CN106917108A - A kind of production technology of magnesium metal - Google Patents
A kind of production technology of magnesium metal Download PDFInfo
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- CN106917108A CN106917108A CN201710164137.4A CN201710164137A CN106917108A CN 106917108 A CN106917108 A CN 106917108A CN 201710164137 A CN201710164137 A CN 201710164137A CN 106917108 A CN106917108 A CN 106917108A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/04—Electrolytic production, recovery or refining of metals by electrolysis of melts of magnesium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
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Abstract
The invention discloses a kind of production technology of magnesium metal, comprise the following steps：Step S1 refining steps：Sulfate ion in the material of removal raw material lake containing magnesium salts and containing boron substance, so that refined end liquid is obtained, the content of sulfate ion is less than 20ppm in the refined whole liquid；Boron contents are less than 1ppm；Step S2 dehydration procedures：The moisture in the refined liquid is removed, so that water-free magnesium chloride granule is obtained；Step S3 electrowinning processes：The water-free magnesium chloride granule is input in electrolytic cell, makes it that electrochemical reaction occur as electrolyte, so that magnesium metal liquid is obtained；Step S4 casting process：The magnesium metal liquid is transported in casting machine and is cast, form magnesium ingot.The production technology of the magnesium metal that the present invention is provided continuous automatic production can go out magnesium metal from salt lake bittern, artificial less investment, and prepared magnesium yield is high, purity is high, with application value very high.
Description
Technical field
The present invention relates to the technical field of magnesium technique processed, and in particular to a kind of use material production of lake containing magnesium salts magnesium metal
Technique.
Background technology
Magnesium metal is based on the superiority and uniqueness of its physical property, has become the extremely wide gold of current application prospect
Category material, its alloy product is widely used in the fields such as automobile, Aeronautics and Astronautics, electronics, be described as by material scholar " when cash equivalent
Category ".At present, magnesium metal production technology is mainly fused salt electrolysis process and thermal reduction, current application it is relatively broad be thermal reduction
Method production technology, it with magnesite and dolomite is raw material production to be, but production process is present, and energy consumption is higher, environmental pollution is tight
The shortcomings of weight, labor strength are big, high-nickel material consumption is big, therefore be not suitable for being widely popularized.
Based on substantial amounts of magnesium ion is contained in salt lake bittern and seawater, domestic and international research institution and metallurgical production enterprise are continuous
Trial extracts MgCl from salt lake bittern and seawater2, so that magnesium metal is produced using the method for electrolysis, but due to salt lake halogen
SO in water and seawater4-, B element be difficult to effectively removal, and crystallization water removing is difficult, therefore, the research is in the shape stagnated
State, fails to complete industrial test.
And also contain substantial amounts of potassium ion simultaneously, in salt lake bittern, with the exploitation of potassium resource, contain in accessory substance
Substantial amounts of magnesium chloride and bischofite are not utilized effectively, therefore not only cause the wasting of resources, also to environment bring compared with
Big pressure.
The content of the invention
It is an object of the invention to provide a kind of production technology of magnesium metal, for solving existing producing magnesium method energy consumption
It is high, environmental pollution is serious, hand labor intensity is big, high-nickel material consumption greatly, while accessory substance is made in potassium resource development process
Into the big problem of environmental pressure.
To achieve these goals, the present invention provides following technical scheme：A kind of production technology of magnesium metal, its feature exists
In comprising the following steps：
Step S1 refining steps：
Sulfate ion in the material of removal raw material lake containing magnesium salts and containing boron substance, it is described to refine so that refined end liquid is obtained
The content of sulfate ion is less than 20ppm in whole liquid；Boron contents are less than 1ppm；
Step S2 dehydration procedures：
The moisture in the refined whole liquid is removed, so that water-free magnesium chloride granule is obtained；
Step S3 electrowinning processes：
The water-free magnesium chloride granule is input in electrolytic cell, makes it that electrochemical reaction occur as electrolyte, to make
Obtain magnesium metal liquid；
Step S4 casting process：
The magnesium metal liquid is transported in casting machine and is cast, form magnesium ingot.
Preferably, the refining step includes primary purification operation S11 and secondary refining operation S12, wherein,
The primary purification operation S11 comprises the following steps：
S11a：Solid matter in raw material lake containing the magnesium salts material is dissolved using hot salt brine, so that the first essence is obtained
Liquid processed；
S11b：First refined liquid mixes with barium chloride solution, removes the sulfate radical in first refined liquid, to make
Obtain the second refined liquid；
S11c：Second refined liquid passes through inorganic membrane filtration unit, so that the 3rd refined liquid is obtained；
The secondary refining operation S12 is by boron polymeric adsorbent, to remove the 3rd essence by the 3rd refined liquid
In liquid processed containing boron substance, refined end liquid is obtained.
Preferably, the dehydration procedure S2 comprises the following steps：
S21：Adjust the pH value of the refined whole liquid so that the pH value of the refined whole liquid is 5.5~6.5；
S22：Heating evaporation is realized to the refined whole liquid, so that the refined end liquid of concentration is obtained, through the concentration after evaporation
The temperature of refined end liquid is more than 190 DEG C；
S23：By the refined end liquid of the concentration by separator, to isolate the gaseous mixture in the refined end liquid of the concentration,
Magnesium chloride concentrate is obtained, the mass fraction of magnesium chloride is more than 50% in the magnesium chloride concentrate；
S24：Granulation operations are realized to the magnesium chloride concentrate, so that water-free magnesium chloride granule, the anhydrous chlorination is obtained
Mass fraction of the water content less than 0.03%, MgOHCl in magnesium granules is less than 0.2%.
Preferably, the granulation operations S24 comprises the following steps：
S24a：The magnesium chloride concentrate is set to pass sequentially through granulation centrifuge and granulation tower, so that the wet pellet of magnesium chloride is obtained；
S24b：Operation is dried to the wet pellet of the magnesium chloride, so that water-free magnesium chloride granule is obtained.
Preferably, the drying process in the step S24b includes air-drying option and hydrogen chloride drying process, wherein,
The air-drying option is by Air Fluidized bed, so that half-dried of magnesium chloride is obtained by the magnesium chloride concentrate
Grain, every mole of magnesium chloride reclaimed water molecule content is less than 1.8 moles in the dry particl of the magnesium chloride half；
The hydrogen chloride drying process is by hydrogen chloride fluid bed, so that anhydrous chlorine is obtained by the dry particl of the magnesium chloride half
Change magnesium granules.
Preferably, the hydrogen chloride drying process is also operated including tail gas clean-up, and the tail gas clean-up operation is to make chlorination
The tail gas that the dry particl of magnesium half is produced during hydrogen chloride fluid bed is dry sequentially passes through spray scrubber and condenser, to go
Except magnesium chloride dust and moisture in the tail gas, it is purified after hydrogen chloride gas put into again it is real in hydrogen chloride drying process
Now utilize.
Further, the hydrogen chloride drying-granulating operation is also operated including tail gas recycle, and the tail gas recycle operation is
The liquid phase discarded object produced during tail gas clean-up is operated is input in Analytic Tower, uses magnesium chloride as broken boiling agent with to hydrogen chloride
Parsing is realized, the hydrogen chloride for parsing is realized utilizing in putting into the hydrogen chloride drying process.
Preferably, the electrowinning process S3 comprises the following steps：
S31：The water-free magnesium chloride granule is mixed with carbon dust and calcirm-fluoride, to form mixing pellet；
S32：The mixing pellet is transported in electrolytic cell and is electrolysed, so that magnesium metal liquid is obtained.
Preferably, the casting process S4 comprises the following steps：
S41：The magnesium metal liquid is transported to foundry；
S42：It is transported in continuous refining furnace after removing the excess electrolyte in the magnesium metal liquid, so that simple metal magnesium is obtained
Liquid；
S43：The simple metal magnesium liquid is transported in casting machine, ingot mould is realized, magnesium ingot is obtained；
S44：Cooling, packing are realized to the magnesium ingot and is stored.
Preferably, the material of lake containing magnesium salts carries the accessory substance containing magnesium after potassium for bittern.
Compared to prior art, the production technology of magnesium metal of the present invention has the advantage that：What the present invention was provided
The production technology of magnesium metal continuous automatic production can go out magnesium metal from salt lake bittern, and artificial less investment, prepared magnesium is produced
Amount is high, purity is high.
Additionally, the raw material in the present invention potassium or other brine treatment techniques can be carried using bittern after accessory substance containing magnesium, both
The wasting of resources is solved the problems, such as, its pressure to environment is decreased, while the metal of high added value can also be prepared
Magnesium, with application value very high.
Brief description of the drawings
By reading the detailed description of hereafter preferred embodiment, various other advantages and benefit is common for this area
Technical staff will be clear understanding.Accompanying drawing is only used for showing the purpose of preferred embodiment, and is not considered as to the present invention
Limitation.In the accompanying drawings：
Fig. 1 shows a kind of flow chart of the production technology of the magnesium metal of preferred embodiment of the invention；
Fig. 2 shows the flow chart of the refining step of preferred embodiment in Fig. 1；
Fig. 3 shows the flow chart of the dehydration procedure of preferred embodiment in Fig. 1；
Fig. 4 shows the flow chart of the electrowinning process of preferred embodiment in Fig. 1；And,
Fig. 5 shows the flow chart of the casting process of preferred embodiment in Fig. 1.
Specific embodiment
The invention provides many applicable creative concepts, the creative concept can be reflected in a large number of on specific
Hereinafter.Specific embodiment described in following embodiments of the present invention is only as specific embodiment of the invention
Exemplary illustration, and be not meant to limit the scope of the invention.
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings.
As shown in figure 1, the present embodiment provides a kind of production technology of magnesium metal, comprise the following steps：
Step S1：Refining step
Sulfate ion in the material of removal raw material lake containing magnesium salts and containing boron substance, prepared refined liquid, in the refined liquid
Sulfate ion content be less than 20ppm；Boron contents are less than 1ppm.
The step specifically includes primary purification operation S11 and secondary refining operation S12, wherein, primary purification operation S11 bags
Include following steps：
S11a：Solid matter in the material of raw material lake containing magnesium salts is dissolved using hot salt brine, is refined with being obtained first
Liquid.
S11b：First refined liquid is mixed with barium chloride solution, the sulfate radical in the first refined liquid is removed, to be obtained second
Refined liquid.
S11c：By the second refined liquid by inorganic membrane filtration unit, so that the 3rd refined liquid is obtained.
Specifically, as shown in Fig. 2 primary purification operation S11 is the industry water that will be exported by First Heat Exchanger via water distribution
Bucket realizes heat exchange in being input to the second heat exchanger with steam, and hot industry water is obtained, and the present embodiment preferably makes the hot industry
The temperature of water reaches more than 90 DEG C.The hot industry water is input in salt dissolving pond again, is mixed with raw material lake containing magnesium salts material
Close, so that solid matter present in the material of raw material lake containing magnesium salts is dissolved, and salt solution, and temperature are formed in salt dissolving pond
It is down to 70 DEG C or so.As hot industry water is constantly delivered to mix with raw material lake containing magnesium salts material in salt dissolving pond, the salt of formation
Water is overflowed in salt water saturation groove from salt dissolving pond, as the first refined liquid.
First refined liquid is conveyed by pipeline in baffling groove, and the barium chloride solution of barium chloride charge pump output is also entered into
Mix with the first refined liquid in baffling groove, the mixed liquor of formation is transported in reaction container so that barium chloride solution and first is refined
Sulfate ion reaction generation barium sulfate precipitate in liquid, after the sulfate ion content 20ppm into salt solution, then by reaction container
In material be pipelined in medial launder, as the second refined liquid.
In order to save the consumption of industry water, the exit of salt water saturation groove is provided with salt water circulating pump, and salt solution is from salt dissolving pond
After overflowing to salt water saturation groove, first, salt water circulating pump and the valve to baffling groove are closed, open salt water circulating pump to salt dissolving pond
Valve, form path, then overflow to salt water energy in salt water saturation groove and return in salt dissolving pond salt dissolving again via pipeline, change
Salt is overflowed in salt water saturation groove again after operating, so as to form the circulatory system between salt water saturation groove and salt dissolving pond.Pass through
Detection to salt solution, when the density and density of magnesium chloride in salt solution reach 34%, that is, shows that salt solution approaches to saturation to form saturated salt
Water, now turns down the valve of salt water circulating pump to salt dissolving pond, and opens the valve of salt water circulating pump to baffling groove so that a part
Saturated brine (i.e. the first refined liquid) be transported in baffling groove along pipeline, the saturated brine of another part then continues to be conveyed
Salt dissolving again is carried out in salt dissolving pond.
The second refined liquid in medial launder is delivered to by inorganic membrane filtration unit using membrane filtration feed pump.In the present embodiment
Inorganic membrane filtration unit using seven and two string " cross-flow " filter types, i.e., coarse filter, the 3rd heat exchanger, filtration cycle tank,
The series connection of filtration cycle pump, inorganic membrane filter and purified salt tank, wherein, inorganic membrane filter uses inoranic membrane to be situated between for filtering
Matter, inoranic membrane refers to the pellicle being made of inorganic material, the function with Selective Separation.Inoranic membrane mistake in the present embodiment
Filter includes single filter component and cascade filtration component, and a pipe is additionally provided between cascade filtration component and filtration cycle tank
Road loop.The second refined liquid exported by membrane filtration feed pump first passes around coarse filter, after filtering the impurity more than 1mm,
It is input in the 3rd heat exchanger, and the steam heat-exchanging in the 3rd heat exchanger, so that the temperature of the second refined liquid rises to 80 DEG C
Left and right, is then enter into filtration cycle tank, and the single filter of inorganic membrane filter is input to via filtration cycle pump
In component, primary concentration salt solution is obtained, the primary concentration salt solution exported through single filter component enters the two of inorganic membrane filter
In level filter assemblies, secondary concentration salt solution is obtained, the secondary concentration salt solution discharge exported through cascade filtration component is a small amount of to salt slurry
In ground, remaining secondary concentration salt solution then by pipeline loop return in filtration cycle tank with the high temperature for coming from the 3rd heat exchanger
Second refined liquid is mixed and exported in inorganic membrane filter again by filtration cycle pump to be refiltered, the interior circulation
Operation is in order to be adjusted into the solid-to-liquid ratio of inorganic membrane filter feed liquid, so as to realize ensureing the material stream in inorganic membrane filter
Speed, controls the purpose of secondary concentration salt solution solid content.The refining filtering salt solution of the filter assemblies at different levels output of inorganic membrane filter
Then discharge and be input in purified salt tank by the infiltration purified liquor outlets at different levels of inorganic membrane filter, as the 3rd refined liquid.
Sulfate radical and solid impurity in raw material can effectively be removed using above-mentioned refining step, it is met finishing operations
It is required that.
Wherein, the secondary refining operation S12 in above-mentioned refining step is by the 3rd refined liquid in primary purification operation S11
By boron polymeric adsorbent, thus in removing the 3rd refined liquid containing boron substance, refined end liquid is obtained.Specifically, in the present embodiment
Boron polymeric adsorbent be the series connection of multiple polymeric adsorbent towers form, bottom of the 3rd refined liquid first from the first polymeric adsorbent tower is entered
Enter, flow to the top of the first polymeric adsorbent tower, the top of the second polymeric adsorbent tower is then entered by serial pipe, flow to second
The bottom of polymeric adsorbent tower, and discharged by the bottom of the second polymeric adsorbent tower, into except boron product surge tank, as refine eventually
Liquid.During being discharged from the second polymeric adsorbent tower bottom, can sample to determine from the second polymeric adsorbent tower bottom row at any time
Boron contents in the feed liquid for going out, so as to control the Boron contents in refined end liquid to be less than 1ppm.
It is noted that after the first polymeric adsorbent tower fails, boron polymeric adsorbent can directly switch to the second absorption tree
Fat tower and the 3rd polymeric adsorbent tower series operation, the first polymeric adsorbent tower then enter reproducer, standby via being in after regeneration
State, realizes the quick of secondary refining operation and is carried out continuously.
The concentration of magnesium chloride is significantly improved in refined whole liquid after being processed via above-mentioned refining step, and impurity content significantly subtracts
Few, particularly sulfate radical content and Boron contents can meet the requirement of final treatment techniques.
Step S2：Dehydration procedure
The moisture in end liquid is refined in removing step S1, so that water-free magnesium chloride granule is obtained.
The step specifically includes tetra- steps of S21~S24：
S21：The pH value of the refined end liquid of regulation so that the pH value of refined end liquid is 5.5~6.5；
S22：Heating evaporation is realized to refined end liquid, so that the refined end liquid of concentration is obtained, refines concentration in evaporation process
The temperature of whole liquid is more than 190 DEG C；
S23：By the refined end liquid of concentration by separator, to isolate the gaseous mixture in the refined end liquid of concentration, so as to be obtained
Magnesium chloride concentrate, the mass fraction of magnesium chloride is more than 50% in magnesium chloride concentrate；
S24：Granulation operations are realized to magnesium chloride concentrate, so that water-free magnesium chloride granule is obtained, in water-free magnesium chloride granule
Water content less than 0.03%, MgOHCl mass fraction be less than 0.2%.
Specifically, as shown in figure 3, will be stored in dehydration storage tank except the refined whole liquid output in boron product surge tank, with
It is easy to the dehydrating operations in later stage.Afterwards, first, the refined whole liquid being dehydrated in storage tank is input in the 4th heat exchanger and is changed with steam
Heat, so that the temperature of refined end liquid rises to 85 DEG C or so, then is entered into neutralizing tank, feed liquid in regulation neutralizing tank
PH value, makes its pH value control between 5.5~6.5, and the feed liquid after neutralization is continued transported in evaporator, to avoid feed liquid peracid
Or cross alkali damage evaporator.In evaporator, first by evaporating preheater so that the temperature of feed liquid rises to more than 120 DEG C, so
Heating evaporation is carried out to it using saturated vapor afterwards, saturated vapor is temperature more than 220 DEG C, more than 2500kPa air pressure, via full
Heated with steam and cause that the temperature of feed liquid reaches more than 190 DEG C, as concentrate refined end liquid.Refined from the concentration of evaporator output
In whole liquid input separator, in the separator, make the moisture that the refined end liquid of concentration is contained within and the mixed gas that HCl is formed from liquid
Separated in phase, magnesium chloride concentrate is obtained.The mass fraction of magnesium chloride is in separator magnesium chloride concentrate out
More than 50%, it is pooled in liquid level tube, the liquid level tube is the buffer unit of granulating system charging.The gaseous mixture separated
Body is into being processed in vapor wash system.Material enters degassing tank from liquid level tube under gravity, in degassing tank
The pressure of material is down to atmospheric pressure, and being input in granulating working procedure via the material of degassing tank carries out granulation operations.
Step S24 granulation operations are as follows：
S24a：Magnesium chloride concentrate is set to pass sequentially through granulation centrifuge and granulation tower, so that the wet pellet of magnesium chloride is obtained；
S24b：Operation is dried to the wet pellet of magnesium chloride, so that water-free magnesium chloride granule is obtained.
Specifically, granulating system includes granulation centrifuge, granulation tower, belt conveyor, bucket elevator, vibratory sieve and wet
Particle feed bin.Magnesium chloride concentrate is sequentially entered in granulation centrifuge and granulation tower, and the granulation tower in the present embodiment is made for spray
Grain tower, magnesium chloride concentrate is scattered in the form of droplet and to the base falls of granulation tower, granulation tower at the top of granulation tower
Bottom constantly export the cold air of reverse convection current, therefore, droplet fall in granulation tower during cold sky with convection current
Gas is contacted so that the temperature of droplet is down to 60 DEG C or so, forms the solid particle of magnesium chloride hydrate, the as wet grain of magnesium chloride
Material.The wet pellet of magnesium chloride is delivered to bucket elevator by the belt conveyer of granulation tower bottom, is conveyed to drying system.In order to carry
The quality of the magnesium chloride pellet that this step high is produced, vibratory sieve is first delivered to by the wet pellet of magnesium chloride in bucket elevator
Sieved, the magnesium chloride wet granular for screening out size qualification is collected in wet granular feed bin, is then conveyed to drying system again.
The buffer unit that above-mentioned wet granular feed bin feeds as drying system.
Preferably, the drying process in step S24b includes air-drying option and hydrogen chloride drying process, wherein, air
Drying process is by Air Fluidized bed, so that the dry particl of magnesium chloride half is obtained, in the dry particl of magnesium chloride half by magnesium chloride concentrate
Every mole of magnesium chloride reclaimed water molecule content is less than 1.8 moles；Hydrogen chloride drying process is that the dry particl of magnesium chloride half is passed through into chlorine
Change hydrogen fluid bed, so that water-free magnesium chloride granule is obtained.
Further, above-mentioned hydrogen chloride drying process also includes tail gas clean-up operation and tail gas recycle operation, tail gas clean-up behaviour
As the tail gas for making the dry particl of magnesium chloride half be produced during hydrogen chloride fluid bed is dry sequentially pass through spray scrubber and
Condenser, to remove magnesium chloride dust and the moisture in tail gas, it is purified after hydrogen chloride gas put into hydrogen chloride drying again
Realize utilizing in operation.Tail gas recycle operation is that the liquid phase discarded object produced during tail gas clean-up is operated is input in Analytic Tower,
Magnesium chloride is used to realize parsing with to hydrogen chloride as extractant, it is real in the hydrogen chloride input hydrogen chloride drying process for parsing
Now utilize.
Specifically, magnesium chloride wet granular is exported from wet granular feed bin, is input into drying system, first in Air Fluidized bed
In hot air with 361 DEG C so that water content is reduced to every mole of magnesium chloride and contains 1.8 moles in magnesium chloride wet granular
Hydrone, formed the dry particl of magnesium chloride half.
Spray scrubber is provided with the top of air dryer, the air dryer during magnesium chloride wet granular is dry
The tail gas that can export of top by spray scrubber to remove magnesium chloride dust, through hydroperoxide scrubbing tower removing a large amount of chlorine
Change hydrogen, continue to purify the impurity in the tail gas to discharge standard by fine purifiation tower, be emitted into air.
The dry particl of magnesium chloride half subsequently enters redrying dehydration in hydrogen chloride drier, and the dry particl of magnesium chloride half is from chlorination
The top layer of hydrogen drier enters, and flows through the hydrogen chloride gas of every layer of column plate and 365 DEG C or so from hydrogen chloride drier bottom input
Body is inversely contacted, so that the water content in the dry particl of magnesium chloride half is reduced to the generation of less than 0.03%, MgOHCl back reactions
Magnesium chloride, so that its mass fraction is reduced to less than 0.2%, forms water-free magnesium chloride granule.Water-free magnesium chloride granule from
The bottom output of hydrogen chloride drier, into cooler, is cooled to less than 75 DEG C in cool drying air, and input bucket type is carried
In the machine of liter, it is transported in vibratory sieve by bucket elevator and is sieved, the bulky grain for screening out enters in useless particle feed bin, closes
The water-free magnesium chloride granule of lattice then enters in anhydrous particle feed bin, and wait enters electrowinning process.
Water-free magnesium chloride granule is obtained via above-mentioned dehydration procedure, electrowinning process is participated in as electrolyte beneficial to it, it is ensured that
The purity and water content of electrolyte, so as to ensure that the purity of magnesium metal liquid after electrolysis.
It is noted that being processed using tail gas clean-up operation from the tail gas of hydrogen chloride drier top output, make
It sequentially passes through spray scrubber to remove magnesium chloride dust, then by condenser to remove moisture content, it is purified after hydrogen chloride
Gas realizes circulation profit in being back to hydrogen chloride drier after compressor exchanges heat into realization in hydrogen chloride indirect heater
With.Because hydrogen chloride is soluble in water, in order to realize the saving to cost, the consumption of hydrogen chloride is reduced, the present embodiment also uses chlorine
Hydrogen chloride in the liquid phase removed in changing hydrogen retrieval operation to being operated in tail gas clean-up is realized further extracting, and is returned in hydrogen chloride
Bring drill to an end in work, the liquid phase removed through hydrogen chloride purifying device is recovered in Analytic Tower, using magnesium chloride as broken boiling agent, can beat
The constant boiling point of one's water breaks and hydrogen chloride so that hydrogen chloride is resolved out, and the hydrogen chloride for parsing is filled into hydrogen chloride drier
Realize recycling.
Tail gas clean-up is operated and the utilization of tail gas recycle operation not only solves the application of hydrogen chloride in this technique to environment
Pollution problem, and improve the utilization rate of hydrogen chloride, play cost-effective effect.
Step S3：Electrowinning process
Water-free magnesium chloride granule is input in electrolytic cell, makes it that electrochemical reaction occur as electrolyte, so that gold is obtained
Category magnesium liquid.
The reaction equation of electrolytic process is：MgCl2(l)→Mg(l)+Cl2(g)。
Specifically include S31~S32 steps：
S31：Water-free magnesium chloride granule is mixed with carbon dust and calcirm-fluoride, to form mixing pellet；
S32：Mixing pellet is transported in electrolytic cell and is electrolysed, so that magnesium metal liquid is obtained.
Specifically, as shown in figure 4, in electrowinning process, first sending out water-free magnesium chloride granule by air-transport system
Penetrate tank to be transported in the water-free magnesium chloride granule feed bin of potroom, water-free magnesium chloride granule is by induction system in electrolytic cell
Realize conveying, above-mentioned induction system includes rotary feeder, ribbon conveyer, high inclination angle conveyer, granule filling feed bin, anhydrous
Magnesium chloride Geldart-D particle sending cans, electrolytic cell intermediate bunker.Water-free magnesium chloride granule is transported to band by rotary feeder first
On formula conveyer, meanwhile, be transported to for a small amount of carbon dust and calcirm-fluoride also by the batcher of bottom by toner and calcirm-fluoride storehouse
On ribbon conveyer, mixing pellet is formed.Calcirm-fluoride has interfacial tension, can improve the tension force of electrolysis of magnesium chloride matter, is conducive to
Magnesium metal liquid enters in collection magnesium room.Carbon dust can lift the electric conductivity of electrolytic process, so as to promote the generation of cell reaction.
Mixing pellet is transported on high inclination angle conveyer by ribbon conveyer, and high inclination angle conveyer will mix pellet conveying
To in granule filling feed bin, mixing pellet is transported to anhydrous magnesium chloride strength by the rotatory feeder valve of granule filling bin bottom
In conveying sending cans, eventually enter into electrolytic cell intermediate bunker.Mix pellet in intermediate bunker to be added to by rotatory feeder valve
In electrolytic cell.In a cell, magnesium chloride is electrolysed in molten condition, and chlorine and magnesium metal are produced during electrolysis,
Wherein, magnesium metal is present in the form of liquid metal magnesium liquid.
During the anode sublimate produced in electrolytic process is pipelined to sack cleaner in the presence of chlorine blower fan
Filtering is realized, the chlorine gas transfer being filtrated to get in anode sublimate to PVC workshops is realized recycling, and other materials are then conveyed
To in anode sublimate dissolving tank, meanwhile, the solid waste settled in chlorine conveying pipelines is also together transported to anode liter
In magnificent thing dissolving tank, with water mixed dissolution after disposed waste liquid in surge tank by being pumped into anode sublimate, after treatment formed
Body refuse is sealed.
Wherein, anode preheating produce waste gas, anode sublimate dissolving produce waste gas, vacuum system produce waste gas with
And the chlorine unification of emergency episode leakage is transported in chlorine exhaust gas purification system, and air is emitted into after treatment.
Step S4：Casting process
Magnesium metal liquid is transported in casting machine and is cast, form magnesium ingot.
The step includes step S41~steps of S44 tetra-：
S41：Magnesium metal liquid is transported to foundry；
S42：It is transported in continuous refining furnace after excess electrolyte in removal magnesium metal liquid, so that simple metal magnesium liquid is obtained；
S43：Simple metal magnesium liquid is transported in casting machine, ingot mould is realized, magnesium ingot is obtained；
S44：Cooling, packing are realized to magnesium ingot and is stored.
Specifically, as shown in figure 5, the magnesium metal liquid that electrolysis is produced is extracted into car of two-maing ladle by vacuum system, by car of two-maing ladle
Foundry is transported to, into casting process.Foundry receives the magnesium metal liquid from electrowinning process, and magnesium metal is removed first
Electrolyte in liquid, the excess electrolyte in in-car magnesium metal liquid that will two-man ladle is discharged into melting salt stove, the metal in car of two-maing ladle
Magnesium liquid realizes refining in being then transported to continuous refining furnace.Continuous refining furnace includes multiple refining furnaces in series-operation, refining furnace
It is a kind of smelting equipment of hot-working industry.Magnesium metal liquid causes metal and non-under gravity during refining
Metal is separated, and isolated simple metal magnesium liquid is siphoned into casting from last furnace chamber of continuous refining furnace by pump of casting
Make and cast in machine, casting is a kind of metal heat processing technique, for the ease of the control conveyed to magnesium metal liquid, in continuous fine
Axle is configured with the import of the transfer pipeline set between furnace and casting machine expel heart pump.Simple metal magnesium liquid enters casting machine,
During simple metal magnesium liquid is cast, after simple metal magnesium liquid is cast to setting height in a mold, by servomotor to pure
Magnesium metal liquid transfer pipeline is lifted so that the imported valve of transfer pipeline is automatically switched off, and simple metal magnesium liquid stops outflow.For
The burning of simple metal magnesium liquid is prevented, after simple metal magnesium liquid injection mould, mould is transferred to by protection gas by ingot mould conveyer
Under cover, the protection gas of shunt offer is distributed with the protection gas hood, specifically, protection gas is dry air, carbon dioxide
And R134a, in the case where gas hood is protected, ingot mould is realized, magnesium ingot is obtained.Magnesium ingot is difficult cooling during solidifying, therefore magnesium ingot is taken off
Delivered to after mould in coolconveyer using Water spray, allow to cool to less than 60 DEG C.Magnesium ingot after cooling is packed and stored up
Deposit.
It is noted that raw material lake containing the magnesium salts material carries the accessory substance containing magnesium after potassium for bittern.
It refers to the technique that potash fertilizer is produced using salt lake bittern that bittern carries potassium, and potassium chloride, magnesium chloride ore deposit are rich in salt lake bittern,
The potassium chloride in bittern is selected as purpose ore deposit using floatation generally, the tail washings after potassium chloride is extracted and be can be used as this implementation
Raw material lake containing magnesium salts material in example.
In order to improve the purity of the magnesium metal prepared by the accessory substance containing magnesium after bittern carries potassium, preferably by the accessory substance containing magnesium
First being tedded via salt pan makes it separate out bischofite, is recycled the bischofite as raw material lake containing magnesium salts material.
The accessory substance containing magnesium after potassium is carried using bittern can be realized recycling it as raw material, both solve the wasting of resources
Problem, decreases its pressure to environment, while the magnesium metal and high concentration chlorine of high added value can also be prepared, has
There is application value very high.
Certainly, the raw material in the present invention can be also not limited to above-mentioned using the accessory substance containing magnesium in other salt lake bittern techniques
Bittern Potassium process.
A kind of production technology of magnesium metal is present embodiments provided, the difficulty that potash fertilizer produces liquid waste processing is on the one hand solved
Topic, the production for cleaning magnesium metal and high concentration chlorine is realized by comprehensive utilization, meets current metallurgy industry to environment friend
The developing direction of good type transformation.On the other hand, the technique can also realize that continuous automatic production goes out magnesium metal from salt lake bittern,
Realize and resource made full use of, and obtained by preparing magnesium metal yield is high, purity is high, with application value very high.
It should be noted that above-described embodiment the present invention will be described rather than limiting the invention, and this
Art personnel can design alternative embodiment without departing from the scope of the appended claims.In claim
In, any reference symbol being located between bracket should not be configured to limitations on claims.Word "comprising" is not excluded for depositing
In element or step not listed in the claims.
Claims (10)
1. a kind of production technology of magnesium metal, it is characterised in that comprise the following steps：
Step S1 refining steps：
Sulfate ion in the material of removal raw material lake containing magnesium salts and containing boron substance, so that refined whole liquid, the refined whole liquid is obtained
The content of middle sulfate ion is less than 20ppm；Boron contents are less than 1ppm；
Step S2 dehydration procedures：
The moisture in the refined whole liquid is removed, so that water-free magnesium chloride granule is obtained；
Step S3 electrowinning processes：
The water-free magnesium chloride granule is input in electrolytic cell, makes it that electrochemical reaction occur as electrolyte, so that gold is obtained
Category magnesium liquid；
Step S4 casting process：
The magnesium metal liquid is transported in casting machine and is cast, form magnesium ingot.
2. the production technology of magnesium metal according to claim 1, it is characterised in that the refining step includes primary purification
Operation S11 and secondary refining operation S12, wherein,
The primary purification operation S11 comprises the following steps：
S11a：Solid matter in raw material lake containing the magnesium salts material is dissolved using hot salt brine, so that the first refined liquid is obtained；
S11b：First refined liquid mixes with barium chloride solution, removes the sulfate radical in first refined liquid, to be obtained the
Two refined liquids；
S11c：Second refined liquid passes through inorganic membrane filtration unit, so that the 3rd refined liquid is obtained；
The secondary refining operation S12 is by boron polymeric adsorbent, to remove the 3rd refined liquid by the 3rd refined liquid
In containing boron substance, refined end liquid is obtained.
3. the production technology of magnesium metal according to claim 1, it is characterised in that the dehydration procedure S2 includes following step
Suddenly：
S21：Adjust the pH value of the refined whole liquid so that the pH value of the refined whole liquid is 5.5~6.5；
S22：Heating evaporation is realized to the refined whole liquid, so that the refined end liquid of concentration is obtained, is refined through the concentration after evaporation
The temperature of whole liquid is more than 190 DEG C；
S23：By the refined end liquid of the concentration by separator, to isolate the gaseous mixture in the refined end liquid of the concentration, it is obtained
Magnesium chloride concentrate, the mass fraction of magnesium chloride is more than 50% in the magnesium chloride concentrate；
S24：Granulation operations are realized to the magnesium chloride concentrate, so that water-free magnesium chloride granule, the anhydrous magnesium chloride is obtained
Mass fraction of the water content less than 0.03%, MgOHCl in grain is less than 0.2%.
4. the production technology of magnesium metal according to claim 3, it is characterised in that the granulation operations S24 includes as follows
Step：
S24a：The magnesium chloride concentrate is set to pass sequentially through granulation centrifuge and granulation tower, so that the wet pellet of magnesium chloride is obtained；
S24b：Operation is dried to the wet pellet of the magnesium chloride, so that water-free magnesium chloride granule is obtained.
5. the production technology of magnesium metal according to claim 4, it is characterised in that the drying process in the step S24b
Including air-drying option and hydrogen chloride drying process, wherein,
The air-drying option be by the magnesium chloride concentrate by Air Fluidized bed, so that magnesium chloride half dry particl is obtained,
Every mole of magnesium chloride reclaimed water molecule content is less than 1.8 moles in the dry particl of the magnesium chloride half；
The hydrogen chloride drying process is by hydrogen chloride fluid bed, so that anhydrous magnesium chloride is obtained by the dry particl of the magnesium chloride half
Particle.
6. the production technology of magnesium metal according to claim 5, it is characterised in that the hydrogen chloride drying process also includes
Tail gas clean-up is operated, and the tail gas clean-up operation is the dry particl of magnesium chloride half is produced during hydrogen chloride fluid bed is dry
Tail gas sequentially pass through spray scrubber and condenser, to remove magnesium chloride dust and the moisture in the tail gas, it is purified after
Hydrogen chloride gas to put into realize in hydrogen chloride drying process again and utilize.
7. the production technology of magnesium metal according to claim 6, it is characterised in that the hydrogen chloride drying-granulating operation is also
Including tail gas recycle operation, the tail gas recycle operation is that the liquid phase discarded object produced during tail gas clean-up is operated is input to parsing
In tower, magnesium chloride is used to realize parsing with to hydrogen chloride as broken boiling agent, the hydrogen chloride for parsing puts into the hydrogen chloride and does
Realize utilizing in dry operation.
8. the production technology of magnesium metal according to claim 1, it is characterised in that the electrowinning process S3 includes following step
Suddenly：
S31：The water-free magnesium chloride granule is mixed with carbon dust and calcirm-fluoride, to form mixing pellet；
S32：The mixing pellet is transported in electrolytic cell and is electrolysed, so that magnesium metal liquid is obtained.
9. the production technology of magnesium metal according to claim 1, it is characterised in that the casting process S4 includes following step
Suddenly：
S41：The magnesium metal liquid is transported to foundry；
S42：It is transported in continuous refining furnace after removing the excess electrolyte in the magnesium metal liquid, so that simple metal magnesium liquid is obtained；
S43：The simple metal magnesium liquid is transported in casting machine, ingot mould is realized, magnesium ingot is obtained；
S44：Cooling, packing are realized to the magnesium ingot and is stored.
10. the production technology of magnesium metal according to claim 1, it is characterised in that the material of lake containing magnesium salts is bittern
Carry the accessory substance containing magnesium after potassium.
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| CN107604119A (en) * | 2017-07-26 | 2018-01-19 | 象州县科学技术情报研究所 | Iron magnesium elements extraction process in barium sulfate production waste liquid |
| CN108396159A (en) * | 2018-03-19 | 2018-08-14 | 青海盐湖工业股份有限公司 | Brine refining device and Brine Purification Process in a kind of salt lake bittern magnesium technology |
| CN108507899A (en) * | 2018-04-04 | 2018-09-07 | 青海盐湖工业股份有限公司 | A kind of electrolytic metal magnesium slot slag analysis method |
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