CN1224478C - Magnesium and magnesium alloy pelletizing method - Google Patents
Magnesium and magnesium alloy pelletizing method Download PDFInfo
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- CN1224478C CN1224478C CN 02133257 CN02133257A CN1224478C CN 1224478 C CN1224478 C CN 1224478C CN 02133257 CN02133257 CN 02133257 CN 02133257 A CN02133257 A CN 02133257A CN 1224478 C CN1224478 C CN 1224478C
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Abstract
The present invention provides a method of granulation by magnesium and magnesium alloy, which belongs to the colored metallurgical technique. The present invention comprises the steps: the liquid-state magnesium, or the magnesium alloy is heated; salt additive is prepared; the liquid-state magnesium, or the magnesium alloy and the salt additive are added to a centrifugal granulation apparatus; the mixture of the liquid-state magnesium, or the magnesium alloy and salt are splashed to form liquid drops under the action of centrifugal force; the liquid drops are cooled by air until the liquid drops are solidified to form a spherical shape, and are coated with a layer of magnesium granules, or magnesium alloy granules of a salt shell, and granules of salt agent. The present invention is characterized in that the salt additive is composed of chloride of magnesium, sodium and kalium, and fluoride; before the salt additive is added to the centrifugal granulation apparatus, the salt additive is heated to the temperature of 800 DEG C from the temperature of 740 DEG C, and formed magnesium liquid drops, or magnesium alloy liquid drops are cooled by air to reach the temperature of 200 to 300 DEG C in a flight track; afterwards, the temperature of the product is reduced to be 100 to 150 DEG C, and the product is sent away by compressed air along a pipeline; then, a roller sieve separates the magnesium granules, or the magnesium alloy granules from the salt additive.
Description
Affiliated technical field
The present invention relates to a kind ofly with magnesium and magnesium alloy process for granulating, is to the improvement of existing technology with magnesium and magnesium alloy granulation, belongs to non-ferrous metallurgy technology.
Background technology
At present; the known salt magnesium grain preparation method that is coated with has several; for example; the method that is coated with salt magnesium grain of producing is disclosed among the United States Patent (USP) № 4186000 and 4410356; be included in mixing that continual injection magnesium and salt mixture (salt mixture is made up of the salt of alkali metal and alkaline-earth metal) do not stop in the crucible (blender); the two ratio is that 42 parts of molten magnesiums account for 58～68% to 58 parts of fuse salts or magnesium in the mixture total weight amount; its objective is magnesium is disperseed to become tiny droplet; from blender, derive the fuse salt that contains thin loose magnesium globule or magnesium alloy pearl then; and make it rapidly cooling in order to avoid be dispersed in magnesium globule or the mutual adhesion of magnesium alloy pearl in the salt; pulverize cooled mixture afterwards; to destroy crisp salt body and to isolate magnesium globule or the Mg-alloy particles that is contained in wherein, the back is exactly that magnesium grain or Mg-alloy particles that the surface is surrounded by the thin salt film of one deck are scatter with pulverous salt again.For guaranteeing nodularization and make magnesium grain or the Mg-alloy particles that granularity meets the requirements, to blender (crucible) in, add a kind of in the following material: MgO, diffusing carbon and boron-containing compound carefully at least.
This method will consume a large amount of salt (account for weight metal 32～58%), even and products obtained therefrom still contains a large amount of salt after mechanical treatment, this certainly will make its serviceability variation.In addition, for not making magnesium globule or the mutual adhesion of magnesium alloy pearl that has disperseed and making spherical particle with designated size, also must add things such as infusibility additive MgO, boron and carbon in fused salt, this also can reduce the quality (containing MgO, boron and carbon etc. in the particle) of final products.
United States Patent (USP) № 3881913 also discloses the preparation method of a kind of magnesium and magnesium alloy particles, this method comprises: molten magnesium or magnesium alloy heating, the salt additives (additive is made up of the halogen compound of magnesium, alkali metal and alkaline-earth metal) that in melt, adds 0.5～20% weight metal, then the mixture centrifugal atomizing of metal and salt is become to drip and make the metal of formation drip cooling in air, the outside promptly scribbled one deck salt film before metal dropped in and solidifies balling-up.The salt additives consumption is 10～20% of a motlten metal weight when producing spherical magnesium grain and Mg-alloy particles in this way, if the salt additives consumption is reduced to below 10%, just can be scaled to the content of irregularly shaped particles in the product (needle-like grain, spindle shape grain etc.), this can make the mobility of particle variation, thereby can make those processes that require good fluidity use this material that difficulty takes place.
The consumption of salt additives big (10～20%) can make the salt content in the particle magnesium increase; this serviceability in finished product has negative effect: the content of main useful component (activated carbon) descends in the particle; hygroscopicity increases, and particle is understood the adhesion caking and had corrosivity under the moisture content effect in atmosphere.The particularly hygroscopic salt (CaCl of tool
2, BaCl
2And MgCl
2) influence bigger.The barium chloride that adds for increase salt agent proportion in the US Patent No 3881913 still is a kind of Toxic.
Need not to add the compound of infusibility when adopting this method in the salt agent, because nodularization problem and granularity control problem are owing to having adopted the centrifugal granulating device and having used different cooling means (droplet of formation in its flight track with the cooling of air stream) and obtained solution.
Summary of the invention
The objective of the invention is to overcome the prior art above shortcomings; by US Patent No 3881913 method that provides is improved; provide a kind of can be in (grain shape aspect every leading indicator; the salt agent content; toxicity etc.) improve particle magnesium quality with magnesium and magnesium alloy process for granulating; this method is by providing more good granulation condition and the particle cooling condition afterwards and the separation condition of salt agent; by the selection that salt additives is formed; to the selection of heating cycle and cooling system and in conjunction with to solidifying the additional machining of back particle, reached the purpose of invention.
What the present invention provided is this with magnesium and magnesium alloy process for granulating; mainly include liquid magnesium or magnesium alloy are heated in 670～720 ℃ the temperature range; the salt additives that preparation is made of the chloride and the fluoride of alkali metal and alkaline-earth metal; liquid magnesium or magnesium alloy and salt additives are added in the centrifugal granulating device simultaneously in the mode that continues to flow; wherein salt accounts for 20% of weight metal; the mixture of liquid magnesium or magnesium alloy and salt splashes under centrifugal action and is refined into drop; the thin drop that looses with the air cooling up to being cured as spherical and scribbling magnesium grain or the Mg-alloy particles and the salt additives particle of one deck salt crust; it is characterized in that this salt additives is is 4～6% by magnesium chloride; sodium chloride is: 33～48%; potassium chloride is: 45～60%; fluorine with the fluorine ionometer in the magnesium fluoride is: 0.2～0.5%; surplus is formed for oxidation of impurities magnesium; this salt additives was heated to 800 ℃ from 740 ℃ earlier before adding the centrifugal granulating device; and the outside that forms is surrounded by the thin magnesium drop or the magnesium alloy drop of loosing of salt additives film; then in its flight track, be cooled to 200～350 ℃ by air; afterwards product being carried along pipeline with compressed air and carried out mechanical treatment and cool to 110～150 ℃, is that the rotary screen of 0.5 * 0.5mm is separated magnesium grain or the same salt additives of having worn into smalls of Mg-alloy particles with the hole order again.
Description of drawings
A kind of process chart that accompanying drawing provides for the present invention with magnesium and magnesium alloy process for granulating.Number in the figure is: 1, liquid magnesium or magnesium alloy, 2, salt additives, 3, the centrifugal granulating device, 4, cooling chamber, 5, air, 6, rotary screen, 7, particle magnesium or particle magnesium alloy.
The specific embodiment
Below in conjunction with accompanying drawing concrete technical scheme of the present invention is described further:
As shown in the figure, in this embodiment that provides, at first the salt additives that chloride and fluoride constituted 2 of magnesium, sodium, potassium is heated to 800 ℃ from 740 ℃ in advance, and is added in the centrifugal granulating device 3 with liquid magnesium or magnesium alloy 1 in the mode of uninterrupted current; Then the thin dispersed metallic tear drop that is surrounded by one deck salt film that generates is cooled to 200 ℃～350 ℃ with air 5 on its flight track in cooling chamber 4, sends into rotary screen 6 afterwards in pipeline so that the salt additives that grinds is screened out with 0.5 * 0.5mm screen cloth; Particle magnesium after will sieving at last or particle magnesium alloy 7 are packed as finished product.
Above-mentioned technological operation is only interosculated and could be guaranteed to produce the high-quality particle, and this situation is confirmed (seeing Table 1) to the test that the present invention did under industrial condition.Listed data are the data that draw on the commerical test device in the table.
Test shows, only just can reach the best combination of its physical property and chemical property based on the salt additives that chloride and fluoride were constituted of magnesium, sodium, potassium.
In this case, the melting temperature of salt mixture may be lower than or be higher than the melting temperature of magnesium or magnesium alloy and its proportion even a little less than (low 0.05～0.1g/cm
3) proportion of particle alloy, the requirement to salt additives in this point and the US Patent No 3881913 is different.Therefore, determine in the present patent application that the basic norm that salt additives is formed is: hygroscopicity is minimum, and toxicity is minimum, and is minimum with the adhesion strength of magnesium grain or Mg-alloy particles.As everyone knows, in fluoride, the hygroscopicity of magnesium fluoride and calcirm-fluoride is minimum, and in chloride, the hygroscopicity of sodium chloride and potassium chloride is minimum.The addition of magnesium chloride must minimum (being not more than 6%), in order that will reduce melting temperature, calcirm-fluoride and magnesium fluoride can reduce the hygroscopicity of salt mixture, but can improve its melting temperature, and have certain toxicity.But adding calcirm-fluoride or the magnesium fluoride salt film ratio that also helps particle surface that combines with sodium chloride on a small quantity is easier to grind and separate.The composition of salt additives can be referring to the test bit scope that provides among the embodiment; but its claimed scope is not limited to test given number range; wherein magnesium chloride is: 4～6%; sodium chloride is: 33～48%; potassium chloride is 45～60%; fluorine with fluorine ionometer in the fluoride (for example calcirm-fluoride or magnesium fluoride) is: 0.2～0.5%, and surplus is an oxidation of impurities magnesium.Salt additives with composition like this is heated to higher temperature (740～800 ℃) in advance to be helped realizing above-mentioned every.
Salt mixture is heated to the temperature higher than metal, and the salt film can drip just that the surface is rapidly wandering comes at magnesium, thereby has prevented that magnesium from contacting with airborne oxygen and burn; And when being cooled fast to 200～350 ℃, then because various physical properties (coefficient of cubical expansion and the compressed coefficient of salt additives and magnesium, surface tension etc.) cause the crisp and be full of cracks of particle surface salt film, this helps at product during along the pneumatic conveying of steel pipe, the salt agent worn into be powder less than 0.5mm, but fast cooling to 100～150 ℃ simultaneously.
Particle must drop to below 350 ℃ during with air cooling-down in flight track, because if be higher than this temperature, magnesium grain (Mg-alloy particles especially, because of its aluminum content higher) might still be in the liquid state.And the speed of the temperature of magnesium and magnesium alloy oxidation near its fusing point (〉=400～450 ℃) time can sharply be accelerated.Cooling to is irrational equally below 200 ℃, because this will strengthen the overall dimensions of granulation chamber and significantly increase cooling air quantity.
In next stage, promptly in the steel pipe road, carry with compressed air and when rubbing the salt agent further cooling be effective and economical.These two kinds of factors of compressed-air actuated mechanism and fast cooling (dropping to 110～150 ℃ from 200～350 ℃) combine, and have guaranteed the salt agent is ground to operating efficiency less than the 0.5mm granularity, are screened out on 0.5 * 0.5mm rotary screen then.
The temperature range that must keep during the rotary screen operation depends on to prevent that screen cloth is by the wetting possibility of water in air vapour.If screen cloth is wetted, then salt agent meeting sticks to eyelet is diminished, thereby rotary screen production capacity is reduced, and the salt agent particle that makes moist is sticked on the metallic particles and enters finished product.
Therefore, from pipeline, come out and when entering rotary screen the temperature of particle should not be lower than 110～150 ℃, this is in order to make its temperature when the sieve tool comes out be not less than 100 ℃, has so just got rid of the possibility of making moist in screening stage and packing stage salt agent afterwards.
Table 1 the present invention and existing technology are with the result of the test of magnesium and magnesium alloy granulation
| Sequence number | Salt additives is formed % (weight) | Metal | Salt agent temperature ℃ | Salt agent consumption % | Chilling temperature in the cooling chamber ℃ | Temperature ℃ before the screening | Product performance | ||||||
| Magnesium chloride | Sodium chloride | Potassium chloride | Barium chloride | Fluorine ion | Magnesia | Salt amount % | Spherolite % | ||||||
| 1 | 10 | 30 | 56 | 3 | 0.6 | 0.4 | Magnesium | 730 | 20 | - | - | 12 | 95 |
| 2 | 14 | 25 | 50 | 10 | 0.7 | 0.3 | Magnesium alloy 9% aluminium 0.8% zinc 0.2% manganese | 720 | 20 | - | - | 10 | 92 |
| 3 | 5 | 40 | 54.5 | 0 | 0.4 | 0.1 | Magnesium | 740 | 20 | 200 | 110 | 2.5 | 99.0 |
| 4 | 5 | 45 | 49.6 | 0 | 0.3 | 0.1 | Magnesium | 800 | 15 | 350 | 150 | 2.0 | 98.5 |
| 5 | 5 | 40 | 54.5 | 0 | 0.4 | 0.1 | Magnesium alloy 9% aluminium 0.75% zinc 0.15 % manganese | 750 | 20 | 200 | 110 | 2.5 | 99.0 |
| 6 | 6 | 40 | 53.6 | 0 | 0.3 | 0.1 | Magnesium alloy 9% aluminium 0.75% zinc 0.15 % manganese | 800 | 18 | 340 | 140 | 3.0 | 98.6 |
Annotate: 1. fluorine ion is the ion concentration of fluorine in calcirm-fluoride or the magnesium fluoride.
2. sequence number 1 and sequence number 2 are the numerical value of prior art, and sequence number 3～sequence number 6 is a test bit of the present invention.
3. particle magnesium sample kept in the atmosphere of humidity after 24 hours, and its weightening finish situation is as follows: sequence number 1 increases 0.7%, and sequence number 2 increases 0.9%, and sequence number 3～sequence number 6 increases 0.3%～0.45%.
Claims (1)
1; a kind of with magnesium and magnesium alloy process for granulating; mainly include liquid magnesium or magnesium alloy are heated in 670～720 ℃ the temperature range; the salt additives that preparation is made of the chloride and the fluoride of alkali metal and alkaline-earth metal; liquid magnesium or magnesium alloy and salt additives are added in the centrifugal granulating device simultaneously in the mode that continues to flow; wherein salt accounts for 20% of weight metal; the mixture of liquid magnesium or magnesium alloy and salt splashes under centrifugal action and is refined into drop; the thin drop that looses with the air cooling up to being cured as spherical and scribbling magnesium grain or the Mg-alloy particles and the salt additives particle of one deck salt crust; it is characterized in that this salt additives is to be by magnesium chloride: 4～6%; sodium chloride is: 33～48%; potassium chloride is: 45～60%; fluorine with the fluorine ionometer in the magnesium fluoride is: 0.2～0.5%; surplus is formed for oxidation of impurities magnesium; this salt additives was heated to 800 ℃ from 740 ℃ earlier before adding the centrifugal granulating device; and the outside that forms is surrounded by the thin magnesium drop or the magnesium alloy drop of loosing of salt additives film; then in its flight track, be cooled to 200～350 ℃ by air; afterwards product being carried along pipeline with compressed air and carried out mechanical treatment and cool to 110～150 ℃, is that the rotary screen of 0.5 * 0.5mm is separated magnesium grain or the same salt additives of having worn into smalls of Mg-alloy particles with the hole order again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02133257 CN1224478C (en) | 2002-10-24 | 2002-10-24 | Magnesium and magnesium alloy pelletizing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02133257 CN1224478C (en) | 2002-10-24 | 2002-10-24 | Magnesium and magnesium alloy pelletizing method |
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| Publication Number | Publication Date |
|---|---|
| CN1491763A CN1491763A (en) | 2004-04-28 |
| CN1224478C true CN1224478C (en) | 2005-10-26 |
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|---|---|---|---|
| CN 02133257 Expired - Fee Related CN1224478C (en) | 2002-10-24 | 2002-10-24 | Magnesium and magnesium alloy pelletizing method |
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|---|---|---|---|---|
| CN101974665B (en) * | 2010-11-29 | 2012-07-04 | 湖南斯瑞摩科技有限公司 | Magnesium, magnesium alloy and wastes thereof based production line for producing particle magnesium desulfurizing agent/particle magnesium alloy desulfurizing agent |
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