CN104194421B - A kind of magnesium eletrolysis carbon pole protects material and application process thereof with immersion-type - Google Patents
A kind of magnesium eletrolysis carbon pole protects material and application process thereof with immersion-type Download PDFInfo
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- CN104194421B CN104194421B CN201410364583.6A CN201410364583A CN104194421B CN 104194421 B CN104194421 B CN 104194421B CN 201410364583 A CN201410364583 A CN 201410364583A CN 104194421 B CN104194421 B CN 104194421B
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Abstract
The invention belongs to molten magnesium chloride electrolysis tech field; particularly to a kind of magnesium eletrolysis carbon pole with immersion-type protection material and application process thereof; containing, for example the raw material of lower percent by weight in this protection material: calcium carbonate 8wt%～27wt%, boric acid 6wt%～15wt%, lithium carbonate 2wt%～8wt%, phosphate 1wt%～5wt%, Polyethylene Glycol 0.5wt%～3wt%, acetic acid 0.1wt%-2wt%, glycerol 0.4wt%-1.5wt%, surplus is water.Described protection material can form protective film on carbon pole surface; in the hot environment of the corrosive gas such as chlorine, steam, oxygen, the consumption of carbon pole can be significantly reduced, the corrosion resistance of intensifier electrode; extend the service life of carbon pole, reduce the production cost of enterprise.
Description
Technical field
The invention belongs to molten magnesium chloride electrolysis tech field, particularly to a kind of magnesium eletrolysis carbon pole with immersion-type protection material and application process thereof.
Background technology
Molten magnesium chloride electrolysis is the main method that the world today produces magnesium, and its yield accounts for more than the 60% of whole magnesium yield.Molten magnesium chloride electrolysis adopt not only can as negative electrode, but also can, as the carbon materials of anode as bipolar electrode, be inserted in the molten magnesium chloride electrolyte of 700 DEG C to 750 DEG C, negative electrode precipitates out magnesium, anode bears chlorine.The own open porosity of magnesium eletrolysis carbon pole (aobvious porosity) higher than 20%, high temperature corrosion gas immerse electrode interior, the combination destroyed between carbon particle along electrode opening hole, and make it come off from electrode surface.During the electrolysis of magnesium chloride, produce the comprehensive function washed away with burn into oxygen and steam oxidation of high temperature chlorine, be in more than molten magnesium chloride electrolysis liquid surface, electrode jaw is susceptible to local corrosion with lower part, occur carbon particle from carbon pole surfacial spalling, carbon pole basal area reduces, lose intensity and conducting function and scrap, enterprise have to ceaselessly change electrode, so not only bring significantly high production cost to enterprise, and have impact on the production efficiency of enterprise, add cost of labor.
By forming etching resistant film on carbon pole surface, it is improve one of its corrosion resistant effective ways.The main component of the anti-oxidation protection material being currently used for steel-making graphite electrode is made up of silicon dioxide, aluminium sesquioxide, titanium oxide, zirconium oxide, boric acid etc., and these materials all generate low-boiling chloride (Silicon chloride., boiling point 57.6 DEG C with high-temperature chlorine solid/liquid/gas reactions；Aluminum chloride, boiling point 178 DEG C；Titanium tetrachloride, boiling point-25 DEG C).These chlorides volatilize so that gaseous state exists at the temperature (700 DEG C～750 DEG C) of closing down magnesium electrolysis bath, it is impossible to form stable corrosion resistant protecting film on carbon pole surface.Namely high-temperature chlorine gas corrosion is not had protective action by existing graphite electrode anit-oxidizing protection material.
The present invention provides a kind of can stop the corrosion to carbon pole of high temperature chlorine, oxygen, steam effectively, thus the immersion-type protection material extending its service life.
Summary of the invention
It is an object of the invention to provide a kind of magnesium eletrolysis carbon pole immersion-type and protect material; this protection material can form the calcium carbonate boron oxide lithium oxide system protective film of densification on carbon pole surface; the heat resistance of this protective film own is higher than 750 DEG C, resistance to chlorine corrosivity is strong in a cell; energy stable existence is in carbon pole surface; reducing the apparent porosity (apparent porosity) of carbon pole stops under high temperature the corrosive gas such as chlorine, oxygen, steam along carbon pole open pores to its internal erosion effectively, extends the service life of carbon pole.
It is a further object to provide above-mentioned protection material and form the application process of protective film on carbon pole surface.
The immersion-type carbon pole protection material of the present invention, is the suspension of a kind of low viscosity, low surface tension.It is dipped in magnesium eletrolysis carbon pole open pores; drying, heat setting after carbon pole surface formed rivet protective film in carbon pole clearance gap; the bonding strength of protective film and carbon pole surface is greatly improved, and protective film has excellent thermal shock resistance.
Corresponding to each raw material used in immersion-type of the present invention protection material, the electrode potential of metal is lower than the electrode potential of magnesium metal, brings objectionable impurities without entering with the electrolysis of magnesium chloride into even if being mixed in electrolyte on a small quantity in magnesium metal.
In order to realize above technique effect, the present invention is achieved through the following technical solutions:
Material protected by a kind of closing down magnesium electrolysis bath immersion-type carbon pole, it is characterised in that: containing, for example the raw material of lower percent by weight in this protection material:
Surplus is water, it is preferred to distilled water.
Protecting in material at described carbon pole, the content of calcium carbonate accounts for the 8wt%～27wt% of raw material gross weight, it is preferred to 17wt%～21wt%.If the content of calcium carbonate is lower than 8wt%, protective film is lithium oxide under 750 DEG C of high temperature--boric oxide glass is too many mutually, and the heat resistance of thin film reduces；If its content is higher than 27wt%, lithium oxide--boric oxide glass is too low mutually, it is impossible to form fine and close and that carbon basal body bonding combined strength bination is high protective film.
The particle diameter of calcium carbonate is less than 5 μm, it is preferred to 0.1-1 μm.If its particle diameter is more than 5 μm, stability in aqueous is bad, and long-term placement is easily generated precipitate and separate；If its particle diameter is less than 0.1 μm, the cost of manufacture making carbon pole protection material is improved decades of times.
It is mainly composed of calcium carbonate as what magnesium eletrolysis carbon pole immersion-type protected protecting film that material formed at electrode surface, is at high temperature calcium chloride (CaCl with the product of chlorine reaction2).The boiling point of calcium chloride is 1935 DEG C, and fusing point is 772 DEG C, is above the use ambient temperature 750 DEG C of carbon pole, and what calcium chloride can be stable is present in electrode surface, dissolves in one of constituent becoming thin film in thin film.
Boric acid adds as filmogen and high-temperature agglomerant component; under high temperature, boric acid becomes boron oxide; just formation lithium oxide boric oxide glass phase can be reacted with lithium carbonate at about 400 DEG C; raise calcium carbonate with temperature and be gradually dissolved in wherein; generate heat resistance and be higher than 900 DEG C, fine and close boron oxide lithium oxide calcium carbonate protective film; meanwhile, the bonding combined strength bination of protective film and carbon pole surface is improved.In protection material, boric acid content is 6wt%～15wt%, it is preferred to 9wt%～10wt%.If its content is lower than 6wt%, the protective film of densification at high temperature can not be formed；If its content is higher than 15wt%, time more than 300 DEG C, because the volatilization of excessive boron oxide causes that the compactness of protective film reduces on the contrary.
Lithium carbonate adds as filmogen and high-temperature agglomerant component, just can react formation lithium oxide boric oxide glass phase with boron oxide at about 400 DEG C, the volatilization of inhibited oxidation boron simultaneously.In protection material, lithium carbonate content is 2wt%～8wt%, it is preferred to 3wt%～5wt%.If its content is lower than 2wt%, then the compactness of protective film is bad；If its content is higher than 8wt%, the heat resisting temperature making protective film is reduced.
Adding phosphate in described carbon pole protective agent, this phosphate is the one in calcium phosphate, dalcium biphosphate, magnesium phosphate, Magnesium biphosphate, aluminum phosphate, aluminium dihydrogen phosphate, sodium phosphate, potassium phosphate.Phosphate can improve the generation temperature of lithium oxide-boric oxide glass phase, dissolves in and improves its softening temperature in glassy phase, improves the heat resisting temperature of protective film.Phosphate, simultaneously as sclerosing agent, can form nonhygroscopic, stable protective film 200 DEG C of temperature below bakings.Meanwhile, phosphate is utilized to adjust in the scope that pH value is 4～6 of colloid solution.In protection material, phosphatic content is 1wt%～5wt%, it is desirable to for 1.5wt%～2.5wt%.If its content is lower than 1wt%, nonhygroscopic thin film cannot be formed under lower temperature (200 DEG C)；But when its content is higher than 5wt%, the stability of immersion-type protection material suspension reduces, and can not at room temperature preserve for a long time because gel polymerisation is too fast.
Protect the viscosity adding Polyethylene Glycol adjustment colloid solution in material at carbon pole, improve the stability of colloidal suspension liquid.In protection material, the addition of Polyethylene Glycol is 0.5wt%～3wt%, it is desirable to for 1.5wt%～2.5wt%.If its content is lower than 0.5wt%, then not having the purpose improving stability of suspension, addition is too much, and viscosity is too high is unfavorable for dip operation.
In described carbon pole protection material, acetic acid and glycerol add in protection material respectively as the dispersant and stabilizer disperseing calcium carbonate fine powder.The addition of acetic acid is 0.1wt%-2wt%, it is preferred to 0.2wt%, and acetic acid substantially generates, with calcium carbonate reaction, the calcium acetate (CH being dissolved in water3COO)2Ca and remain in the product.
The addition 0.4wt%-1.5wt% of glycerol.It is preferably 0.5wt%; in order to reduce the specific surface tension of protection material, improve protection material suspension and carbon pole affinity (wettability), be conducive to protection material to the dipping in carbon pole minute aperture; meanwhile, the addition of glycerol also improves the stability of protection material suspension.
Described calcium carbonate, boric acid, lithium carbonate and the 30%-40% that phosphatic weight sum is raw material total amount；Described Polyethylene Glycol, acetic acid, G & W the 60-70% that weight sum is raw material total amount.The carbon pole immersion-type protection material suspension that such proportioning prepares at room temperature can be stored 3 months; wherein dispersed particle does not precipitate; viscosity, without notable rising, is entirely capable of meeting the transport of commercial Application middle and long distance, long time stored to stability of material requirement.
Described protection material is suspension dispersion liquid, and its apparent viscosity is less than 100mPa 〃 s, and surface tension is lower than 80mN/m.
Above-mentioned magnesium eletrolysis carbon pole immersion-type is protected material be impregnated in the clearance gap of carbon pole and be attached to carbon pole surface by the method adopting Dipping or evacuation decompression immersion coating, drying, form rivet protective film in carbon pole clearance gap on carbon pole surface after heat setting, its step includes: be impregnated in by carbon pole sample in magnesium eletrolysis carbon pole immersion-type protection material, take out after in soaking 20～40 minutes, dry under 18 DEG C～30 DEG C conditions, then heat up gradually, toast 2 hours at the temperature of 200 DEG C～220 DEG C.
Pickup is carbon pole sample weight the 3～4% of described magnesium eletrolysis carbon pole immersion-type protection material；At the temperature of 200-220 DEG C after baking, the gross weight weightening finish 1.0%～1.2% of carbon pole sample.
The invention has the beneficial effects as follows:
1, described magnesium eletrolysis carbon pole immersion-type protection material can form protective film on carbon pole surface; the heat resisting temperature of this protecting film is higher than 900 DEG C; what under high temperature, energy was stable is attached to carbon pole surface; the apparent porosity making carbon pole is reduced to less than 8% by 24%; significantly reduce the surface area of carbon pole, improve the ability of carbon pole corrosion resistance high temperature chlorine and oxygen, vapor corrosion.
2, chlorine, steam, nitrogen mixed gas hot environment in, described immersion-type carbon pole protection material can significantly reduce the etching extent of carbon pole.The loss of weight percent of the carbon pole sample of dipping protection material is lower than 25.6%, and the loss of weight percent being not impregnated with the carbon pole sample of protection material is 53.4%.
3, in magnesium chloride electrolytic cell, described immersion-type carbon pole protection material can make the corrosion depletion rate of carbon pole reduce by more than 80%, extends more than 4 times electrode life.
Accompanying drawing explanation
Fig. 1 is the apparent porosity comparison diagram of dipping the closing down magnesium electrolysis bath immersion-type carbon pole protection material prepared by embodiment 4 and the carbon pole sample being not impregnated with protection material.
Fig. 2 is that the closing down magnesium electrolysis bath immersion-type carbon pole being impregnated with prepared by embodiment 1 to embodiment 6 is protected material and is not impregnated with the carbon pole sample protecting material loss of weight percent comparison diagram after heating corrosion-resistant test.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
The mean diameter of the calcium carbonate used in following embodiment is 0.2 μm, phosphate employing dalcium biphosphate, and other all uses chemical pure medicine, water self-control distilled water.
Embodiment 1
The raw material components of described magnesium eletrolysis electrode protection immersion-type carbon materials comprises 27.0wt% calcium carbonate, 6.0wt% boric acid, 2.0wt% lithium carbonate, 2.0wt% dalcium biphosphate, 1.5wt% Polyethylene Glycol, 0.5wt% glycerol, 0.2wt% acetic acid, 60.8wt% water.After protecting material filming with magnesium eletrolysis carbon pole with immersion-type, solid constituent calculates, and calcium carbonate content is 72.9wt%, and boric acid content is 22.2wt%, and lithium carbonate content is 7.4wt%, and biphosphate calcium content is 7.4wt%.
Embodiment 2
The raw material components of described magnesium eletrolysis carbon pole immersion-type protection material comprises 15.0wt% calcium carbonate, 15.0wt% boric acid, 5.0wt% lithium carbonate, 2.0wt% dalcium biphosphate, 1.5wt% Polyethylene Glycol, 0.5wt% glycerol, 0.2wt% acetic acid, 60.8wt% water.After protecting material filming with magnesium eletrolysis carbon pole with immersion-type, solid constituent calculates, and calcium carbonate content is 40.5wt%, and boric acid content is 40.5wt%, and lithium carbonate content is 18.5wt%, and biphosphate calcium content is 5.4wt%.
Embodiment 3
The raw material components of described magnesium eletrolysis carbon pole immersion-type protection material comprises 23.0wt% calcium carbonate, 7.0wt% boric acid, 5.0wt% lithium carbonate, 2.0wt% dalcium biphosphate, 1.5wt% Polyethylene Glycol, 0.5wt% glycerol, 0.2wt% acetic acid, 60.8wt% water.After protecting material filming with magnesium eletrolysis carbon pole with immersion-type, solid constituent calculates, and calcium carbonate content is 62.2wt%, and boric acid content is 18.9wt%, and lithium carbonate content is 13.5wt%, and biphosphate calcium content is 5.4wt%.
Embodiment 4
The raw material components of described magnesium eletrolysis carbon pole immersion-type protection material comprises 21.0wt% calcium carbonate, 10.5wt% boric acid, 3.5wt% lithium carbonate, 2.0wt% dalcium biphosphate, 1.5wt% Polyethylene Glycol, 0.5wt% glycerol, 0.2wt% acetic acid, 60.8wt% water.After protecting material filming with magnesium eletrolysis carbon pole with immersion-type, solid constituent calculates, and calcium carbonate content is 56.8wt%, and boric acid content is 28.4wt%, and lithium carbonate content is 9.5wt%, and biphosphate calcium content is 5.4wt%.
In the immersion-type protection material that carbon pole sample dipping is prepared in the present embodiment; after the temperature calcination of 600 DEG C～800 DEG C, its apparent porosity is reduced to about 8% by 24%; namely the surface area of carbon pole is greatly reduced, and substantially increases the corrosion resistance of carbon pole sample.It is not impregnated with the control sample protecting material apparent porosity after the temperature calcination of 600 DEG C～800 DEG C and is then risen to about 28% by about 24%, specifically as shown in Figure 1.
Embodiment 5
The raw material components of described magnesium eletrolysis carbon pole immersion-type protection material comprises 19.0wt% calcium carbonate, 11.0wt% boric acid, 5.0wt% lithium carbonate, 2.0wt% dalcium biphosphate, 1.5wt% Polyethylene Glycol, 0.5wt% glycerol, 0.2wt% acetic acid, 60.8wt% water.After protecting material filming with magnesium eletrolysis carbon pole with immersion-type, solid constituent calculates, and calcium carbonate content is 51.4wt%, and boric acid content is 29.7wt%, and lithium carbonate content is 13.2wt%, and biphosphate calcium content is 13.5wt%.
Embodiment 6
The raw material components of described magnesium eletrolysis electrode protection immersion-type carbon materials comprises 17.0wt%, calcium carbonate, 12.0wt% boric acid, 3.0wt% lithium carbonate, 5.0wt% dalcium biphosphate, 1.5wt% Polyethylene Glycol, 0.5wt% glycerol, 0.2wt% acetic acid, 60.8wt% water.After protecting material filming with magnesium eletrolysis carbon pole with immersion-type, solid constituent calculates, and calcium carbonate content is 42.1wt%, and boric acid content is 31.6wt%, and lithium carbonate content is 10.5wt%, and biphosphate calcium content is 15.8wt%.
Corrosion resistance is tested:
From apparent porosity be 24.3%, purity be 99.99% carbon pole cut the cylindrical sample of diameter 10mm, high 30mm.Sample is divided into two groups, and one group of practical example 1 of dipping is to the protection material prepared by practical example 6, and another is organized sample as a comparison and does not do the process of dipping protection material.
Sample is respectively put into practical example 1 to the protection material of practical example 6, soaks and take out from protection material for about 30 minutes, after the room temperature through 1 day is dried, standby after toasting 2 hours at 200 DEG C.Pickup is carbon element sample weight the 3～4% of protection material.After 200 DEG C of bakings, the weightening finish of sample is 1.0～1.2%.Dried sample is weighed, as the weight of sample before corrosion testing.
The sample of dipping protection material and the sample being not impregnated with protection material are put on the sample bench of the tube type resistance furnace that two ends seal simultaneously, is warming up to 750 DEG C of constant temperature 24 hours.In thermostatic process, in the flask of 120 DEG C, instill concentrated hydrochloric acid generation chlorine to enclosing manganese oxide particle, constant temperature, pass in the boiler tube that chlorine is imported tube type resistance furnace by nitrogen.The chlorine contained exhaust gas that tube type resistance furnace is discharged is by emptying after 4 sodium hydroxide solution tanks absorptions.
In stove, take out sample, remove with the hairbrush loose dust by specimen surface and carbon granule, be weighed as the weight of sample after corrosion.
Sample weight × 100% before sample loss of weight percentage ratio=(before corrosion sample weight after sample weight-corrosion) ÷ corrosion
Test result is as shown in Figure 2; temperature be 750 DEG C, in the environment of chlorine, steam, nitrogen mixed gas; the loss of weight percent of the carbon pole sample of dipping protection material is lower than 25.6%, and the loss of weight percent being not impregnated with the carbon pole sample of protection material is 53.4%；Particularly the loss of weight percent of practical 4,5,6 three samples of example is lower than 6.2%, is only not impregnated with the 1/9 of sample loss of weight percent.It is indicated above that protection material prepared by the present invention can be greatly improved carbon pole corrosion resistance in high-temperature chlorine gas and water steam.
Corrosion-resistant comparative evaluation test in magnesium chloride electrolytic cell:
The carbon pole of protection material prepared by the present invention will be impregnated with and do not use the carbon pole of protection material to be immersed in electrolysis of magnesium chloride liquid simultaneously; the practical service environment of carbon pole is observed their surface corrosion situation, the corrosivity of their high temperature resistant chlorine of comparative evaluation, steam, oxygen etc..
The method that carbon pole dipping protection material adopts evacuation decompression dipping.After dipping protection material, electrode weightening finish 1.82wt%, 220 DEG C of bakings 6 as a child rear electrode weightening finish 0.51wt%.
Above-mentioned dipping protection material and do not impregnate after the carbon pole of protection material uses 23 days in a cell, the electrode surface being not impregnated with protection material reaches 37mm because burn into peels off the depth capacity causing surface recessed, and average every day, corrosion thickness was about 1.6mm；Corresponding, impregnated of the carbon pole of protection material, to employ 111 days recessed depth capacitys in rear surface be 28mm, and average every day, corrosion thickness was about 0.25mm；It is indicated above; in magnesium chloride electrolytic cell; the corrosion rate using the carbon pole of the immersion-type protection material of the present invention does not only use the 16% of the carbon pole of protection material; namely immersion-type protection material can make the corrosion rate of carbon pole reduce by more than 84%, extends its service life more than 4 times.
The above is presently preferred embodiments of the present invention, but the present invention should not be limited to this embodiment disclosure of that.So every without departing from the equivalence completed under spirit disclosed in this invention or amendment, both fall within the scope of protection of the invention.
Claims (4)
1. a magnesium eletrolysis carbon pole immersion-type protects material, it is characterised in that: containing, for example the raw material of lower percent by weight in this protection material:
Described magnesium eletrolysis carbon pole immersion-type protection material is by Dipping or evacuation decompression dipping; material is protected to be immersed in the open pores of carbon pole magnesium eletrolysis carbon pole immersion-type; dry through 18-30 DEG C, after the temperature of 200-220 DEG C is toasted, then form protective film.
2. magnesium eletrolysis carbon pole immersion-type according to claim 1 protects material, it is characterised in that: the 17wt%～21wt% that calcium carbonate is raw material gross weight contained in described electrode protection material, the particle diameter of this calcium carbonate is less than 5 μm.
3. magnesium eletrolysis carbon pole immersion-type according to claim 1 protects material, it is characterised in that: described phosphate is the one in calcium phosphate, dalcium biphosphate, magnesium phosphate, Magnesium biphosphate, sodium phosphate, potassium phosphate.
4. magnesium eletrolysis carbon pole immersion-type according to claim 1 protects material; it is characterized in that: described protection material is suspension dispersion liquid; its apparent viscosity is less than 100mPa s, and surface tension, lower than 80mN/m, can be impregnated in the open pores of carbon pole.
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| JPS6131309A (en) * | 1984-07-23 | 1986-02-13 | Tokai Carbon Co Ltd | Antioxidizing agent of graphite electrode for steel making |
| CN101343753A (en) * | 2008-08-15 | 2009-01-14 | 昆明理工大学 | Electrode coated with high temperature oxidation resistant ceramic paint and manufacture method thereof |
| CN101985764A (en) * | 2010-10-08 | 2011-03-16 | 九台市科工碳业有限责任公司 | Antioxidation processing method of graphite anode for preparing calcium by electrolysis |
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