydrate (MgCl2·6H2O) draw ratio is added after mix homogeneously
For in the chlorination dehydration furnace of 3.5:1, mixture thickness in stove is 38cm, and mixed material adds different
The torrid zone is heated: first heat 0.2 hour at 200 DEG C, then 250 DEG C of heating 0.2 hour, finally
Heat 5.0 hours at 450 DEG C, obtain anhydrous magnesium chloride.Anhydrous magnesium chloride is discharged from furnace bottom discharging opening,
New a collection of mixture material is added by the charge door on stove top.In this experiment, with the chlorine without water of crystallization
The feeding quantity changing magnesium is 1.00 weight portion meters, and the feeding quantity of ammonium chloride is 0.56 weight portion.Fig. 4 is this enforcement
The XRD figure spectrum of anhydrous magnesium chloride prepared by example.
According to above-mentioned measuring method, the anhydrous magnesium chloride obtained is characterized.Its result is as follows:
Sample composition is carried out XRD material phase analysis, and composition is anhydrous MgCl2；To sample precipitation after water-soluble
Thing titrates, and the weight recording magnesium oxide is the 0.06% of anhydrous magnesium chloride；Moisture in sample is carried out
Measuring, recording moisture in sample is 0.08%.
Embodiment 13
1070g ammonium chloride and 1436g hydrated magnesium chloride (MgCl2·2.7H2O) major diameter is added after mix homogeneously
Ratio is in the chlorination dehydration furnace of 3.5:1, and mixture thickness in stove is 43cm, and mixed material is different
Heating tape is heated: first heat 3.5 hours at 80 DEG C, then 300 DEG C of heating 0.2 hour, finally
Heat 2.5 hours at 450 DEG C, obtain anhydrous magnesium chloride.Anhydrous magnesium chloride is discharged from furnace bottom discharging opening,
New a collection of mixture material is added by the charge door on stove top.In this experiment, with the chlorine without water of crystallization
The feeding quantity changing magnesium is 1.00 weight portion meters, and the feeding quantity of ammonium chloride is 1.13 weight portions.
According to above-mentioned measuring method, the anhydrous magnesium chloride obtained is characterized.Its result is as follows:
Sample composition is carried out XRD material phase analysis, and composition is anhydrous MgCl2；To sample precipitation after water-soluble
Thing titrates, and the weight recording magnesium oxide is the 0.04% of anhydrous magnesium chloride；Moisture in sample is carried out
Measuring, recording moisture in sample is 0.06%.
Embodiment 14
2140g ammonium chloride and 1238g hydrated magnesium chloride (MgCl2·1.6H2O) major diameter is added after mix homogeneously
Ratio is in the chlorination dehydration furnace of 15:1, and mixture thickness in stove is 126cm, and mixed material is different
Heating tape is heated: first heats 2.0 hours at 120 DEG C, then heats 2.0 hours at 350 DEG C,
After 650 DEG C heat 1.5 hours, obtain anhydrous magnesium chloride.Anhydrous magnesium chloride is discharged from furnace bottom discharging opening,
New a collection of mixture material is added by the charge door on stove top.In this experiment, with the chlorine without water of crystallization
The feeding quantity changing magnesium is 1.00 weight portion meters, and the feeding quantity of ammonium chloride is 2.25 weight portions.
According to above-mentioned measuring method, the anhydrous magnesium chloride obtained is characterized.Its result is as follows:
Sample composition is carried out XRD material phase analysis, and composition is anhydrous MgCl2；To sample precipitation after water-soluble
Thing titrates, and the weight recording magnesium oxide is the 0.03% of anhydrous magnesium chloride；Moisture in sample is carried out
Measuring, recording moisture in sample is 0.07%.
Embodiment 15
5320g ammonium chloride and 123.8g hydrated magnesium chloride (MgCl2·1.6H2O) major diameter is added after mix homogeneously
Ratio is in the chlorination dehydration furnace of 15:1, and mixture thickness in stove is 126cm, and mixed material is different
Heating tape is heated: first heats 3.5 hours at 150 DEG C, then heats 2.5 hours at 400 DEG C,
After 700 DEG C heat 2.5 hours, obtain anhydrous magnesium chloride.Anhydrous magnesium chloride is discharged from furnace bottom discharging opening,
New a collection of mixture material is added by the charge door on stove top.In this experiment, with the chlorine without water of crystallization
The feeding quantity changing magnesium is 1.00 weight portion meters, and the feeding quantity of ammonium chloride is 56 weight portions.
According to above-mentioned measuring method, the anhydrous magnesium chloride obtained is characterized.Its result is as follows:
Sample composition is carried out XRD material phase analysis, and composition is anhydrous MgCl2；To sample precipitation after water-soluble
Thing titrates, and the weight recording magnesium oxide is the 0.02% of anhydrous magnesium chloride；Moisture in sample is carried out
Measuring, recording moisture in sample is 0.04%.
By the result of above example it will be seen that prepare anhydrous chlorination at the magnesium oxide that utilizes according to the present invention
In anhydrous magnesium chloride prepared by the technique of magnesium and device, can be by harmful substance magnesium oxide relative to anhydrous chlorine
The content changing magnesium controls to the upper limit as commercial Application that is 0.5%.It addition, through optimization after, permissible
Harmful substance magnesium oxide is controlled to less than 0.1% relative to the content of anhydrous magnesium chloride, has reached the world advanced
The requirement to raw material of the electrolytic magnesium technique.
Applicant states, the present invention illustrates detailed process equipment and the technique of the present invention by above-described embodiment
Flow process, but the invention is not limited in above-mentioned detailed process equipment and technological process, i.e. do not mean that the present invention
Have to rely on above-mentioned detailed process equipment and technological process could be implemented.Person of ordinary skill in the field should
This understands, any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and auxiliary element
Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (18)
1. a preparation facilities for anhydrous magnesium chloride, for chlorination dehydration furnace, it is characterised in that described chlorination takes off
Water stove includes that preheating zone, top (11), middle part double salt form band (12), bottom takes off ammonium band (13) and passes through
The storage bin (8) that what discharging opening (4) connected have certain sealing, wherein, the length of described chlorination dehydration furnace
Footpath ratio >=2:1, described storage bin (8) has inert atmosphere, and described chlorination dehydration furnace also includes gas overflowing mouth
(2) and discharging opening (4), described chlorination dehydration furnace also includes agitating device (3).
2. device as claimed in claim 1, it is characterised in that the heating-up temperature of described preheating zone (11)
For 50-200 DEG C, described middle part double salt forms the heating-up temperature of band (12) and is 250-400 DEG C, and described bottom takes off
The heating-up temperature of ammonium band (13) is 420-750 DEG C.
3. device as claimed in claim 1, it is characterised in that the heating-up temperature of described preheating zone (11)
For 80-150 DEG C.
4. device as claimed in claim 1, it is characterised in that described middle part double salt forms band (12)
Heating-up temperature is 300-400 DEG C.
5. device as claimed in claim 1, it is characterised in that described bottom takes off the heating of ammonium band (13)
Temperature is 450-700 DEG C.
6. device as claimed in claim 1, it is characterised in that the draw ratio of described chlorination dehydration furnace is >=
3.5:1。
7. the method utilizing device described in claim 1 to prepare anhydrous magnesium chloride, comprises the steps:
A magnesium oxide is mixed by () with ammonium chloride；
B (), by heating in step (a) gained mixture addition chlorination dehydration furnace, prepares anhydrous magnesium chloride；
C () anhydrous magnesium chloride is discharged while, repeat step (a) and (b), it is achieved continuous prodution.
8. the method utilizing device described in claim 1 to prepare anhydrous magnesium chloride, comprises the steps:
A molecular formula is MgCl by ()2·mH2The hydrated magnesium chloride of O mixes with ammonium chloride；Or by magnesium oxide with point
Minor is MgCl2·mH2The hydrated magnesium chloride of O mixes with ammonium chloride；
Wherein, m ＞ 0；
B (), by heating in step (a) gained mixture addition chlorination dehydration furnace, prepares anhydrous magnesium chloride；
C () anhydrous magnesium chloride is discharged while, repeat step (a) and (b), it is achieved continuous prodution.
9. method as claimed in claim 7, it is characterised in that be 1.00 weight with the feeding quantity of magnesium oxide
Part meter, the feeding quantity of ammonium chloride is 2.60-25.00 weight portion.
10. method as claimed in claim 7, it is characterised in that be 1.00 weights with the feeding quantity of magnesium oxide
Amount part meter, the feeding quantity of ammonium chloride is 2.70-20.10 weight portion.
11. methods as claimed in claim 8, it is characterised in that 6 >=m ＞ 0.
12. methods as claimed in claim 8, it is characterised in that with the magnesium chloride without water of crystallization, or
Magnesium oxide is 1.00 weight portion meters with the feeding quantity of the magnesium chloride without water of crystallization, and the feeding quantity of ammonium chloride is
0.28-60.00 weight portion.
13. methods as claimed in claim 8, it is characterised in that with the magnesium chloride without water of crystallization, or
Magnesium oxide is 1.00 weight portion meters with the feeding quantity of the magnesium chloride without water of crystallization, and the feeding quantity of ammonium chloride is
0.28-56.00 weight portion.
14. method as claimed in claim 7 or 8, it is characterised in that described mixture is in preheating zone
Heat time heating time is 0.2-5.0h；The heat time heating time forming band at double salt is 0.2-5.0h；When the heating of de-ammonium band
Between be 0.5-5.0h.
15. method as claimed in claim 7 or 8, it is characterised in that described mixture is in preheating zone
Heat time heating time is 0.2-3.5h；The heat time heating time forming band at double salt is 0.2-2.5h；When the heating of de-ammonium band
Between be 0.5-2.5h.
16. methods as claimed in claim 7 or 8, it is characterised in that described in step (b), mixture exists
Thickness in chlorination dehydration furnace is not less than 10cm.
17. methods as claimed in claim 7 or 8, it is characterised in that described in step (b), mixture exists
Thickness in chlorination dehydration furnace is not less than 15cm.
18. methods as claimed in claim 7 or 8, it is characterised in that the ammonia that produces in step (b),
Hydrogen chloride and ammonium chloride are discharged through gas overflowing mouth (2), and carry out reclaiming to recycle.
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| CN107500319A (en) * | 2017-09-12 | 2017-12-22 | 中国科学院青海盐湖研究所 | A kind of preparation method of anhydrous magnesium chloride |
| CN108298573B (en) * | 2018-04-13 | 2020-11-24 | 上海泰坦科技股份有限公司 | Preparation method of anhydrous yttrium chloride |
| CN109607581B (en) * | 2019-02-19 | 2023-08-29 | 河北工业大学 | Device and method for preparing anhydrous magnesium chloride by using ammonium chloride and magnesium carbonate |
| CN113106497B (en) * | 2021-04-09 | 2022-04-01 | 河北大有镁业有限责任公司 | Method for continuously producing raw materials for electrolytic rare earth magnesium alloy by utilizing hydrolysis-chlorination coupling reaction |
| CN112899728B (en) * | 2021-04-09 | 2021-11-16 | 河北大有镁业有限责任公司 | Ammonium carnallite dehydration material and method for preparing magnesium electrolyte melt by using same |
| CN113479917B (en) * | 2021-08-02 | 2022-08-12 | 青海盐湖工业股份有限公司 | Method and process for preparing anhydrous magnesium chloride |
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