CN103466649B - A kind of self-spreading metallurgical legal system is for the clean preparation method of ultra fine boride powder - Google Patents
A kind of self-spreading metallurgical legal system is for the clean preparation method of ultra fine boride powder Download PDFInfo
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Abstract
Self-spreading metallurgical legal system, for a clean preparation method for ultra fine boride powder, is carried out according to the following steps: (1) by ball milling after the mixing of metal oxide, boron oxide and magnesium powder, then is pressed into blank, puts into self-propagating reaction stove and causes self-propagating reaction; Naturally cool to normal temperature, obtain thick product; (2) thick product is adopted Leaching in Hydrochloric Acid after fragmentation, filter and obtain solid phase and leach liquor; (3) leach the solid phase washing and drying obtained, make ultra fine boride powder; (4) the mode process leach liquor of spray-wall interaction is adopted; Obtain nanoscale magnesium and pyrolysis tail gas; Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns leaching process and recycles.The present invention adopts the mode of self-spreading metallurgical to produce superfine powder, have that raw materials cost is low, energy consumption is low, simple to operate, the features such as low are required to processing condition, and the purity of product is high, granularity is little, powder activity is high.
Description
Technical field
The invention belongs to metallurgical technology field, particularly a kind of self-spreading metallurgical legal system is for the clean preparation method of ultra fine boride powder.
Background technology
Superfine powder technology of preparing is with modern high technology and new material industry, one that grows up as microelectronics and information technology, high-performance ceramics and refractory materials, polymer composites materials, biochemical industry, aerospace, new forms of energy etc. and conventional industries technical progress and comprehensive utilization of resources and deep processing etc. new engineering, an emerging integrated technology science, significant to the development of modern high technology industry.
The technology of preparing of superfine powder from large scope can be divided into the current industrial use of vapor phase process, liquid phase method and solid phase method maximum be comminuting method, using aforesaid method to prepare superfine powder, to there is energy consumption high more, the shortcomings such as cost is high, complex process.Compared with aforementioned production method, adopt self-spreading metallurgical method to produce the superfine powders such as refractory metal powder, amorphous boron powder or boride ceramics powder to have that raw materials cost is low, energy consumption is low, simple to operate, the features such as low are required to processing condition, and the purity of product is high, granularity is little, powder activity is high.Self-propagating High-temperature Synthesis Process and metallurgical extract technology combine by Northeastern University, (patent No. is respectively ZL200510047297.8 for the new technology of superfine powder to have invented self-spreading metallurgical legal system, ZL200510047308.2, ZL201010233471.9, ZL201010233478.0, ZL200810011972.5), by raw material mixing such as oxide compound and reductive agent magnesium powder, be placed in self-propagating reaction stove after being pressed into base sample, self-propagating reaction is caused with local igniting or the constant temperature means such as to detonate, cooling obtains the thick product of product disperse in spongiform magnesium oxide matrix, then be at room temperature that leaching agent directly leaches thick product with diluted acid, filtering separation obtains superfine powder, a large amount of acid magnesium-containing waste solutions is created at leaching process owing to introducing acid leaching process.
Summary of the invention
For the problems referred to above that self-spreading metallurgical legal system exists for superfine powder process, the invention provides the clean preparation method of a kind of self-spreading metallurgical legal system for ultra fine boride powder, namely hydrochloric acid is adopted to be the thick product that leaching agent leaching SHS process obtains, removing magnesium oxide wherein, filtering separation obtains superfine powder and magnesium chloride solution, then magnesium chloride solution is directly carried out spray-wall interaction and obtain nanoscale magnesium powder, obtain hydrogen chloride gas simultaneously, hydrogen chloride gas can return leaching process recycle after absorbing, realize the cleaner production of this process.
Self-spreading metallurgical legal system of the present invention is carried out according to the following steps for the clean preparation method of ultra fine boride powder:
1, be milled to granularity≤0.5 μm after metal oxide, boron oxide and magnesium powder being mixed, be then pressed into blank, put into self-propagating reaction stove and cause self-propagating reaction; Described metal oxide is ytterbium oxide, cerium oxide, zirconium white, lanthanum trioxide, Neodymium trioxide, Samarium trioxide, calcium oxide or titanium oxide;
After self-propagating reaction terminates, reaction product naturally cools to normal temperature, obtains thick product, and the metal boride disperse in thick product is in spongy magnesium oxide matrix;
2, by thick product after fragmentation, adopt the mode of Leaching in Hydrochloric Acid to be separated magnesium oxide wherein; Leaching the concentration of hydrochloric acid adopted is 1 ~ 5mol/L; The liquid-solid ratio of hydrochloric acid and thick product is (4 ~ 20): 1ml/g, leaches the mode of mode or the high temperature leaching in confined conditions adopting normal temperature to leach; When normal temperature leaches, extraction temperature is 25 ~ 90 DEG C, extraction time is 10 ~ 40h; When high temperature leaches, extraction temperature is 100 ~ 150 DEG C, extraction time is 30 ~ 180min; Filter after leaching and obtain solid phase and leach liquor;
3, leach the solid phase washing obtained and remove impurity, then moisture is removed in oven dry, makes the ultra fine boride powder of purity by weight >=99%;
4, the mode process leach liquor of spray-wall interaction is adopted; Spray-wall interaction by atomizing nozzle, leach liquor is carried out atomization winding-up in high temperature pyrolysis stove under the pressure of 0.13 ~ 0.6MPa, and reheating solution obtains nanoscale magnesium and pyrolysis tail gas; Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns leaching process and recycles; Pyrolysis temperature in high temperature pyrolysis stove is 200 ~ 700 DEG C, pyrolysis time is 0.5 ~ 60min.
In aforesaid method, pressure when being pressed into blank is 40 ~ 70MPa.
In aforesaid method, when metal oxide is ytterbium oxide, blending ratio is ytterbium oxide in mass ratio: boron oxide: magnesium powder=100:(100 ~ 115): (135 ~ 160), when metal oxide is cerium oxide, blending ratio is cerium oxide in mass ratio: boron oxide: magnesium powder=100:(110 ~ 130): (160 ~ 185), when metal oxide is zirconium white, blending ratio is zirconium white in mass ratio: boron oxide: magnesium powder=100:(60 ~ 65): (105 ~ 122), when metal oxide is lanthanum trioxide, blending ratio is lanthanum trioxide in mass ratio: boron oxide: magnesium powder=100:(120 ~ 135): (160 ~ 185), when metal oxide is Neodymium trioxide, blending ratio is Neodymium trioxide in mass ratio: boron oxide: magnesium powder=100:(118 ~ 132): (160 ~ 185), when metal oxide is Samarium trioxide, blending ratio is Samarium trioxide in mass ratio: boron oxide: magnesium powder=100:(115 ~ 127): (155 ~ 180), when metal oxide is calcium oxide, blending ratio is calcium oxide in mass ratio: boron oxide: magnesium powder=100:(335 ~ 390): (450 ~ 515), when metal oxide is titanium oxide, blending ratio is titanium oxide in mass ratio: boron oxide: magnesium powder=100:(90 ~ 95): (155 ~ 180).
The general formula of above-mentioned self-propagating reaction is as follows:
MeO
x+y/2B
2O
3+(x+3y/2)Mg=MeB
y+(x+3y/2)MgO+△H
Wherein Me is Y, Ce, Zr, La, Nd, Sm, Ca or Ti, and △ H represents the reaction heat of self-propagating reaction generating process reaction release;
In aforesaid method, leaching process reaction is as follows:
MgO+2HCl=MgCl
2+H
2O；
In aforesaid method, the reaction of thermal decomposition process is as follows:
MgCl
2+H
2O=MgO+2HCl。
Above-mentioned ultra fine boride powder is the titanium boride powder of the ytterbium boride powder of granularity≤300nm, the cerium boride powder of granularity≤400nm, the boronation zirconium powder of granularity≤400nm, the lanthanum boride powder of granularity 0.8 ~ 3.0 μm, the neodymium boride powder of granularity≤0.5 μm, the samarium boride powder of granularity≤0.5 μm, the boronation calcium powder of granularity 0.8 ~ 2.5 μm or granularity≤0.5 μm.
In above-mentioned leach liquor, the mass concentration of magnesium chloride is 50 ~ 300g/L.
Above-mentioned nanoscale magnesium granularity be 80 ~ 390nm.
The concentration of the hydrochloric acid that above-mentioned hydrogenchloride is formed after absorbing is 1 ~ 5mol/L.
In aforesaid method, self-propagating reaction is divided into direct initiation and constant temperature to detonate two kinds; Direct initiation is direct heating blank in air atmosphere, and till self-propagating reaction occurs, now can form dazzling flame, and have a large amount of cigarettes to volatilize, the temperature of reaction system raises rapidly; Constant temperature detonates and refers in air atmosphere, heating blank, and temperature controls between 720 ~ 950 DEG C, and till self-propagating reaction occurs, now can form dazzling flame, and have a large amount of cigarettes to volatilize, the temperature of reaction system raises rapidly.
Because self-propagating reaction occurs under the air atmosphere opened wide, and self-propagating reaction temperature is very high, and in reaction process, the gasification of metal magnesium amount, can cause a large amount of volatilization loss of Mg, and such Mg will be not enough; In order to make up the volatilization loss of Mg, the present invention is MAGNESIUM METAL more excessive than reaction theory requirement 5 ~ 25% when preparing burden; Simpler in order to make self-propagating reaction operate, self-propagating reaction also can adopt partial points pyrogenic process to cause.
Compared with traditional superfine powder technology of preparing, feature of the present invention and beneficial effect are:
(1) adopt the mode of self-spreading metallurgical to produce superfine powder, have that raw materials cost is low, energy consumption is low, simple to operate, the features such as low are required to processing condition, and the purity of product is high, granularity is little, powder activity is high;
(2) adopt the mode process magnesium chloride solution of spray-wall interaction, reaction efficiency is high, can obtain nanoscale magnesium products, improve added value of product;
(3) acid that produces of production process and water can realize recycle by thermal decomposition process, achieve whole process without useless clean
Produce.
Accompanying drawing explanation
Fig. 1 is the clean preparation method process flow diagram of a kind of self-spreading metallurgical legal system of the present invention for ultra fine boride powder.
Embodiment
The magnesium powder, boron oxide, ytterbium oxide, cerium oxide, zirconium white, lanthanum trioxide, Neodymium trioxide, Samarium trioxide, calcium oxide and the titanium oxide that adopt in the embodiment of the present invention are technical grade product, granularity all≤0.5mm.
The self-propagating reaction stove adopted in the embodiment of the present invention is the disclosed self-propagating reaction stove of patent " ZL200510047308.2 ", and this Reaktionsofen is made up of reaction vessel, well heater, sight glass, transformer, function recording instrument, thermopair, gas valve.
In the embodiment of the present invention, the time of self-propagating reaction is 5 ~ 90s.
In the embodiment of the present invention, solid phase water carried out filtration washing in washing, and the acid wash water of acquisition is used for the moisture of Leaching in Hydrochloric Acid process replenish loss.
In the embodiment of the present invention, drying time is at least 24h.
The high temperature pyrolysis stove adopted in the embodiment of the present invention is tube furnace.
In the embodiment of the present invention be pressed into blank time the blank that is pressed into be the cylindric of diameter 5-10cm.
The equipment that in the embodiment of the present invention, ball milling adopts is high energy ball mill.
Embodiment 1
Be milled to granularity≤0.5 μm after ytterbium oxide, boron oxide and magnesium powder being mixed, be then pressed into blank, put into self-propagating reaction stove and cause self-propagating reaction; Blending ratio is ytterbium oxide in mass ratio: boron oxide: magnesium powder=100:100:135; Pressure when being pressed into blank is 40MPa;
After self-propagating reaction terminates, reaction product naturally cools to normal temperature, obtains thick product, and the ytterbium boride disperse in thick product is in spongy magnesium oxide matrix;
By thick product after fragmentation, the mode of employing Leaching in Hydrochloric Acid is separated magnesium oxide wherein; Leaching the concentration of hydrochloric acid adopted is 1mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 4:1ml/g, and leach the mode adopting normal temperature to leach, extraction temperature is 25 DEG C, extraction time is 40h; Filter after leaching and obtain solid phase and leach liquor; In leach liquor, the mass concentration of magnesium chloride is 50g/L;
Leach the solid phase washing obtained and remove impurity, then moisture is removed in oven dry, make the ultra-fine ytterbium boride powder of purity by weight >=99%, granularity is at 150 ~ 300nm;
Adopt the mode process leach liquor of spray-wall interaction; Spray-wall interaction by atomizing nozzle, leach liquor is carried out atomization winding-up in high temperature pyrolysis stove under the pressure of 0.13MPa, and reheating solution obtains nanoscale magnesium and pyrolysis tail gas; Nanoscale magnesium granularity be 80 ~ 150nm;
Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns leaching process and recycles, and the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 1mol/L; Pyrolysis temperature in high temperature pyrolysis stove is 500 DEG C, pyrolysis time is 5min.
Embodiment 2
Method is with embodiment 1, and difference is:
(1) blending ratio is ytterbium oxide in mass ratio: boron oxide: magnesium powder=100:115:160; Pressure when being pressed into blank is 50MPa;
(2) leaching the concentration of hydrochloric acid adopted is 3mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 8:1ml/g, and leach the mode adopting normal temperature to leach, extraction temperature is 50 DEG C, extraction time is 20h; In leach liquor, the mass concentration of magnesium chloride is 150g/L;
(3) spray-wall interaction leach liquor is carried out atomization winding-up in high temperature pyrolysis stove by atomizing nozzle under the pressure of 0.25MPa, nanoscale magnesium granularity be 100 ~ 220nm, the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 3mol/L; Pyrolysis temperature is 700 DEG C, pyrolysis time is 0.5min.
Embodiment 3
Method is with embodiment 1, and difference is:
(1) blending ratio is ytterbium oxide in mass ratio: boron oxide: magnesium powder=100:109:142; Pressure when being pressed into blank is 60MPa;
(2) leaching the concentration of hydrochloric acid adopted is 5mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 20:1ml/g, and leach the mode adopting normal temperature to leach, extraction temperature is 90 DEG C, extraction time is 10h; In leach liquor, the mass concentration of magnesium chloride is 300g/L;
(3) spray-wall interaction leach liquor is carried out atomization winding-up in high temperature pyrolysis stove by atomizing nozzle under the pressure of 0.6MPa, nanoscale magnesium granularity be 320 ~ 390nm, the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 5mol/L; Pyrolysis temperature is 200 DEG C, pyrolysis time is 60min.
Embodiment 4
Be milled to granularity≤0.5 μm after cerium oxide, boron oxide and magnesium powder being mixed, be then pressed into blank, put into self-propagating reaction stove and cause self-propagating reaction; Blending ratio is cerium oxide in mass ratio: boron oxide: magnesium powder=100:110:160; Pressure when being pressed into blank is 40MPa;
After self-propagating reaction terminates, reaction product naturally cools to normal temperature, obtains thick product, and the cerium boride disperse in thick product is in spongy magnesium oxide matrix;
By thick product after fragmentation, the mode of employing Leaching in Hydrochloric Acid is separated magnesium oxide wherein; Leaching the concentration of hydrochloric acid adopted is 1mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 4:1ml/g, and leach the mode adopting normal temperature to leach, extraction temperature is 25 DEG C, extraction time is 40h; Filter after leaching and obtain solid phase and leach liquor; In leach liquor, the mass concentration of magnesium chloride is 50g/L;
Leach the solid phase washing obtained and remove impurity, then moisture is removed in oven dry, make the ultra-fine cerium boride powder of purity by weight >=99%, granularity is at 150 ~ 400nm;
Adopt the mode process leach liquor of spray-wall interaction; Spray-wall interaction by atomizing nozzle, leach liquor is carried out atomization winding-up in high temperature pyrolysis stove under the pressure of 0.13MPa, and reheating solution obtains nanoscale magnesium and pyrolysis tail gas; Nanoscale magnesium granularity be 80 ~ 150nm;
Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns leaching process and recycles, and the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 1mol/L; Pyrolysis temperature in high temperature pyrolysis stove is 500 DEG C, pyrolysis time is 5min.
Embodiment 5
Method is with embodiment 1, and difference is:
(1) blending ratio is cerium oxide in mass ratio: boron oxide: magnesium powder=100:130:185; Pressure when being pressed into blank is 50MPa;
(2) leaching the concentration of hydrochloric acid adopted is 3mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 8:1ml/g, and leach the mode adopting normal temperature to leach, extraction temperature is 50 DEG C, extraction time is 20h; In leach liquor, the mass concentration of magnesium chloride is 150g/L;
(3) spray-wall interaction leach liquor is carried out atomization winding-up in high temperature pyrolysis stove by atomizing nozzle under the pressure of 0.25MPa, nanoscale magnesium granularity be 100 ~ 220nm, the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 3mol/L; Pyrolysis temperature is 700 DEG C, pyrolysis time is 0.5min.
Embodiment 6
Method is with embodiment 1, and difference is:
(1) blending ratio is cerium oxide in mass ratio: boron oxide: magnesium powder=100:120:175; Pressure when being pressed into blank is 60MPa;
(2) leaching the concentration of hydrochloric acid adopted is 5mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 20:1ml/g, and leach the mode adopting normal temperature to leach, extraction temperature is 90 DEG C, extraction time is 10h; In leach liquor, the mass concentration of magnesium chloride is 300g/L;
(3) spray-wall interaction leach liquor is carried out atomization winding-up in high temperature pyrolysis stove by atomizing nozzle under the pressure of 0.6MPa, nanoscale magnesium granularity be 320 ~ 390nm, the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 5mol/L; Pyrolysis temperature is 200 DEG C, pyrolysis time is 60min.
Embodiment 7
Be milled to granularity≤0.5 μm after zirconium white, boron oxide and magnesium powder being mixed, be then pressed into blank, put into self-propagating reaction stove and cause self-propagating reaction; Blending ratio is zirconium white in mass ratio: boron oxide: magnesium powder=100:60:105; Pressure when being pressed into blank is 70MPa;
After self-propagating reaction terminates, reaction product naturally cools to normal temperature, obtains thick product, and the zirconium boride 99.5004323A8ure disperse in thick product is in spongy magnesium oxide matrix;
By thick product after fragmentation, the mode of employing Leaching in Hydrochloric Acid is separated magnesium oxide wherein; Leaching the concentration of hydrochloric acid adopted is 4mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 5:1ml/g, and leach the mode adopting high temperature in confined conditions to leach, extraction temperature is 100 ~ 150 DEG C, extraction time is 180min; Filter after leaching and obtain solid phase and leach liquor; In leach liquor, the mass concentration of magnesium chloride is 60g/L;
Leach the solid phase washing obtained and remove impurity, then moisture is removed in oven dry, make the ultra-fine boronation zirconium powder of purity by weight >=99%, granularity is at 200 ~ 400nm;
Adopt the mode process leach liquor of spray-wall interaction; Spray-wall interaction by atomizing nozzle, leach liquor is carried out atomization winding-up in high temperature pyrolysis stove under the pressure of 0.15MPa, and reheating solution obtains nanoscale magnesium and pyrolysis tail gas; Nanoscale magnesium granularity be 280 ~ 360nm;
Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns leaching process and recycles, and the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 4mol/L; Pyrolysis temperature in high temperature pyrolysis stove is 300 DEG C, pyrolysis time is 40min.
Embodiment 8
Method is with embodiment 1, and difference is:
(1) blending ratio is zirconium white in mass ratio: boron oxide: magnesium powder=100:65:122; Pressure when being pressed into blank is 60MPa;
(2) leaching the concentration of hydrochloric acid adopted is 2mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 10:1ml/g, and leach the mode adopting high temperature in confined conditions to leach, extraction temperature is 100 ~ 150 DEG C, extraction time is 90min; In leach liquor, the mass concentration of magnesium chloride is 200g/L;
(3) spray-wall interaction leach liquor is carried out atomization winding-up in high temperature pyrolysis stove by atomizing nozzle under the pressure of 0.4MPa, nanoscale magnesium granularity be 180 ~ 300nm, the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 2mol/L; Pyrolysis temperature is 400 DEG C, pyrolysis time is 30min.
Embodiment 9
Method is with embodiment 1, and difference is:
(1) blending ratio is zirconium white in mass ratio: boron oxide: magnesium powder=100:63:110; Pressure when being pressed into blank is 50MPa;
(2) leaching the concentration of hydrochloric acid adopted is 5mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 18:1ml/g, and leach the mode adopting high temperature in confined conditions to leach, extraction temperature is 100 ~ 150 DEG C, extraction time is 30min; In leach liquor, the mass concentration of magnesium chloride is 220g/L;
(3) spray-wall interaction leach liquor is carried out atomization winding-up in high temperature pyrolysis stove by atomizing nozzle under the pressure of 0.5MPa, nanoscale magnesium granularity be 180 ~ 250nm, the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 5mol/L; Pyrolysis temperature is 300 DEG C, pyrolysis time is 10min.
Embodiment 10
Be milled to granularity≤0.5 μm after lanthanum trioxide, boron oxide and magnesium powder being mixed, be then pressed into blank, put into self-propagating reaction stove and cause self-propagating reaction; Blending ratio is lanthanum trioxide in mass ratio: boron oxide: magnesium powder=100:120:160; Pressure when being pressed into blank is 40MPa;
After self-propagating reaction terminates, reaction product naturally cools to normal temperature, obtains thick product, and the lanthanum boride disperse in thick product is in spongy magnesium oxide matrix;
By thick product after fragmentation, the mode of employing Leaching in Hydrochloric Acid is separated magnesium oxide wherein; Leaching the concentration of hydrochloric acid adopted is 4mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 6:1ml/g, and leach the mode adopting normal temperature to leach, extraction temperature is 90 DEG C, extraction time is 10h; Filter after leaching and obtain solid phase and leach liquor; In leach liquor, the mass concentration of magnesium chloride is 220g/L;
Leach the solid phase washing obtained and remove impurity, then moisture is removed in oven dry, make the ultra-fine lanthanum boride powder of purity by weight >=99%, granularity is at 0.8 ~ 3.0 μm;
Adopt the mode process leach liquor of spray-wall interaction; Spray-wall interaction by atomizing nozzle, leach liquor is carried out atomization winding-up in high temperature pyrolysis stove under the pressure of 0.2MPa, and reheating solution obtains nanoscale magnesium and pyrolysis tail gas; Nanoscale magnesium granularity be 110 ~ 220nm;
Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns leaching process and recycles, and the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 4mol/L; Pyrolysis temperature in high temperature pyrolysis stove is 200 DEG C, pyrolysis time is 1min.
Embodiment 11
Method is with embodiment 1, and difference is:
(1) blending ratio is lanthanum trioxide in mass ratio: boron oxide: magnesium powder=100:135:185; Pressure when being pressed into blank is 50MPa;
(2) leaching the concentration of hydrochloric acid adopted is 3mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 12:1ml/g, and leach the mode adopting normal temperature to leach, extraction temperature is 25 DEG C, extraction time is 40h; In leach liquor, the mass concentration of magnesium chloride is 105g/L;
(3) spray-wall interaction leach liquor is carried out atomization winding-up in high temperature pyrolysis stove by atomizing nozzle under the pressure of 0.3MPa, nanoscale magnesium granularity be 280 ~ 390nm, the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 3mol/L; Pyrolysis temperature is 700 DEG C, pyrolysis time is 50min.
Embodiment 12
Method is with embodiment 1, and difference is:
(1) blending ratio is lanthanum trioxide in mass ratio: boron oxide: magnesium powder=100:130:170; Pressure when being pressed into blank is 60MPa;
(2) leaching the concentration of hydrochloric acid adopted is 2mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 20:1ml/g, and leach the mode adopting normal temperature to leach, extraction temperature is 80 DEG C, extraction time is 15h; In leach liquor, the mass concentration of magnesium chloride is 120g/L;
(3) spray-wall interaction leach liquor is carried out atomization winding-up in high temperature pyrolysis stove by atomizing nozzle under the pressure of 0.4MPa, nanoscale magnesium granularity be 80 ~ 120nm, the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 2mol/L; Pyrolysis temperature is 200 DEG C, pyrolysis time is 60min.
Embodiment 13
Be milled to granularity≤0.5 μm after Neodymium trioxide, boron oxide and magnesium powder being mixed, be then pressed into blank, put into self-propagating reaction stove and cause self-propagating reaction; Blending ratio is Neodymium trioxide in mass ratio: boron oxide: magnesium powder=100:118:160; Pressure when being pressed into blank is 70MPa;
After self-propagating reaction terminates, reaction product naturally cools to normal temperature, obtains thick product, and the neodymium boride disperse in thick product is in spongy magnesium oxide matrix;
By thick product after fragmentation, the mode of employing Leaching in Hydrochloric Acid is separated magnesium oxide wherein; Leaching the concentration of hydrochloric acid adopted is 1mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 4:1ml/g, leaches that the mode extraction temperature adopting high temperature in confined conditions to leach is 100 ~ 150 DEG C, extraction time is 100min; Filter after leaching and obtain solid phase and leach liquor; In leach liquor, the mass concentration of magnesium chloride is 50g/L;
Leach the solid phase washing obtained and remove impurity, then moisture is removed in oven dry, make the ultra-fine neodymium boride powder of purity by weight >=99%, granularity is at 0.2 ~ 0.5 μm;
Adopt the mode process leach liquor of spray-wall interaction; Spray-wall interaction by atomizing nozzle, leach liquor is carried out atomization winding-up in high temperature pyrolysis stove under the pressure of 0.5MPa, and reheating solution obtains nanoscale magnesium and pyrolysis tail gas; Nanoscale magnesium granularity be 90 ~ 160nm;
Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns leaching process and recycles, and the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 1mol/L; Pyrolysis temperature in high temperature pyrolysis stove is 300 DEG C, pyrolysis time is 40min.
Embodiment 14
Method is with embodiment 1, and difference is:
(1) blending ratio is Neodymium trioxide in mass ratio: boron oxide: magnesium powder=100:132:185; Pressure when being pressed into blank is 60MPa;
(2) leaching the concentration of hydrochloric acid adopted is 2mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 10:1ml/g, and leach the mode adopting high temperature in confined conditions to leach, extraction temperature is 100 ~ 150 DEG C, extraction time is 60min; In leach liquor, the mass concentration of magnesium chloride is 120g/L;
(3) spray-wall interaction leach liquor is carried out atomization winding-up in high temperature pyrolysis stove by atomizing nozzle under the pressure of 0.6MPa, nanoscale magnesium granularity be 120 ~ 230nm, the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 2mol/L; Pyrolysis temperature is 400 DEG C, pyrolysis time is 20min.
Embodiment 15
Method is with embodiment 1, and difference is:
(1) blending ratio is Neodymium trioxide in mass ratio: boron oxide: magnesium powder=100:122:171; Pressure when being pressed into blank is 50MPa;
(2) leaching the concentration of hydrochloric acid adopted is 3mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 20:1ml/g, and leach the mode adopting high temperature in confined conditions to leach, extraction temperature is 100 ~ 150 DEG C, extraction time is 150min; In leach liquor, the mass concentration of magnesium chloride is 180g/L;
(3) spray-wall interaction leach liquor is carried out atomization winding-up in high temperature pyrolysis stove by atomizing nozzle under the pressure of 0.18MPa, nanoscale magnesium granularity be 180 ~ 290nm, the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 3mol/L; Pyrolysis temperature is 500 DEG C, pyrolysis time is 10min.
Embodiment 16
Be milled to granularity≤0.5 μm after Samarium trioxide, boron oxide and magnesium powder being mixed, be then pressed into blank, put into self-propagating reaction stove and cause self-propagating reaction; Blending ratio is Samarium trioxide in mass ratio: boron oxide: magnesium powder=100:115:155; Pressure when being pressed into blank is 40MPa;
After self-propagating reaction terminates, reaction product naturally cools to normal temperature, obtains thick product, and the samarium boride disperse in thick product is in spongy magnesium oxide matrix;
By thick product after fragmentation, the mode of employing Leaching in Hydrochloric Acid is separated magnesium oxide wherein; Leaching the concentration of hydrochloric acid adopted is 4mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 18:1ml/g, and leach the mode adopting normal temperature to leach, extraction temperature is 25 DEG C, extraction time is 40h; Filter after leaching and obtain solid phase and leach liquor; In leach liquor, the mass concentration of magnesium chloride is 210g/L;
Leach the solid phase washing obtained and remove impurity, then moisture is removed in oven dry, make the ultra-fine samarium boride powder of purity by weight >=99%, granularity is at 0.35 ~ 0.5 μm;
Adopt the mode process leach liquor of spray-wall interaction; Spray-wall interaction by atomizing nozzle, leach liquor is carried out atomization winding-up in high temperature pyrolysis stove under the pressure of 0.24MPa, and reheating solution obtains nanoscale magnesium and pyrolysis tail gas; Nanoscale magnesium granularity be 200 ~ 300nm;
Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns leaching process and recycles, and the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 4mol/L; Pyrolysis temperature in high temperature pyrolysis stove is 600 DEG C, pyrolysis time is 50min.
Embodiment 17
Method is with embodiment 1, and difference is:
(1) blending ratio is Samarium trioxide in mass ratio: boron oxide: magnesium powder=100:127:180; Pressure when being pressed into blank is 50MPa;
(2) leaching the concentration of hydrochloric acid adopted is 5mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 16:1ml/g, and leach the mode adopting normal temperature to leach, extraction temperature is 90 DEG C, extraction time is 10h; In leach liquor, the mass concentration of magnesium chloride is 240g/L;
(3) spray-wall interaction leach liquor is carried out atomization winding-up in high temperature pyrolysis stove by atomizing nozzle under the pressure of 0.35MPa, nanoscale magnesium granularity be 200 ~ 290nm, the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 5mol/L; Pyrolysis temperature is 700 DEG C, pyrolysis time is 0.5min.
Embodiment 18
Method is with embodiment 1, and difference is:
(1) blending ratio is Samarium trioxide in mass ratio: boron oxide: magnesium powder=100:123:169; Pressure when being pressed into blank is 60MPa;
(2) leaching the concentration of hydrochloric acid adopted is 5mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 10:1ml/g, and leach the mode adopting normal temperature to leach, extraction temperature is 30 DEG C, extraction time is 30h; In leach liquor, the mass concentration of magnesium chloride is 150g/L;
(3) spray-wall interaction leach liquor is carried out atomization winding-up in high temperature pyrolysis stove by atomizing nozzle under the pressure of 0.48MPa, nanoscale magnesium granularity be 80 ~ 160nm, the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 5mol/L; Pyrolysis temperature is 700 DEG C, pyrolysis time is 1min.
Embodiment 19
Be milled to granularity≤0.5 μm after calcium oxide, boron oxide and magnesium powder being mixed, be then pressed into blank, put into self-propagating reaction stove and cause self-propagating reaction; Blending ratio is calcium oxide in mass ratio: boron oxide: magnesium powder=100:335:450; Pressure when being pressed into blank is 70MPa;
After self-propagating reaction terminates, reaction product naturally cools to normal temperature, obtains thick product, and the calcium boride disperse in thick product is in spongy magnesium oxide matrix;
By thick product after fragmentation, the mode of employing Leaching in Hydrochloric Acid is separated magnesium oxide wherein; Leaching the concentration of hydrochloric acid adopted is 4mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 6:1ml/g, and leach the mode adopting high temperature in confined conditions to leach, extraction temperature is 100 ~ 150 DEG C, extraction time is 120min; Filter after leaching and obtain solid phase and leach liquor; In leach liquor, the mass concentration of magnesium chloride is 80g/L;
Leach the solid phase washing obtained and remove impurity, then moisture is removed in oven dry, make the ultra-fine boronation calcium powder of purity by weight >=99%, granularity is at 0.8 ~ 2.5 μm;
Adopt the mode process leach liquor of spray-wall interaction; Spray-wall interaction by atomizing nozzle, leach liquor is carried out atomization winding-up in high temperature pyrolysis stove under the pressure of 0.55MPa, and reheating solution obtains nanoscale magnesium and pyrolysis tail gas; Nanoscale magnesium granularity be 160 ~ 220nm;
Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns leaching process and recycles, and the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 4mol/L; Pyrolysis temperature in high temperature pyrolysis stove is 600 DEG C, pyrolysis time is 5min.
Embodiment 20
Method is with embodiment 1, and difference is:
(1) blending ratio is calcium oxide in mass ratio: boron oxide: magnesium powder=100:390:515; Pressure when being pressed into blank is 60MPa;
(2) leaching the concentration of hydrochloric acid adopted is 3mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 10:1ml/g, and leach the mode adopting high temperature in confined conditions to leach, extraction temperature is 100 ~ 150 DEG C, extraction time is 90min; In leach liquor, the mass concentration of magnesium chloride is 90g/L;
(3) spray-wall interaction leach liquor is carried out atomization winding-up in high temperature pyrolysis stove by atomizing nozzle under the pressure of 0.6MPa, nanoscale magnesium granularity be 140 ~ 190nm, the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 3mol/L; Pyrolysis temperature is 500 DEG C, pyrolysis time is 20min.
Embodiment 21
Method is with embodiment 1, and difference is:
(1) blending ratio is calcium oxide in mass ratio: boron oxide: magnesium powder=100:365:495; Pressure when being pressed into blank is 50MPa;
(2) leaching the concentration of hydrochloric acid adopted is 2mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 15:1ml/g, and leach the mode adopting high temperature in confined conditions to leach, extraction temperature is 100 ~ 150 DEG C, extraction time is 60min; In leach liquor, the mass concentration of magnesium chloride is 100g/L;
(3) spray-wall interaction leach liquor is carried out atomization winding-up in high temperature pyrolysis stove by atomizing nozzle under the pressure of 0.13MPa, nanoscale magnesium granularity be 220 ~ 300nm, the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 2mol/L; Pyrolysis temperature is 300 DEG C, pyrolysis time is 40min.
Embodiment 22
Be milled to granularity≤0.5 μm after titanium oxide, boron oxide and magnesium powder being mixed, be then pressed into blank, put into self-propagating reaction stove and cause self-propagating reaction; Blending ratio is titanium oxide in mass ratio: boron oxide: magnesium powder=100:90:155; Pressure when being pressed into blank is 40MPa;
After self-propagating reaction terminates, reaction product naturally cools to normal temperature, obtains thick product, and the titanium boride disperse in thick product is in spongy magnesium oxide matrix;
By thick product after fragmentation, the mode of employing Leaching in Hydrochloric Acid is separated magnesium oxide wherein; Leaching the concentration of hydrochloric acid adopted is 1mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 5:1ml/g, and leach the mode adopting normal temperature to leach, extraction temperature is 25 DEG C, extraction time is 40h; Filter after leaching and obtain solid phase and leach liquor; In leach liquor, the mass concentration of magnesium chloride is 60g/L;
Leach the solid phase washing obtained and remove impurity, then moisture is removed in oven dry, make the ultra-fine titanium boride powder of purity by weight >=99%, granularity is at 0.1 ~ 0.5 μm;
Adopt the mode process leach liquor of spray-wall interaction; Spray-wall interaction by atomizing nozzle, leach liquor is carried out atomization winding-up in high temperature pyrolysis stove under the pressure of 0.26MPa, and reheating solution obtains nanoscale magnesium and pyrolysis tail gas; Nanoscale magnesium granularity be 320 ~ 390nm;
Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns leaching process and recycles, and the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 1mol/L; Pyrolysis temperature in high temperature pyrolysis stove is 200 DEG C, pyrolysis time is 60min.
Embodiment 23
Method is with embodiment 1, and difference is:
(1) blending ratio is titanium oxide in mass ratio: boron oxide: magnesium powder=100:95:180; Pressure when being pressed into blank is 50MPa;
(2) leaching the concentration of hydrochloric acid adopted is 2mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 10:1ml/g, and leach the mode adopting normal temperature to leach, extraction temperature is 90 DEG C, extraction time is 10h; In leach liquor, the mass concentration of magnesium chloride is 70g/L;
(3) spray-wall interaction leach liquor is carried out atomization winding-up in high temperature pyrolysis stove by atomizing nozzle under the pressure of 0.45MPa, nanoscale magnesium granularity be 280 ~ 340nm, the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 2mol/L; Pyrolysis temperature is 200 DEG C, pyrolysis time is 60min.
Embodiment 24
Method is with embodiment 1, and difference is:
(1) blending ratio is titanium oxide in mass ratio: boron oxide: magnesium powder=100:92:168; Pressure when being pressed into blank is 60MPa;
(2) leaching the concentration of hydrochloric acid adopted is 3mol/L; The liquid-solid ratio of hydrochloric acid and thick product is 20:1ml/g, and leach the mode adopting normal temperature to leach, extraction temperature is 50 DEG C, extraction time is 20h; In leach liquor, the mass concentration of magnesium chloride is 110g/L;
(3) spray-wall interaction leach liquor is carried out atomization winding-up in high temperature pyrolysis stove by atomizing nozzle under the pressure of 0.6MPa, nanoscale magnesium granularity be 180 ~ 280nm, the concentration of the hydrochloric acid that hydrogenchloride is formed after absorbing is 3mol/L; Pyrolysis temperature is 700 DEG C, pyrolysis time is 0.5min.
Claims (3)
1. self-spreading metallurgical legal system is for a clean preparation method for ultra fine boride powder, it is characterized in that carrying out according to the following steps:
(1) be milled to granularity≤0.5 μm after metal oxide, boron oxide and magnesium powder being mixed, be then pressed into blank, put into self-propagating reaction stove and cause self-propagating reaction, described metal oxide is ytterbium oxide, cerium oxide, zirconium white, Neodymium trioxide, Samarium trioxide, calcium oxide or titanium oxide, after self-propagating reaction terminates, reaction product naturally cools to normal temperature, obtains thick product, and the metal boride disperse in thick product is in spongy magnesium oxide matrix, when metal oxide is ytterbium oxide, blending ratio is ytterbium oxide in mass ratio: boron oxide: magnesium powder=100:(100 ~ 115): (135 ~ 160), when oxide compound is cerium oxide, blending ratio is cerium oxide in mass ratio: boron oxide: magnesium powder=100:(110 ~ 130): (160 ~ 185), when oxide compound is zirconium white, blending ratio is zirconium white in mass ratio: boron oxide: magnesium powder=100:(60 ~ 65): (105 ~ 122), when oxide compound is Neodymium trioxide, blending ratio is niobium oxides in mass ratio: boron oxide: magnesium powder=100:(118 ~ 132): (160 ~ 185), when oxide compound is Samarium trioxide, blending ratio is Samarium trioxide in mass ratio: boron oxide: magnesium powder=100:(115 ~ 127): (155 ~ 180), when oxide compound is calcium oxide, blending ratio is calcium oxide in mass ratio: boron oxide: magnesium powder=100:(335 ~ 390): (450 ~ 515), when oxide compound is titanium oxide, blending ratio is titanium oxide in mass ratio: boron oxide: magnesium powder=100:(90 ~ 95): (155 ~ 180), pressure when being wherein pressed into blank is 40 ~ 70MPa,
(2) by thick product after fragmentation, adopt the mode of Leaching in Hydrochloric Acid to be separated magnesium oxide wherein; Leaching the concentration of hydrochloric acid adopted is 1 ~ 5mol/L; The liquid-solid ratio of hydrochloric acid and thick product is (4 ~ 20): 1ml/g, leaches the mode of mode or the high temperature leaching in confined conditions adopting normal temperature to leach; When normal temperature leaches, extraction temperature is 25 ~ 90 DEG C, extraction time is 10 ~ 40h; When high temperature leaches, extraction temperature is 100 ~ 150 DEG C, extraction time is 30 ~ 180min; Filter after leaching and obtain solid phase and leach liquor;
(3) leach the solid phase washing obtained and remove impurity, then moisture is removed in oven dry, makes the ultra fine boride powder of purity by weight >=99%; Described ultra fine boride powder is the titanium boride powder of the ytterbium boride powder of granularity≤300nm, the cerium boride powder of granularity≤400nm, the boronation zirconium powder of granularity≤400nm, the neodymium boride powder of granularity≤0.5 μm, the samarium boride powder of granularity≤0.5 μm, the boronation calcium powder of granularity 0.8 ~ 2.5 μm or granularity≤0.5 μm;
(4) the mode process leach liquor of spray-wall interaction is adopted; Spray-wall interaction by atomizing nozzle, leach liquor is carried out atomization winding-up in high temperature pyrolysis stove under the pressure of 0.13 ~ 0.6MPa, and reheating solution obtains nanoscale magnesium and pyrolysis tail gas; Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns leaching process and recycles; Pyrolysis temperature in high temperature pyrolysis stove is 200 ~ 700 DEG C, pyrolysis time is 0.5 ~ 60min; Described nanoscale magnesium granularity be 80 ~ 390nm.
2. a kind of self-spreading metallurgical legal system according to claim 1 is for the clean preparation method of ultra fine boride powder, it is characterized in that the mass concentration of magnesium chloride in described leach liquor is 50 ~ 300g/L.
3. a kind of self-spreading metallurgical legal system according to claim 1 is for the clean preparation method of ultra fine boride powder, it is characterized in that the concentration of the hydrochloric acid that described hydrogenchloride is formed after absorbing is 1 ~ 5mol/L.
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