CN108190950A - The preparation method and device of zirconium dioxide - Google Patents
The preparation method and device of zirconium dioxide Download PDFInfo
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- CN108190950A CN108190950A CN201810116917.6A CN201810116917A CN108190950A CN 108190950 A CN108190950 A CN 108190950A CN 201810116917 A CN201810116917 A CN 201810116917A CN 108190950 A CN108190950 A CN 108190950A
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- C01—INORGANIC CHEMISTRY
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- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
Abstract
The invention discloses the preparation method and device of a kind of zirconium dioxide, this method includes the following steps：1) by solid zirconium chloride, heating sublimation is gaseous state zirconium chloride in evaporator；2) gaseous state zirconium chloride and hydrogen, oxygen or air are lighted a fire in burner, combustion reaction generation solid zirconium dioxide, hydrogen chloride obtain the first mixture after reaction.The preparation method of zirconium dioxide in the present invention prepares solid zirconium dioxide by ignition reaction, realizes the self-sufficiency of heat in burner, so as to save energy, reduces production cost.
Description
Technical field
The invention belongs to zirconium dioxide production technical fields, and in particular to the preparation method and device of a kind of zirconium dioxide.
Background technology
According to the difference of technique, the preparation process of zirconium oxide can be divided into chemical method (wet processing) and electric smelting method (dry method work
Skill) two kinds, electric smelting method is that by a step electric arc furnaces, the melting at a high temperature of 2300 DEG C obtains by zircon sand and coke or petroleum coke
Obtain zirconium oxide.Chemical method is that zircon sand is converted into zirconium oxychloride first, and zirconium oxychloride decomposes generation zirconium oxide at high temperature again.
The major defect of electric smelting method is that product purity is relatively low, and the electric smelting zirconium purity of domestic production at present is average 98.5%, limits electricity
Molten application of the zirconium oxide in high-end product field.Chemical method prepares zirconium oxide process complexity, while can also generate a large amount of
Waste liquid, production cost is high.
The prior art prepares zirconium oxide, complex process using the method for zirconium chloride hydrolysis.Therefore it develops a kind of new
The zirconium dioxide preparation method technical barrier that is difficult to overcome into those skilled in the art.
Invention content
The technical problems to be solved by the invention are for above-mentioned deficiency in the prior art, provide a kind of titanium dioxide
The preparation method and device of zirconium solve conventional chemical methods and prepare complex process during zirconium dioxide, and production cost is high to ask
Topic.
Solve present invention problem used by technical solution be to provide a kind of preparation method of zirconium dioxide, including with
Lower step：
1) by solid zirconium chloride, heating sublimation is gaseous state zirconium chloride in evaporator；
2) gaseous state zirconium chloride and hydrogen, oxygen or air are lighted a fire in burner, combustion reaction generation solid
Zirconium dioxide, hydrogen chloride obtain the first mixture after reaction.
Preferably, the temperature in the step 2) in burner is 500~1000 DEG C.
Preferably, in the step 2), after igniting reaction, exothermic heat of reaction causes the temperature in burner to be maintained at 500
~1000 DEG C.By adjusting the air inflow of the oxygen in combustion reactor to control temperature in burner be 500~1000 DEG C.
Preferably, the heating temperature in the step 1) in evaporator is 400~550 DEG C.
Preferably, it is further comprising the steps of after the step 2)：
3) the first mixture is passed into the first deduster and be dusted, the solid zirconium dioxide quilt in the first mixture
It separates, and the first dedusting tail gas separated.
Preferably, in step 2) when gaseous state zirconium chloride and hydrogen, oxygen are lighted a fire in burner, hydrogen
Molal quantity：The molal quantity of oxygen：The molal quantity of zirconium chloride=(2~2.5)：1：(1~1.1).First mixture includes：Dioxy
Change zirconium content (solid), hydrogen chloride, zirconium chloride, hydrogen, trace oxygen, trace amounts of water vapor.
Preferably, the boiling point of zirconium chloride<Temperature in first deduster<The boiling point of zirconium dioxide.
Preferably, the temperature in the first deduster is 400~1000 DEG C.Under normal temperature and pressure, the boiling point of zirconium chloride is
331 DEG C, the boiling point of zirconium dioxide is 4300 DEG C.
Preferably, it is further comprising the steps of after the step 3)：
4) the first dedusting tail gas is passed into cooler and cooled down, by the gaseous state zirconium chloride in the first dedusting tail gas
Solid zirconium chloride is cooled to, obtains cooling mixture；Cooling mixture includes：Hydrogen chloride, zirconium chloride, hydrogen, micro amount of oxygen
Gas, trace amounts of water vapor, micro zirconium dioxide.
5) cooling mixture is passed through the second deduster to be dusted, the solid zirconium chloride cooled down in mixture is detached
Get off, and the second dedusting tail gas separated；Second dedusting tail gas includes：Hydrogen chloride, hydrogen, trace oxygen.
6) the second dedusting tail gas is passed through oxygen-eliminating device and carries out deoxygenation, obtain oxygen-eliminating device tail gas, oxygen-eliminating device tail gas includes chlorination
Hydrogen and hydrogen.Oxygen-eliminating device tail gas includes：Hydrogen chloride, hydrogen.
Preferably, the temperature cooled down in the step 4) through subcooler is 150~220 DEG C.
Preferably, when gaseous state zirconium chloride is lighted a fire with hydrogen, air in burner in step 2), hydrogen
Molal quantity：The molal quantity of oxygen in air：The molal quantity of zirconium chloride=(2~2.5):(1~1.5):1.First mixture packet
It includes：Hydrogen chloride, nitrogen, zirconium dioxide (solid), trace oxygen, trace amounts of water vapor, trace hydrogen.
Preferably, it is further comprising the steps of after the step 3)：
4) the first dedusting tail gas is passed into the adsorbing chlorinated hydrogen in absorption tower, the tower reactor on absorption tower is absorbed the tower reactor of tower
Liquid, the tower top on absorption tower are absorbed tower tail gas, and tail gas from absorption tower is vented；First dedusting tail gas includes：Hydrogen chloride,
Nitrogen, oxygen, micro water vapor, trace hydrogen.
Tail gas from absorption tower includes：Nitrogen, oxygen, micro-moisture, trace hydrogen.
5) tower bottoms on absorption tower is passed through Analytic Tower parsing hydrogen chloride, Analytic Tower tail gas is obtained in the tower top of Analytic Tower,
Analytic Tower tail gas includes hydrogen chloride.Analytic Tower tail gas includes：Hydrogen chloride, water.
Preferably, it is further comprising the steps of after the step 5)：
6) tower bottoms of the tower bottoms of Analytic Tower and/or absorption tower is passed into the tower top on absorption tower, as absorption tower
Leacheate.
The present invention also provides a kind of preparation facilities of zirconium dioxide, including：
Evaporator, for being gaseous state zirconium chloride by solid zirconium chloride heating sublimation；
Burner is connect with evaporator, and burner is for gaseous state zirconium chloride and hydrogen, oxygen or air in burner
It lights a fire, combustion reaction generation solid zirconium dioxide, hydrogen chloride obtain the first mixture after reaction.
Preferably, the preparation facilities of the zirconium dioxide further includes：
Mixer is set between evaporator and burner, and is connect respectively with evaporator, burner, and mixer is used for
Gaseous state zirconium chloride is mixed with the hydrogen being passed through in it.
Preferably, the gas distributor for being passed through material into burner, gas distributor are provided in burner
Including：Inner ring channel positioned at center is coated on middle ring channel outside inner ring channel in a ring, is coated on outside middle ring channel
Outer ring channel in a ring, inner ring channel are used to be passed through the gaseous mixture of gaseous state zirconium chloride and hydrogen, and middle ring channel is used to be passed through
Oxygen or air, outer ring channel are used to be passed through the gaseous mixture of gaseous state zirconium chloride and hydrogen.
Preferably, the preparation facilities of the zirconium dioxide further includes：
First deduster, connect with burner, and the first deduster is used to be dusted the first mixture being passed through in it,
Solid zirconium dioxide in first mixture is separated, and the first dedusting tail gas separated.
Preferably, the preparation facilities of the zirconium dioxide further includes：
Cooler is connect with the first deduster, and cooler is for cooling down the first dedusting tail gas, by four chlorination of gaseous state
Zirconium is cooled to solid zirconium chloride, obtains cooling mixture；
Second deduster, connect with cooler, and the second deduster is dusted for that will cool down mixture, cools down mixture
In solid zirconium chloride separated, and the second dedusting tail gas separated；
Oxygen-eliminating device is connect with the second deduster, and oxygen-eliminating device is used to the second dedusting tail gas carrying out deoxygenation, obtains oxygen-eliminating device tail
Gas, oxygen-eliminating device tail gas include hydrogen chloride and hydrogen.
Preferably, the preparation facilities of the zirconium dioxide further includes：
Absorption tower is connect with the first deduster, and absorption tower is used for the first dedusting tail gas adsorption hydrogen chloride, on absorption tower
Tower reactor is absorbed the tower bottoms of tower, and the tower top on absorption tower is absorbed tower tail gas, and tail gas from absorption tower is vented；
Analytic Tower is connect with absorption tower, and Analytic Tower is used to parse hydrogen chloride to the tower bottoms on absorption tower, in the tower of Analytic Tower
Top obtains Analytic Tower tail gas, and Analytic Tower tail gas includes hydrogen chloride.
Preferably, the tower top on the tower reactor of Analytic Tower and absorption tower connects, and the tower bottoms of Analytic Tower is passed into absorption tower
Tower top, the leacheate as absorption tower；And/or
The tower reactor on absorption tower and the tower top on absorption tower connect, and the tower bottoms on absorption tower is passed into the tower top on absorption tower, as
The leacheate on absorption tower.
The preparation method of zirconium dioxide in the present invention prepares solid zirconium dioxide by ignition reaction, realizes
The self-sufficiency of heat in burner, so as to save energy, reduces production cost.
Description of the drawings
Fig. 1 is the structure diagram of the preparation facilities of the zirconium dioxide in the embodiment of the present invention 2；
Fig. 2 is the structure diagram of the preparation facilities of the zirconium dioxide in the embodiment of the present invention 5；
Fig. 3 is the front view of the gas distributor in the embodiment of the present invention 2,5；
Fig. 4 is the vertical view of the gas distributor in the embodiment of the present invention 2,5.
In figure：1- evaporators；2- mixers；3- burners；4- gas distributors；5- inner ring channels；6- middle ring channels；7-
Outer ring channel；The first dedusters of 8-；9- coolers；The second dedusters of 10-；11- oxygen-eliminating devices；12- absorption towers；13- bottom of towe acid solutions
Circulating pump；14- overhead reflux liquid spray throwers；15- Analytic Towers；16- heaters.
Specific embodiment
For those skilled in the art is made to more fully understand technical scheme of the present invention, below in conjunction with the accompanying drawings and specific embodiment party
Formula is described in further detail the present invention.
Embodiment 1
The present embodiment provides a kind of preparation methods of zirconium dioxide, include the following steps：
1) by solid zirconium chloride, heating sublimation is gaseous state zirconium chloride in evaporator；
2) gaseous state zirconium chloride and hydrogen, oxygen or air are lighted a fire in burner, combustion reaction generation solid
Zirconium dioxide, hydrogen chloride obtain the first mixture after reaction.
The present embodiment also provides a kind of preparation facilities of zirconium dioxide, including：
Evaporator, for being gaseous state zirconium chloride by solid zirconium chloride heating sublimation；
Burner is connect with evaporator, and burner is for gaseous state zirconium chloride and hydrogen, oxygen or air in burner
It lights a fire, combustion reaction generation solid zirconium dioxide, hydrogen chloride obtain the first mixture after reaction.
The preparation method of zirconium dioxide in the present embodiment prepares solid zirconium dioxide by ignition reaction, realizes
The self-sufficiency of heat, so as to save energy, reduces production cost in burner.
Embodiment 2
As shown in Figure 1, the present embodiment also provides a kind of preparation facilities of zirconium dioxide, including：
Evaporator 1, for being gaseous state zirconium chloride by solid zirconium chloride heating sublimation；Specifically, in the present embodiment
The main material of evaporator 1 is carbon steel, stainless steel, and evaporator 1 is internally provided with silicon nitride, zirconium oxide, aluminium oxide or its mixing
The Wear-resistant, high-temperature resistant that object is formed is ceramic-lined, and 1 outside of evaporator is provided with heating arrangements, and mode of heating is using resistance heating, spoke
Penetrate one kind in heating, sensing heating.Evaporator 1 to the pipeline between 3 import of burner is internally provided with silicon nitride, oxidation
The Wear-resistant, high-temperature resistant that zirconium, aluminium oxide or its mixture are formed is ceramic-lined, while equipped with electric tracing and heat preservation.
Mixer 2 is connect with evaporator 1, and is connect respectively with evaporator 1, burner 3, and mixer 2 is used for gaseous state four
Zirconium chloride is mixed with the hydrogen being passed through in it；
Burner 3 is connect with 2 device of mixer, and burner 3 is used for gaseous state zirconium chloride and hydrogen to being passed through the mixing in it
Gas is lighted a fire with the oxygen being passed through in it, and combustion reaction generation solid zirconium dioxide, hydrogen chloride obtain the first mixing after reaction
Object；The gas distributor 4 for being passed through material into burner 3, as shown in Figure 3,4, gas distributor are provided in burner 3
4 include：Inner ring channel 5 positioned at center is coated on middle ring channel 6 outside inner ring channel 5 in a ring, is coated on middle ring and leads to
Outer ring channel 7 outside road 6 in a ring, inner ring channel 5 are used to be passed through the gaseous mixture of gaseous state zirconium chloride and hydrogen, middle ring channel 6
For being passed through oxygen, outer ring channel 7 is used to be passed through the gaseous mixture of gaseous state zirconium chloride and hydrogen.The main material of burner 3 is
The heat-resisting material of 800H steel is internally provided with the Wear-resistant, high-temperature resistant that silicon nitride, zirconium oxide, aluminium oxide or its composite material are formed
Ceramic-lined, combustion reactor bottom is equipped with gas distributor 4, forms the anti-of imflammable gas hydrogen package oxidant oxygen
Answer condition, it is ensured that oxidant reaction is complete in reaction process.
First deduster 8, connect with burner 3, and the first deduster 8 is used to remove the first mixture being passed through in it
Dirt, the solid zirconium dioxide in the first mixture are separated, and the first dedusting tail gas separated；Preferably,
First deduster 8 is sack cleaner, and filter core uses metal agglomeration filter core or cloth-bag type filter core.
Cooler 9 is connect with the first deduster 8, and cooler 9 is for cooling down the first dedusting tail gas, by gaseous state four
Zirconium chloride is cooled to solid zirconium chloride, obtains cooling mixture；Preferably, cooler 9 uses tubular heat exchanger, uses
Refrigerant be recirculated water or steam condensate.
Second deduster 10, connect with cooler 9, and the second deduster 10 is dusted for that will cool down mixture, cools down
Solid zirconium chloride in mixture is separated, and the second dedusting tail gas separated；
Oxygen-eliminating device 11 is connect with the second deduster 10, and oxygen-eliminating device 11 is used to the second dedusting tail gas carrying out deoxygenation, is removed
Oxygen device tail gas, oxygen-eliminating device tail gas include hydrogen chloride and hydrogen.Oxygen-eliminating device 11 passes through change using silica gel and/or molecular sieve as adsorbent
The mode of temperature absorption or pressure-variable adsorption realizes the removal of the oxygen in the second dedusting tail gas.
The present embodiment provides a kind of methods that zirconium dioxide is prepared using above device, include the following steps：
1) using refined solid zirconium chloride as raw material, by solid zirconium chloride, heating sublimation is gaseous state four in evaporator 1
Zirconium chloride, the heating temperature in evaporator 1 are 480 DEG C.
2) after gaseous state zirconium chloride is mixed with excessive hydrogen in mixer 2, enter by gas distributor 4 and burn
It is uniform with oxygen mix in the exit of gas distributor 4 in reactor, the molal quantity of hydrogen：The molal quantity of oxygen：Four chlorinations
Molal quantity=2.5 of zirconium:1:1.15, igniting, it is mixed to obtain first for reaction generation zirconium dioxide powder, hydrogen chloride gas after reaction
Object is closed, after igniting reaction, exothermic heat of reaction causes the temperature in burner 3 to be maintained at 500~1000 DEG C.By adjusting combustion reaction
The air inflow of oxygen in device is come to control temperature in burner 3 be 500~1000 DEG C.Zirconium chloride slightly mistake in reaction process
Amount, hydrogen is excessive, and the reaction was complete for oxygen.First mixture includes：Zirconium dioxide content 15-20mol% (solid), hydrogen chloride contain
It measures 65-75mol%, zirconium chloride content 1-5mol%, hydrogen content 5-10mol%, oxygen content and is less than 0.1mol%, water steaming
Vapour content is less than 0.1mol%.
3) the zirconium dioxide powder in the first mixture is passed under the action of air-flow in the first deduster 8 and removed
Dirt, the boiling point of zirconium chloride<Temperature in first deduster 8<The boiling point of zirconium dioxide, the solid titanium dioxide in the first mixture
Zirconium is separated, and the first dedusting tail gas separated.Specifically, the temperature in the first deduster 8 in the present embodiment
Spend is 400~1000 DEG C.Solid zirconium dioxide is discharged by the deslagging pipeline that 8 bottom of the first deduster connects.First dedusting tail
Gas bag includes：Zirconium dioxide content is less than 0.1mol%, hydrogen chloride content 75-90mol%, zirconium chloride content 2-5mol%, hydrogen
Gas content 10-15mol%, oxygen content are less than 0.1mol%, vapour content is less than 0.1mol%.
4) the first dedusting tail gas is passed into cooler 9 and cooled down, the temperature that cooler 9 is cooled down for 180~
220℃.Unreacted zirconium chloride steam in first dedusting tail gas is cooled to solid zirconium chloride, obtains cooling mixing
Object.The variation of the amount of substance does not occur for cooling procedure, and cooling mixture includes：Zirconium dioxide content is less than 0.1mol%, chlorination
Hydrogen content 75-90mol%, zirconium chloride content 2-5mol%, hydrogen content 10-15mol%, oxygen content are less than
0.1mol%, vapour content are less than 0.1mol%.
5) cooling mixture is passed through the second deduster 10 to be dusted, the solid zirconium chloride cooled down in mixture is divided
From getting off, and the second dedusting tail gas separated；The deslagging that solid zirconium chloride is connected by 10 bottom of the second deduster
Pipeline is discharged.Second dedusting tail gas includes：Hydrogen chloride content 85-90mol%, hydrogen content 10-15mol%, oxygen content are small
In 0.1mol%.
6) the second dedusting tail gas is passed through oxygen-eliminating device 11 and carries out deoxygenation, obtain oxygen-eliminating device tail gas, oxygen-eliminating device tail gas includes chlorine
Change hydrogen and hydrogen.Oxygen-eliminating device tail gas includes the mixed gas of the higher hydrogen chloride of purity and hydrogen, trichlorosilane can be used as to give birth to
Chlorinating agent during production.In the present embodiment, chlorine element fully recycles in reaction process, solves problem of environmental pollution,
Improve economic benefit simultaneously.Oxygen-eliminating device tail gas includes：Hydrogen chloride content 85-90mol%, hydrogen content 10-15mol%.
The preparation method of zirconium dioxide in the present embodiment prepares solid zirconium dioxide by ignition reaction, realizes
The self-sufficiency of heat, so as to save energy, reduces production cost in burner 3.The chlorination generated in ignition reaction
Hydrogen fully recycles, and solves problem of environmental pollution, improves economic benefit.
Embodiment 3
The present embodiment provides a kind of preparation method of zirconium dioxide, using the preparation facilities of the zirconium dioxide in embodiment 2,
Method in the present embodiment is distinguished as with the method in embodiment 2：
In step 1), the heating temperature in evaporator 1 is 420 DEG C；
In step 2), the molal quantity of hydrogen：The molal quantity of oxygen：Molal quantity=2.3 of zirconium chloride:1:1.1.
Embodiment 4
The present embodiment provides a kind of preparation method of zirconium dioxide, using the preparation facilities of the zirconium dioxide in embodiment 2,
Method in the present embodiment is distinguished as with the method in embodiment 2：
In step 1), the heating temperature in evaporator 1 is 530 DEG C；
In step 2), the molal quantity of hydrogen：The molal quantity of oxygen：Molal quantity=2.2 of zirconium chloride:1:1.2.
Embodiment 5
As shown in Fig. 2, the present embodiment also provides a kind of preparation facilities of zirconium dioxide, including：
Evaporator 1, for being gaseous state zirconium chloride by solid zirconium chloride heating sublimation；
Mixer 2 is connect with evaporator 1, and is connect respectively with evaporator 1, burner 3, and mixer 2 is used for gaseous state four
Zirconium chloride is mixed with the hydrogen being passed through in it；
Burner 3 is connect with 2 device of mixer, and burner 3 is used for gaseous state zirconium chloride and hydrogen to being passed through the mixing in it
Gas is lighted a fire with the air being passed through in it, and combustion reaction generation solid zirconium dioxide, hydrogen chloride obtain the first mixing after reaction
Object；The gas distributor 4 for being passed through material into burner 3, as shown in Figure 3,4, gas distributor are provided in burner 3
4 include：Inner ring channel 5 positioned at center is coated on middle ring channel 6 outside inner ring channel 5 in a ring, is coated on middle ring and leads to
Outer ring channel 7 outside road 6 in a ring, inner ring channel 5 are used to be passed through the gaseous mixture of gaseous state zirconium chloride and hydrogen, middle ring channel 6
For being passed through oxygen or air, outer ring channel 7 is used to be passed through the gaseous mixture of gaseous state zirconium chloride and hydrogen.
First deduster 8, connect with burner 3, and the first deduster 8 is used to remove the first mixture being passed through in it
Dirt, the solid zirconium dioxide in the first mixture are separated, and the first dedusting tail gas separated；
Absorption tower 12 is connect with the first deduster 8, and absorption tower 12 is used for the first dedusting tail gas adsorption hydrogen chloride, is being inhaled
The tower reactor for receiving tower 12 is absorbed the tower bottoms of tower 12, and the tower top on absorption tower 12 is absorbed tower tail gas, by tail gas from absorption tower
It is vented；Absorption tower 12 includes：Bottom of towe acid cycle pump 13, overhead reflux liquid spray thrower 14, bottom of towe acid cycle pump 13 are used
It is parsed in the tower bottoms on absorption tower 12 is pumped into Analytic Tower 15, overhead reflux liquid spray thrower 14 is used for absorption tower 12
The liquid at top is sprayed.
Analytic Tower 15 is connect with absorption tower 12, and Analytic Tower 15 is used to parse hydrogen chloride to the tower bottoms on absorption tower 12, is solving
The tower top of analysis tower 15 obtains Analytic Tower tail gas, and Analytic Tower tail gas includes hydrogen chloride, the tower reactor of Analytic Tower 15 and the tower on absorption tower 12
Top connection, the tower bottoms of Analytic Tower 15 are passed into the tower top on absorption tower 12, the leacheate as absorption tower 12；The tower on absorption tower 12
Kettle is connect with the tower top on absorption tower 12, and bottom of towe acid cycle pump 13 is additionally operable to the tower bottoms on absorption tower 12 being pumped into absorption tower 12
Tower top, the leacheate as absorption tower 12.15 bottom of Analytic Tower setting having heaters 16 is used to heat.
The present embodiment provides a kind of methods that zirconium dioxide is prepared using above device, include the following steps：
1) using refined solid zirconium chloride as raw material, by solid zirconium chloride, heating sublimation is gaseous state four in evaporator 1
Zirconium chloride, the heating temperature in evaporator 1 are 400 DEG C.
2) after gaseous state zirconium chloride is mixed with excessive hydrogen in mixer 2, enter by gas distributor 4 and burn
It is uniform with oxygen mix in the exit of gas distributor 4 in reactor, the molal quantity of hydrogen：The molal quantity of oxygen in air：
Molal quantity=2.1 of zirconium chloride：1.3：1, igniting, it is mixed to obtain first for reaction generation solid zirconium dioxide, hydrogen chloride after reaction
Object is closed, after igniting reaction, exothermic heat of reaction causes the temperature in burner 3 to be maintained at 500~1000 DEG C.In reaction process, hydrogen,
Air excess, the reaction was complete for zirconium chloride.First mixture includes：Hydrogen chloride content 35-45mol%, nitrogen content 45-
55mol%, zirconium dioxide content 5-15mol% (solid), oxygen content 0-5mol%, vapour content 0-1mol%, hydrogen
Content is less than 0.1mol%.
3) the first mixture is passed into the first deduster 8 and be dusted, the solid zirconium dioxide in the first mixture
It is separated, and the first dedusting tail gas separated.First dedusting tail gas includes：Hydrogen chloride content 40-45mol%,
Nitrogen content 50-55mol%, oxygen content 1-5mol%, water vapour content 0-1mol%, hydrogen content are less than 0.1mol%.
4) the first dedusting tail gas is passed into 12 adsorbing chlorinated hydrogen of absorption tower, the tower reactor on absorption tower 12 is absorbed tower 12
Tower bottoms, the tower top on absorption tower 12 is absorbed tower tail gas, tail gas from absorption tower is vented.Absorption tower 12 is with dilute hydrochloric acid
For absorbent, the first dedusting tail gas enters absorption tower 12 from the bottom on absorption tower 12, process is moved up in absorption tower 12
In with the tower top on absorption tower 12 spray and lower acid solution carry out gas-liquid contact, the hydrogen chloride in the first dedusting tail gas is absorbed, suction
The tail gas from absorption tower that the tower top of receipts tower 12 obtains includes nitrogen, oxygen, can directly be vented, and the tower bottoms on absorption tower 12 is highly concentrated
Spend hydrochloric acid.Tail gas from absorption tower includes：Nitrogen content 90-98mol%, oxygen content 2-5mol%, moisture 0-1mol%, hydrogen
Gas content is less than 0.1mol%.
5) tower bottoms on absorption tower 12 is passed through Analytic Tower 15 and parses hydrogen chloride, Analytic Tower is obtained in the tower top of Analytic Tower 15
Tail gas, Analytic Tower tail gas include hydrogen chloride.15 bottom of Analytic Tower sets having heaters 16, and heater 16 heats so that Analytic Tower 15
The temperature of bottom is 70~85 DEG C, and the hydrogen chloride gas in acid solution in Analytic Tower 15 is transferred to by liquid phase in gas phase, is parsed
The hydrogen chloride gas come is discharged by the tower top of Analytic Tower 15, and Analytic Tower tail gas is discharged by the tower top of Analytic Tower 15, may be used as three
The chlorinating agent of chlorine hydrogen silicon synthesis procedure.In the present embodiment, chlorine element fully recycles in reaction process, solves environmental pollution
Problem, while improve economic benefit.Analytic Tower tail gas includes：99vol% hydrogen chloride, 1vol% water.
6) tower bottoms of the tower bottoms of Analytic Tower 15 and/or absorption tower 12 is passed into the tower top on absorption tower 12, as suction
Receive the leacheate of tower 12.The tower bottoms of the Analytic Tower 15 of low concentration obtained after being parsed by Analytic Tower 15 is passed into absorption tower 12
Tower top.
The preparation method of zirconium dioxide in the present embodiment prepares solid zirconium dioxide by ignition reaction, realizes
The self-sufficiency of heat, so as to save energy, reduces production cost in burner 3.The chlorination generated in ignition reaction
Hydrogen fully recycles, and solves problem of environmental pollution, improves economic benefit.
Embodiment 6
The present embodiment provides a kind of preparation method of zirconium dioxide, using the preparation facilities of the zirconium dioxide in embodiment 5,
Method in the present embodiment is distinguished as with the method in embodiment 5：
In step 1), the heating temperature in evaporator 1 is 500 DEG C；
In step 2), the molal quantity of hydrogen：The molal quantity of oxygen：Molal quantity=2.15 of zirconium chloride：1.1：1.
Embodiment 7
The present embodiment provides a kind of preparation method of zirconium dioxide, using the preparation facilities of the zirconium dioxide in embodiment 5,
Method in the present embodiment is distinguished as with the method in embodiment 5：
In step 1), the heating temperature in evaporator 1 is 550 DEG C；
In step 2), the molal quantity of hydrogen：The molal quantity of oxygen：Molal quantity=2.2 of zirconium chloride：1.5：1.
It is understood that the principle that embodiment of above is intended to be merely illustrative of the present and the exemplary implementation that uses
Mode, however the present invention is not limited thereto.For those skilled in the art, in the essence for not departing from the present invention
In the case of refreshing and essence, various changes and modifications can be made therein, these variations and modifications are also considered as protection scope of the present invention.
Claims (17)
1. a kind of preparation method of zirconium dioxide, which is characterized in that include the following steps：
1) by solid zirconium chloride, heating sublimation is gaseous state zirconium chloride in evaporator；
2) gaseous state zirconium chloride and hydrogen, oxygen or air are lighted a fire in burner, combustion reaction generation solid dioxy
Change zirconium, hydrogen chloride, the first mixture is obtained after reaction.
2. the preparation method of zirconium dioxide according to claim 1, which is characterized in that in the step 2) in burner
Temperature is 500~1000 DEG C.
3. the preparation method of zirconium dioxide according to claim 1, which is characterized in that further included after the step 2)
Following steps：
3) the first mixture is passed into the first deduster and be dusted, the solid zirconium dioxide in the first mixture is detached
Get off, and the first dedusting tail gas separated.
4. the preparation method of zirconium dioxide according to claim 3, which is characterized in that when gaseous state zirconium chloride in step 2)
When being lighted a fire in burner with hydrogen, oxygen, the molal quantity of hydrogen：The molal quantity of oxygen：The molal quantity of zirconium chloride=
(2.2~2.5):1:(1.1~1.2).
5. the preparation method of zirconium dioxide according to claim 4, which is characterized in that the boiling point of zirconium chloride<First removes
Temperature in dirt device<The boiling point of zirconium dioxide.
6. the preparation method of zirconium dioxide according to claim 4 or 5, which is characterized in that further included after the step 3)
Following steps：
4) the first dedusting tail gas is passed into cooler and cooled down, the gaseous state zirconium chloride in the first dedusting tail gas is cooled down
For solid zirconium chloride, cooling mixture is obtained；
5) cooling mixture is passed through the second deduster to be dusted, cools down the solid zirconium chloride in mixture by under separation
Come, and the second dedusting tail gas separated；
6) the second dedusting tail gas is passed through oxygen-eliminating device and carries out deoxygenation, obtain oxygen-eliminating device tail gas, oxygen-eliminating device tail gas include hydrogen chloride and
Hydrogen.
7. the preparation method of zirconium dioxide according to claim 6, which is characterized in that through subcooler in the step 4)
The temperature cooled down is 150~220 DEG C.
8. the preparation method of zirconium dioxide according to claim 3, which is characterized in that when gaseous state zirconium chloride in step 2)
When being lighted a fire in burner with hydrogen, air, the molal quantity of hydrogen：The molal quantity of oxygen in air：Zirconium chloride rubs
That number=(2.1~2.2)：(1.1~1.5)：1.
9. the preparation method of zirconium dioxide according to claim 8, which is characterized in that further included after the step 3) following
Step：
4) the first dedusting tail gas being passed into the adsorbing chlorinated hydrogen in absorption tower, the tower reactor on absorption tower is absorbed the tower bottoms of tower,
Tower top on absorption tower is absorbed tower tail gas, and tail gas from absorption tower is vented；
5) tower bottoms on absorption tower is passed through Analytic Tower parsing hydrogen chloride, obtains Analytic Tower tail gas in the tower top of Analytic Tower, parse
Tower tail gas includes hydrogen chloride.
10. the preparation method of zirconium dioxide according to claim 9, which is characterized in that further included after the step 5)
Following steps：
6) tower bottoms of the tower bottoms of Analytic Tower and/or absorption tower is passed into the tower top on absorption tower, the elution as absorption tower
Liquid.
11. a kind of preparation facilities of zirconium dioxide, which is characterized in that including：
Evaporator, for being gaseous state zirconium chloride by solid zirconium chloride heating sublimation；
Burner is connect with evaporator, and burner carries out for gaseous state zirconium chloride with hydrogen, oxygen or air in burner
Igniting, combustion reaction generation solid zirconium dioxide, hydrogen chloride, obtains the first mixture after reaction.
12. the preparation facilities of zirconium dioxide according to claim 11, which is characterized in that further include：
Mixer is set between evaporator and burner, and is connect respectively with evaporator, burner, and mixer is used for gas
State zirconium chloride is mixed with the hydrogen being passed through in it.
13. the preparation facilities of zirconium dioxide according to claim 11, which is characterized in that be provided in burner for
The gas distributor of material is passed through in burner, gas distributor includes：Inner ring channel positioned at center is coated on inner ring
Middle ring channel outside channel in a ring is coated on outer ring channel in a ring outside middle ring channel, and inner ring channel is for being passed through gaseous state
The gaseous mixture of zirconium chloride and hydrogen, for being passed through oxygen or air, outer ring channel is used to be passed through four chlorination of gaseous state middle ring channel
The gaseous mixture of zirconium and hydrogen.
14. the preparation facilities of the zirconium dioxide according to claim 11~13 any one, which is characterized in that further include：
First deduster, connect with burner, and the first deduster is for being dusted the first mixture being passed through in it, and first
Solid zirconium dioxide in mixture is separated, and the first dedusting tail gas separated.
15. the preparation facilities of zirconium dioxide according to claim 14, which is characterized in that further include：
Cooler is connect with the first deduster, and cooler is cold by gaseous state zirconium chloride for being cooled down to the first dedusting tail gas
But it is solid zirconium chloride, obtains cooling mixture；
Second deduster, connect with cooler, and the second deduster is dusted for that will cool down mixture, cools down in mixture
Solid zirconium chloride is separated, and the second dedusting tail gas separated；
Oxygen-eliminating device is connect with the second deduster, and oxygen-eliminating device is used to the second dedusting tail gas carrying out deoxygenation, obtains oxygen-eliminating device tail gas,
Oxygen-eliminating device tail gas includes hydrogen chloride and hydrogen.
16. the preparation facilities of zirconium dioxide according to claim 14, which is characterized in that further include：
Absorption tower is connect with the first deduster, and absorption tower is used for the first dedusting tail gas adsorption hydrogen chloride, the tower reactor on absorption tower
Be absorbed the tower bottoms of tower, and the tower top on absorption tower is absorbed tower tail gas, and tail gas from absorption tower is vented；
Analytic Tower is connect with absorption tower, and Analytic Tower is used to parse hydrogen chloride to the tower bottoms on absorption tower, is obtained in the tower top of Analytic Tower
To Analytic Tower tail gas, Analytic Tower tail gas includes hydrogen chloride.
17. the preparation facilities of zirconium dioxide according to claim 16, which is characterized in that the tower reactor of Analytic Tower and absorption tower
Tower top connection, the tower bottoms of Analytic Tower is passed into the tower top on absorption tower, the leacheate as absorption tower；And/or
The tower reactor on absorption tower and the tower top on absorption tower connect, and the tower bottoms on absorption tower is passed into the tower top on absorption tower, as absorption
The leacheate of tower.
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