CN103466649A - Cleaner production method for preparing superfine boride powder through self-propagating metallurgy method - Google Patents
Cleaner production method for preparing superfine boride powder through self-propagating metallurgy method Download PDFInfo
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Abstract
A cleaner production method for preparing superfine boride powder through a self-propagating metallurgy method is carried out according to the following steps: (1) mixing and conducting ball-milling on metallic oxide, boric oxide and magnesium powder, then compacting into a blank, putting the blank into a self-propagating reaction furnace to cause a self-propagating reaction, and naturally cooling to the room temperature to obtain a coarse product; (2) using hydrochloric acid to leach the coarse product after breaking, and filtering to obtain a solid phase and a leaching agent; (3) washing and drying the leached solid phase and making the solid phase into ultrafine boride powder; (4) processing the leaching agent through a spray-pyrolysis mode to obtain a nanoscale magnesium oxide and pyrolysis tail gas, wherein the hydrogen chloride in the pyrolysis tail gas is absorbed to form hydrochloric acid and is circularly used back in the leaching process. The cleaner production method producing the ultrafine boride powder through the self-propagating metallurgy mode has the characteristics of low material cost, low energy consumption, simple operation, low requirement on process conditions and the like, and the product is high in purity, small in particle size and high in powder activity.
Description
Technical field
The invention belongs to metallurgical technology field, particularly the clean preparation method of the standby Superfine Boron compound powder of a kind of self-spreading metallurgical legal system.
Background technology
The superfine powder technology of preparing is to follow modern high technology and new material industry, the new engineering grown 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., be 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, use aforesaid method to prepare superfine powder and exist energy consumption high more, the shortcomings such as cost is high, complex process.With aforementioned production method, compare, adopt the 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, processing condition are required to the characteristics such as low, and the purity of product is high, granularity is little, powder activity is high.Northeastern University combines Self-propagating High-temperature Synthesis Process and metallurgical extract technology, (patent No. is respectively ZL200510047297.8 to have invented the new technology of the standby superfine powder of self-spreading metallurgical legal system, ZL200510047308.2, ZL201010233471.9, ZL201010233478.0, ZL200810011972.5), being about to the raw materials such as oxide compound and reductive agent magnesium powder mixes, after being pressed into the base sample, be placed in the self-propagating reaction stove, cause self-propagating reaction with means such as part igniting or constant temperature detonate, the cooling thick product of product disperse in spongiform magnesium oxide matrix that obtain, then the diluted acid of at room temperature take leaches thick product as leaching agent is direct, filtering separation obtains superfine powder, produced a large amount of acid magnesium-containing waste solutions owing to having introduced acid leaching process at leaching process.
Summary of the invention
The problems referred to above that exist for the standby superfine powder process of self-spreading metallurgical legal system, the invention provides the clean preparation method of the standby Superfine Boron compound powder of a kind of self-spreading metallurgical legal system, adopting hydrochloric acid is that leaching agent leaches the synthetic thick product obtained of self propagating high temperature, remove magnesium oxide wherein, filtering separation obtains superfine powder and magnesium chloride solution, then the thermolysis of magnesium chloride solution directly being sprayed obtains the nano level magnesium oxide powder, obtain hydrogen chloride gas simultaneously, hydrogen chloride gas can return to the leaching process recycle after absorbing, realize the cleaner production of this process.
The clean preparation method of the standby Superfine Boron compound powder of self-spreading metallurgical legal system of the present invention carries out according to the following steps:
1, by after metal oxide, boron oxide and the mixing of magnesium powder, being milled to granularity≤0.5 μ m, then be pressed into blank, put into the 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 finishes, 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 separate magnesium oxide wherein; Leaching the concentration of hydrochloric acid adopted is 1 ~ 5mol/L; Hydrochloric acid is (4 ~ 20): 1ml/g with the liquid-solid ratio of thick product, leaches the mode that adopts normal temperature to leach or the mode that high temperature leaches in confined conditions; When normal temperature leaches, extraction temperature is that 25 ~ 90 ℃, extraction time are 10 ~ 40h; When high temperature leaches, extraction temperature is that 100 ~ 150 ℃, extraction time are 30 ~ 180min; Filter after leaching and obtain solid phase and leach liquor;
3, impurity is removed in the solid phase washing that leaching obtains, then dries removal moisture, makes the Superfine Boron compound powder of weight purity >=99%;
4, adopt the mode of spraying thermolysis to process leach liquor; The spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.13 ~ 0.6MPa, then pyrolysis obtains nano level magnesium oxide and pyrolysis tail gas; Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns to leaching process and recycles; Pyrolysis temperature in the high temperature pyrolysis stove is that 200 ~ 700 ℃, pyrolysis time are 0.5 ~ 60min.
In aforesaid method, the pressure while 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 that the reaction of self-propagating reaction generating process discharges;
In aforesaid method, the 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。
The neodymium boride powder of the boronation zirconium powder of the ytterbium boride powder that above-mentioned Superfine Boron compound powder is granularity≤300nm, the cerium boride powder of granularity≤400nm, granularity≤400nm, the lanthanum boride powder of granularity 0.8 ~ 3.0 μ m, granularity≤0.5 μ m, the samarium boride powder of granularity≤0.5 μ m, the boronation calcium powder of granularity 0.8 ~ 2.5 μ m or the titanium boride powder of granularity≤0.5 μ m.
In above-mentioned leach liquor, the mass concentration of magnesium chloride is 50 ~ 300g/L.
The magnesian granularity of above-mentioned nano level is 80 ~ 390 nm.
The concentration of the hydrochloric acid that above-mentioned hydrogenchloride forms after absorbing is 1 ~ 5mol/L.
In aforesaid method, self-propagating reaction is divided into direct initiation and constant temperature detonates two kinds; Direct initiation is direct heating blank under air atmosphere, until self-propagating reaction occurs, now can form dazzling flame, and have a large amount of cigarettes to volatilize, and the temperature of reaction system raises rapidly; Constant temperature detonates and refers under air atmosphere, the heating blank, and temperature is controlled between 720 ~ 950 ℃, until self-propagating reaction occurs, now can form dazzling flame, and have a large amount of cigarettes to volatilize, and the temperature of reaction system raises rapidly.
Because self-propagating reaction is to occur under unlimited air atmosphere, and the self-propagating reaction temperature is very high, and in reaction process, the gasification of MAGNESIUM METAL amount, can cause a large amount of volatilization loss of Mg, and Mg will be not enough like this; In order to make up the volatilization loss of Mg, the present invention when batching MAGNESIUM METAL than reaction theory requirement excessive 5 ~ 25%; In order to make the self-propagating reaction operation simpler, self-propagating reaction also can adopt the partial points pyrogenic process to cause.
With traditional superfine powder technology of preparing, compare, characteristics 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, processing condition are required to the characteristics such as low, and the purity of product is high, granularity is little, powder activity is high;
(2) adopt the mode of spraying thermolysis to process magnesium chloride solution, reaction efficiency is high, can obtain the nano level magnesium oxide product, has improved added value of product;
(3) production process produces acid and water can be realized recycle by thermal decomposition process, have realized that whole process is without useless clean
Produce.
The accompanying drawing explanation
The clean preparation method process flow diagram that Fig. 1 is the standby Superfine Boron compound powder of a kind of self-spreading metallurgical legal system of the present invention.
Embodiment
Magnesium powder, boron oxide, ytterbium oxide, cerium oxide, zirconium white, lanthanum trioxide, Neodymium trioxide, Samarium trioxide, calcium oxide and the titanium oxide adopted in the embodiment of the present invention is 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 consists 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, washing is that the solid phase water is filtered to washing, and the acid wash water of acquisition is for the moisture of Leaching in Hydrochloric Acid process replenish loss.
In the embodiment of the present invention, drying time is 24h at least.
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 the time 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 μ m after ytterbium oxide, boron oxide and magnesium powder are mixed, then be pressed into blank, put into the 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 while being pressed into blank is 40MPa;
After self-propagating reaction finishes, reaction product naturally cools to normal temperature, obtains thick product, and the ytterbium boride disperse in thick product is in spongy magnesium oxide matrix;
After fragmentation, adopt the mode of Leaching in Hydrochloric Acid to separate magnesium oxide wherein thick product; Leaching the concentration of hydrochloric acid adopted is 1mol/L; Hydrochloric acid is 4:1ml/g with the liquid-solid ratio of thick product, leaches the mode that adopts normal temperature to leach, and extraction temperature is that 25 ℃, extraction time are 40h; Filter after leaching and obtain solid phase and leach liquor; In leach liquor, the mass concentration of magnesium chloride is 50g/L;
Impurity is removed in the solid phase washing that leaching obtains, then dries removal moisture, makes the ultra-fine ytterbium boride powder of weight purity >=99%, and granularity is at 150 ~ 300nm;
Adopt the mode of spraying thermolysis to process leach liquor; The spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.13MPa, then pyrolysis obtains nano level magnesium oxide and pyrolysis tail gas; The magnesian granularity of nano level is 80 ~ 150 nm;
Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns to leaching process and recycles, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 1mol/L; Pyrolysis temperature in the high temperature pyrolysis stove is that 500 ℃, pyrolysis time are 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 while being pressed into blank is 50MPa;
(2) leaching the concentration of hydrochloric acid adopted is 3mol/L; Hydrochloric acid is 8:1ml/g with the liquid-solid ratio of thick product, leaches the mode that adopts normal temperature to leach, and extraction temperature is that 50 ℃, extraction time are 20h; In leach liquor, the mass concentration of magnesium chloride is 150g/L;
(3) the spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.25MPa, and the magnesian granularity of nano level is 100 ~ 220 nm, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 3mol/L; Pyrolysis temperature is that 700 ℃, pyrolysis time are 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 while being pressed into blank is 60MPa;
(2) leaching the concentration of hydrochloric acid adopted is 5mol/L; Hydrochloric acid is 20:1ml/g with the liquid-solid ratio of thick product, leaches the mode that adopts normal temperature to leach, and extraction temperature is that 90 ℃, extraction time are 10h; In leach liquor, the mass concentration of magnesium chloride is 300g/L;
(3) the spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.6MPa, and the magnesian granularity of nano level is 320 ~ 390 nm, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 5mol/L; Pyrolysis temperature is that 200 ℃, pyrolysis time are 60min.
Embodiment 4
Be milled to granularity≤0.5 μ m after cerium oxide, boron oxide and magnesium powder are mixed, then be pressed into blank, put into the 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 while being pressed into blank is 40MPa;
After self-propagating reaction finishes, reaction product naturally cools to normal temperature, obtains thick product, and the cerium boride disperse in thick product is in spongy magnesium oxide matrix;
After fragmentation, adopt the mode of Leaching in Hydrochloric Acid to separate magnesium oxide wherein thick product; Leaching the concentration of hydrochloric acid adopted is 1mol/L; Hydrochloric acid is 4:1ml/g with the liquid-solid ratio of thick product, leaches the mode that adopts normal temperature to leach, and extraction temperature is that 25 ℃, extraction time are 40h; Filter after leaching and obtain solid phase and leach liquor; In leach liquor, the mass concentration of magnesium chloride is 50g/L;
Impurity is removed in the solid phase washing that leaching obtains, then dries removal moisture, makes the ultra-fine cerium boride powder of weight purity >=99%, and granularity is at 150 ~ 400nm;
Adopt the mode of spraying thermolysis to process leach liquor; The spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.13MPa, then pyrolysis obtains nano level magnesium oxide and pyrolysis tail gas; The magnesian granularity of nano level is 80 ~ 150 nm;
Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns to leaching process and recycles, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 1mol/L; Pyrolysis temperature in the high temperature pyrolysis stove is that 500 ℃, pyrolysis time are 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 while being pressed into blank is 50MPa;
(2) leaching the concentration of hydrochloric acid adopted is 3mol/L; Hydrochloric acid is 8:1ml/g with the liquid-solid ratio of thick product, leaches the mode that adopts normal temperature to leach, and extraction temperature is that 50 ℃, extraction time are 20h; In leach liquor, the mass concentration of magnesium chloride is 150g/L;
(3) the spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.25MPa, and the magnesian granularity of nano level is 100 ~ 220 nm, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 3mol/L; Pyrolysis temperature is that 700 ℃, pyrolysis time are 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 while being pressed into blank is 60MPa;
(2) leaching the concentration of hydrochloric acid adopted is 5mol/L; Hydrochloric acid is 20:1ml/g with the liquid-solid ratio of thick product, leaches the mode that adopts normal temperature to leach, and extraction temperature is that 90 ℃, extraction time are 10h; In leach liquor, the mass concentration of magnesium chloride is 300g/L;
(3) the spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.6MPa, and the magnesian granularity of nano level is 320 ~ 390 nm, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 5mol/L; Pyrolysis temperature is that 200 ℃, pyrolysis time are 60min.
Embodiment 7
Be milled to granularity≤0.5 μ m after zirconium white, boron oxide and magnesium powder are mixed, then be pressed into blank, put into the 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 while being pressed into blank is 70MPa;
After self-propagating reaction finishes, 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;
After fragmentation, adopt the mode of Leaching in Hydrochloric Acid to separate magnesium oxide wherein thick product; Leaching the concentration of hydrochloric acid adopted is 4mol/L; Hydrochloric acid is 5:1ml/g with the liquid-solid ratio of thick product, and leaching and adopting the mode that high temperature leaches in confined conditions, extraction temperature is that 100 ~ 150 ℃, extraction time are 180min; Filter after leaching and obtain solid phase and leach liquor; In leach liquor, the mass concentration of magnesium chloride is 60g/L;
Impurity is removed in the solid phase washing that leaching obtains, then dries removal moisture, makes the ultra-fine boronation zirconium powder of weight purity >=99%, and granularity is at 200 ~ 400 nm;
Adopt the mode of spraying thermolysis to process leach liquor; The spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.15MPa, then pyrolysis obtains nano level magnesium oxide and pyrolysis tail gas; The magnesian granularity of nano level is 280 ~ 360 nm;
Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns to leaching process and recycles, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 4mol/L; Pyrolysis temperature in the high temperature pyrolysis stove is that 300 ℃, pyrolysis time are 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 while being pressed into blank is 60MPa;
(2) leaching the concentration of hydrochloric acid adopted is 2mol/L; Hydrochloric acid is 10:1ml/g with the liquid-solid ratio of thick product, and leaching and adopting the mode that high temperature leaches in confined conditions, extraction temperature is that 100 ~ 150 ℃, extraction time are 90min; In leach liquor, the mass concentration of magnesium chloride is 200g/L;
(3) the spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.4MPa, and the magnesian granularity of nano level is 180 ~ 300 nm, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 2mol/L; Pyrolysis temperature is that 400 ℃, pyrolysis time are 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 while being pressed into blank is 50MPa;
(2) leaching the concentration of hydrochloric acid adopted is 5mol/L; Hydrochloric acid is 18:1ml/g with the liquid-solid ratio of thick product, and leaching and adopting the mode that high temperature leaches in confined conditions, extraction temperature is that 100 ~ 150 ℃, extraction time are 30min; In leach liquor, the mass concentration of magnesium chloride is 220g/L;
(3) the spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.5MPa, and the magnesian granularity of nano level is 180 ~ 250 nm, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 5mol/L; Pyrolysis temperature is that 300 ℃, pyrolysis time are 10min.
Embodiment 10
Be milled to granularity≤0.5 μ m after lanthanum trioxide, boron oxide and magnesium powder are mixed, then be pressed into blank, put into the 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 while being pressed into blank is 40MPa;
After self-propagating reaction finishes, reaction product naturally cools to normal temperature, obtains thick product, and the lanthanum boride disperse in thick product is in spongy magnesium oxide matrix;
After fragmentation, adopt the mode of Leaching in Hydrochloric Acid to separate magnesium oxide wherein thick product; Leaching the concentration of hydrochloric acid adopted is 4mol/L; Hydrochloric acid is 6:1ml/g with the liquid-solid ratio of thick product, leaches the mode that adopts normal temperature to leach, and extraction temperature is that 90 ℃, extraction time are 10h; Filter after leaching and obtain solid phase and leach liquor; In leach liquor, the mass concentration of magnesium chloride is 220g/L;
Impurity is removed in the solid phase washing that leaching obtains, then dries removal moisture, makes the ultra-fine lanthanum boride powder of weight purity >=99%, and granularity is at 0.8 ~ 3.0 μ m;
Adopt the mode of spraying thermolysis to process leach liquor; The spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.2MPa, then pyrolysis obtains nano level magnesium oxide and pyrolysis tail gas; The magnesian granularity of nano level is 110 ~ 220 nm;
Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns to leaching process and recycles, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 4mol/L; Pyrolysis temperature in the high temperature pyrolysis stove is that 200 ℃, pyrolysis time are 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 while being pressed into blank is 50MPa;
(2) leaching the concentration of hydrochloric acid adopted is 3mol/L; Hydrochloric acid is 12:1ml/g with the liquid-solid ratio of thick product, leaches the mode that adopts normal temperature to leach, and extraction temperature is that 25 ℃, extraction time are 40h; In leach liquor, the mass concentration of magnesium chloride is 105g/L;
(3) the spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.3MPa, and the magnesian granularity of nano level is 280 ~ 390 nm, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 3mol/L; Pyrolysis temperature is that 700 ℃, pyrolysis time are 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 while being pressed into blank is 60MPa;
(2) leaching the concentration of hydrochloric acid adopted is 2mol/L; Hydrochloric acid is 20:1ml/g with the liquid-solid ratio of thick product, leaches the mode that adopts normal temperature to leach, and extraction temperature is that 80 ℃, extraction time are 15h; In leach liquor, the mass concentration of magnesium chloride is 120g/L;
(3) the spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.4MPa, and the magnesian granularity of nano level is 80 ~ 120 nm, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 2mol/L; Pyrolysis temperature is that 200 ℃, pyrolysis time are 60min.
Embodiment 13
Be milled to granularity≤0.5 μ m after Neodymium trioxide, boron oxide and magnesium powder are mixed, then be pressed into blank, put into the 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 while being pressed into blank is 70MPa;
After self-propagating reaction finishes, reaction product naturally cools to normal temperature, obtains thick product, and the neodymium boride disperse in thick product is in spongy magnesium oxide matrix;
After fragmentation, adopt the mode of Leaching in Hydrochloric Acid to separate magnesium oxide wherein thick product; Leaching the concentration of hydrochloric acid adopted is 1mol/L; Hydrochloric acid is 4:1ml/g with the liquid-solid ratio of thick product, and leaching and adopting high temperature leaches in confined conditions mode extraction temperature is that 100 ~ 150 ℃, extraction time are 100min; Filter after leaching and obtain solid phase and leach liquor; In leach liquor, the mass concentration of magnesium chloride is 50g/L;
Impurity is removed in the solid phase washing that leaching obtains, then dries removal moisture, makes the ultra-fine neodymium boride powder of weight purity >=99%, and granularity is at 0.2 ~ 0.5 μ m;
Adopt the mode of spraying thermolysis to process leach liquor; The spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.5MPa, then pyrolysis obtains nano level magnesium oxide and pyrolysis tail gas; The magnesian granularity of nano level is 90 ~ 160 nm;
Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns to leaching process and recycles, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 1mol/L; Pyrolysis temperature in the high temperature pyrolysis stove is that 300 ℃, pyrolysis time are 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 while being pressed into blank is 60MPa;
(2) leaching the concentration of hydrochloric acid adopted is 2mol/L; Hydrochloric acid is 10:1ml/g with the liquid-solid ratio of thick product, and leaching and adopting the mode that high temperature leaches in confined conditions, extraction temperature is that 100 ~ 150 ℃, extraction time are 60min; In leach liquor, the mass concentration of magnesium chloride is 120g/L;
(3) the spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.6MPa, and the magnesian granularity of nano level is 120 ~ 230 nm, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 2mol/L; Pyrolysis temperature is that 400 ℃, pyrolysis time are 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 while being pressed into blank is 50MPa;
(2) leaching the concentration of hydrochloric acid adopted is 3mol/L; Hydrochloric acid is 20:1ml/g with the liquid-solid ratio of thick product, and leaching and adopting the mode that high temperature leaches in confined conditions, extraction temperature is that 100 ~ 150 ℃, extraction time are 150min; In leach liquor, the mass concentration of magnesium chloride is 180g/L;
(3) the spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.18MPa, and the magnesian granularity of nano level is 180 ~ 290 nm, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 3mol/L; Pyrolysis temperature is that 500 ℃, pyrolysis time are 10min.
Embodiment 16
Be milled to granularity≤0.5 μ m after Samarium trioxide, boron oxide and magnesium powder are mixed, then be pressed into blank, put into the 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 while being pressed into blank is 40MPa;
After self-propagating reaction finishes, reaction product naturally cools to normal temperature, obtains thick product, and the samarium boride disperse in thick product is in spongy magnesium oxide matrix;
After fragmentation, adopt the mode of Leaching in Hydrochloric Acid to separate magnesium oxide wherein thick product; Leaching the concentration of hydrochloric acid adopted is 4mol/L; Hydrochloric acid is 18:1ml/g with the liquid-solid ratio of thick product, leaches the mode that adopts normal temperature to leach, and extraction temperature is that 25 ℃, extraction time are 40h; Filter after leaching and obtain solid phase and leach liquor; In leach liquor, the mass concentration of magnesium chloride is 210g/L;
Impurity is removed in the solid phase washing that leaching obtains, then dries removal moisture, makes the ultra-fine samarium boride powder of weight purity >=99%, and granularity is at 0.35 ~ 0.5 μ m;
Adopt the mode of spraying thermolysis to process leach liquor; The spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.24MPa, then pyrolysis obtains nano level magnesium oxide and pyrolysis tail gas; The magnesian granularity of nano level is 200 ~ 300 nm;
Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns to leaching process and recycles, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 4mol/L; Pyrolysis temperature in the high temperature pyrolysis stove is that 600 ℃, pyrolysis time are 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 while being pressed into blank is 50MPa;
(2) leaching the concentration of hydrochloric acid adopted is 5mol/L; Hydrochloric acid is 16:1ml/g with the liquid-solid ratio of thick product, leaches the mode that adopts normal temperature to leach, and extraction temperature is that 90 ℃, extraction time are 10h; In leach liquor, the mass concentration of magnesium chloride is 240g/L;
(3) the spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.35MPa, and the magnesian granularity of nano level is 200 ~ 290 nm, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 5mol/L; Pyrolysis temperature is that 700 ℃, pyrolysis time are 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 while being pressed into blank is 60MPa;
(2) leaching the concentration of hydrochloric acid adopted is 5mol/L; Hydrochloric acid is 10:1ml/g with the liquid-solid ratio of thick product, leaches the mode that adopts normal temperature to leach, and extraction temperature is that 30 ℃, extraction time are 30h; In leach liquor, the mass concentration of magnesium chloride is 150g/L;
(3) the spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.48MPa, and the magnesian granularity of nano level is 80 ~ 160 nm, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 5mol/L; Pyrolysis temperature is that 700 ℃, pyrolysis time are 1min.
Embodiment 19
Be milled to granularity≤0.5 μ m after calcium oxide, boron oxide and magnesium powder are mixed, then be pressed into blank, put into the 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 while being pressed into blank is 70MPa;
After self-propagating reaction finishes, reaction product naturally cools to normal temperature, obtains thick product, and the calcium boride disperse in thick product is in spongy magnesium oxide matrix;
After fragmentation, adopt the mode of Leaching in Hydrochloric Acid to separate magnesium oxide wherein thick product; Leaching the concentration of hydrochloric acid adopted is 4mol/L; Hydrochloric acid is 6:1ml/g with the liquid-solid ratio of thick product, and leaching and adopting the mode that high temperature leaches in confined conditions, extraction temperature is that 100 ~ 150 ℃, extraction time are 120min; Filter after leaching and obtain solid phase and leach liquor; In leach liquor, the mass concentration of magnesium chloride is 80g/L;
Impurity is removed in the solid phase washing that leaching obtains, then dries removal moisture, makes the ultra-fine boronation calcium powder of weight purity >=99%, and granularity is at 0.8 ~ 2.5 μ m;
Adopt the mode of spraying thermolysis to process leach liquor; The spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.55MPa, then pyrolysis obtains nano level magnesium oxide and pyrolysis tail gas; The magnesian granularity of nano level is 160 ~ 220 nm;
Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns to leaching process and recycles, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 4mol/L; Pyrolysis temperature in the high temperature pyrolysis stove is that 600 ℃, pyrolysis time are 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 while being pressed into blank is 60MPa;
(2) leaching the concentration of hydrochloric acid adopted is 3mol/L; Hydrochloric acid is 10:1ml/g with the liquid-solid ratio of thick product, and leaching and adopting the mode that high temperature leaches in confined conditions, extraction temperature is that 100 ~ 150 ℃, extraction time are 90min; In leach liquor, the mass concentration of magnesium chloride is 90g/L;
(3) the spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.6MPa, and the magnesian granularity of nano level is 140 ~ 190 nm, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 3mol/L; Pyrolysis temperature is that 500 ℃, pyrolysis time are 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 while being pressed into blank is 50MPa;
(2) leaching the concentration of hydrochloric acid adopted is 2mol/L; Hydrochloric acid is 15:1ml/g with the liquid-solid ratio of thick product, and leaching and adopting the mode that high temperature leaches in confined conditions, extraction temperature is that 100 ~ 150 ℃, extraction time are 60min; In leach liquor, the mass concentration of magnesium chloride is 100g/L;
(3) the spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.13MPa, and the magnesian granularity of nano level is 220 ~ 300 nm, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 2mol/L; Pyrolysis temperature is that 300 ℃, pyrolysis time are 40min.
Embodiment 22
Be milled to granularity≤0.5 μ m after titanium oxide, boron oxide and magnesium powder are mixed, then be pressed into blank, put into the 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 while being pressed into blank is 40MPa;
After self-propagating reaction finishes, reaction product naturally cools to normal temperature, obtains thick product, and the titanium boride disperse in thick product is in spongy magnesium oxide matrix;
After fragmentation, adopt the mode of Leaching in Hydrochloric Acid to separate magnesium oxide wherein thick product; Leaching the concentration of hydrochloric acid adopted is 1mol/L; Hydrochloric acid is 5:1ml/g with the liquid-solid ratio of thick product, leaches the mode that adopts normal temperature to leach, and extraction temperature is that 25 ℃, extraction time are 40h; Filter after leaching and obtain solid phase and leach liquor; In leach liquor, the mass concentration of magnesium chloride is 60g/L;
Impurity is removed in the solid phase washing that leaching obtains, then dries removal moisture, makes the ultra-fine titanium boride powder of weight purity >=99%, and granularity is at 0.1 ~ 0.5 μ m;
Adopt the mode of spraying thermolysis to process leach liquor; The spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.26MPa, then pyrolysis obtains nano level magnesium oxide and pyrolysis tail gas; The magnesian granularity of nano level is 320 ~ 390 nm;
Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns to leaching process and recycles, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 1mol/L; Pyrolysis temperature in the high temperature pyrolysis stove is that 200 ℃, pyrolysis time are 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 while being pressed into blank is 50MPa;
(2) leaching the concentration of hydrochloric acid adopted is 2mol/L; Hydrochloric acid is 10:1ml/g with the liquid-solid ratio of thick product, leaches the mode that adopts normal temperature to leach, and extraction temperature is that 90 ℃, extraction time are 10h; In leach liquor, the mass concentration of magnesium chloride is 70g/L;
(3) the spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.45MPa, and the magnesian granularity of nano level is 280 ~ 340 nm, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 2mol/L; Pyrolysis temperature is that 200 ℃, pyrolysis time are 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 while being pressed into blank is 60MPa;
(2) leaching the concentration of hydrochloric acid adopted is 3mol/L; Hydrochloric acid is 20:1ml/g with the liquid-solid ratio of thick product, leaches the mode that adopts normal temperature to leach, and extraction temperature is that 50 ℃, extraction time are 20h; In leach liquor, the mass concentration of magnesium chloride is 110g/L;
(3) the spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.6MPa, and the magnesian granularity of nano level is 180 ~ 280 nm, and the concentration of the hydrochloric acid that hydrogenchloride forms after absorbing is 3mol/L; Pyrolysis temperature is that 700 ℃, pyrolysis time are 0.5min.
Claims (6)
1. the clean preparation method of the standby Superfine Boron compound powder of a self-spreading metallurgical legal system is characterized in that carrying out according to the following steps:
(1) by after metal oxide, boron oxide and the mixing of magnesium powder, being milled to granularity≤0.5 μ m, then be pressed into blank, put into the 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 finishes, 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 separate magnesium oxide wherein; Leaching the concentration of hydrochloric acid adopted is 1 ~ 5mol/L; Hydrochloric acid is (4 ~ 20): 1ml/g with the liquid-solid ratio of thick product, leaches the mode that adopts normal temperature to leach or the mode that high temperature leaches in confined conditions; When normal temperature leaches, extraction temperature is that 25 ~ 90 ℃, extraction time are 10 ~ 40h; When high temperature leaches, extraction temperature is that 100 ~ 150 ℃, extraction time are 30 ~ 180min; Filter after leaching and obtain solid phase and leach liquor;
(3) impurity is removed in the solid phase washing that leaching obtains, then dries removal moisture, makes the Superfine Boron compound powder of weight purity >=99%;
(4) adopt the mode of spraying thermolysis to process leach liquor; The spraying thermolysis is by atomizing nozzle, leach liquor to be carried out to the atomization winding-up in the high temperature pyrolysis stove under the pressure of 0.13 ~ 0.6MPa, then pyrolysis obtains nano level magnesium oxide and pyrolysis tail gas; Hydrogenchloride in pyrolysis tail gas forms hydrochloric acid after absorbing, and returns to leaching process and recycles; Pyrolysis temperature in the high temperature pyrolysis stove is that 200 ~ 700 ℃, pyrolysis time are 0.5 ~ 60min.
2. a kind of self-spreading metallurgical legal system according to claim 1 is for the clean preparation method of Superfine Boron compound powder, it is characterized in that 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 lanthanum trioxide, blending ratio is lanthanum trioxide in mass ratio: boron oxide: magnesium powder=100:(120 ~ 135): (160 ~ 185), 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).
3. the clean preparation method of the standby Superfine Boron compound powder of a kind of self-spreading metallurgical legal system according to claim 1, is characterized in that the ytterbium boride powder that described Superfine Boron compound powder is 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 μ m, the neodymium boride powder of granularity≤0.5 μ m, the samarium boride powder of granularity≤0.5 μ m, the boronation calcium powder of granularity 0.8 ~ 2.5 μ m or the titanium boride powder of granularity≤0.5 μ m.
4. a kind of self-spreading metallurgical legal system according to claim 1 is for the clean preparation method of Superfine Boron compound powder, and the mass concentration that it is characterized in that magnesium chloride in described leach liquor is 50 ~ 300g/L.
5. the clean preparation method of the standby Superfine Boron compound powder of a kind of self-spreading metallurgical legal system according to claim 1, is characterized in that the magnesian granularity of described nano level is 80 ~ 390 nm.
6. the clean preparation method of the standby Superfine Boron compound powder of a kind of self-spreading metallurgical legal system according to claim 1, is characterized in that the concentration of the hydrochloric acid that described hydrogenchloride forms after absorbing is 1 ~ 5mol/L.
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| CN107236868A (en) * | 2017-05-23 | 2017-10-10 | 东北大学 | A kind of method that multistage drastic reduction prepares high-melting metal powder |
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