CN108190950B - Preparation method of zirconium dioxide - Google Patents
Preparation method of zirconium dioxide Download PDFInfo
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- CN108190950B CN108190950B CN201810116917.6A CN201810116917A CN108190950B CN 108190950 B CN108190950 B CN 108190950B CN 201810116917 A CN201810116917 A CN 201810116917A CN 108190950 B CN108190950 B CN 108190950B
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Abstract
The invention discloses a preparation method of zirconium dioxide, which comprises the following steps: 1) heating and sublimating solid zirconium tetrachloride into gaseous zirconium tetrachloride in an evaporator; 2) igniting gaseous zirconium tetrachloride and hydrogen, oxygen or air in a combustor, carrying out combustion reaction to generate solid zirconium dioxide and hydrogen chloride, and obtaining a first mixture after the reaction. According to the preparation method of zirconium dioxide, solid zirconium dioxide is prepared through ignition combustion reaction, so that self-supply of heat in a combustor is realized, energy is saved, and production cost is reduced.
Description
Technical Field
The invention belongs to the technical field of zirconium dioxide production, and particularly relates to a preparation method of zirconium dioxide.
Background
According to the difference of the process, the preparation process of zirconia can be divided into two processes of chemical method (wet process) and electric melting method (dry process), wherein the electric melting method is to melt zircon sand and coke or petroleum coke in a one-step electric arc furnace at the high temperature of 2300 ℃ to obtain zirconia. The chemical method is that the zircon sand is firstly converted into zirconium oxychloride, and the zirconium oxychloride is decomposed at high temperature to generate zirconium oxide. The main disadvantage of the electric melting method is that the purity of the product is low, the average purity of the electric melting zirconium produced at present in China is 98.5%, and the application of the electric melting zirconium oxide in the field of high-end products is limited. The chemical method for preparing the zirconium oxide has complex process, also produces a large amount of waste liquid and has high production cost.
In the prior art, zirconium tetrachloride hydrolysis is adopted to prepare zirconium oxide, and the process is complex. The development of a novel process for preparing zirconium dioxide has therefore been a technical barrier which is difficult for the person skilled in the art to overcome.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of zirconium dioxide aiming at the defects in the prior art, and solve the problems of complex process and high production cost in the traditional chemical method for preparing zirconium dioxide.
The technical scheme adopted for solving the technical problem of the invention is to provide a preparation method of zirconium dioxide, which comprises the following steps:
1) heating and sublimating solid zirconium tetrachloride into gaseous zirconium tetrachloride in an evaporator;
2) igniting gaseous zirconium tetrachloride and hydrogen, oxygen or air in a combustor, carrying out combustion reaction to generate solid zirconium dioxide and hydrogen chloride, and obtaining a first mixture after the reaction.
Preferably, the temperature in the combustor in the step 2) is 500-1000 ℃.
Preferably, in the step 2), after the ignition reaction, the reaction releases heat so that the temperature in the combustor is maintained at 500-1000 ℃. The temperature in the combustor is controlled to be 500-1000 ℃ by adjusting the air inflow of oxygen in the combustion reactor.
Preferably, the heating temperature in the evaporator in the step 1) is 400-550 ℃.
Preferably, the following steps are further included after the step 2):
3) and introducing the first mixture into a first dust remover for dust removal, separating solid zirconium dioxide in the first mixture, and obtaining separated first dust removal tail gas.
Preferably, when the gaseous zirconium tetrachloride is ignited with hydrogen and oxygen in the burner in step 2), the molar ratio of hydrogen: molar number of oxygen: the molar number of zirconium tetrachloride is (2-2.5): 1: (1-1.1). The first mixture includes: zirconium dioxide content (solids), hydrogen chloride, zirconium tetrachloride, hydrogen, trace amounts of oxygen, and trace amounts of water vapor.
Preferably, the boiling point of zirconium tetrachloride < the temperature in the first precipitator < the boiling point of zirconium dioxide.
Preferably, the temperature in the first dust collector is 400 to 1000 ℃. Under normal temperature and pressure, the boiling point of zirconium tetrachloride is 331 ℃ and the boiling point of zirconium dioxide is 4300 ℃.
Preferably, the method further comprises the following steps after the step 3):
4) introducing the first dedusting tail gas into a cooler for cooling, and cooling gaseous zirconium tetrachloride in the first dedusting tail gas into solid zirconium tetrachloride to obtain a cooled mixture; cooling the mixture comprises: hydrogen chloride, zirconium tetrachloride, hydrogen, trace oxygen, trace water vapor and trace zirconium dioxide.
5) Introducing the cooled mixture into a second dust remover for dust removal, separating solid zirconium tetrachloride in the cooled mixture, and obtaining separated second dust removal tail gas; the second dust removal tail gas comprises: hydrogen chloride, hydrogen and trace oxygen.
6) And introducing the second dedusting tail gas into a deaerator for deaerating to obtain deaerator tail gas, wherein the deaerator tail gas comprises hydrogen chloride and hydrogen. The deaerator tail gas includes: hydrogen chloride, hydrogen.
Preferably, the temperature for cooling by the cooler in the step 4) is 150-220 ℃.
Preferably, when the gaseous zirconium tetrachloride in step 2) is ignited with hydrogen and air in the burner, the molar ratio of hydrogen: number of moles of oxygen in air: the molar number of zirconium tetrachloride is (2-2.5): 1-1.5): 1. The first mixture includes: hydrogen chloride, nitrogen, zirconium dioxide (solid), trace oxygen, trace water vapor and trace hydrogen.
Preferably, the method further comprises the following steps after the step 3):
4) introducing the first dust removal tail gas into an absorption tower to adsorb hydrogen chloride, obtaining tower bottom liquid of the absorption tower at a tower bottom of the absorption tower, obtaining tail gas of the absorption tower at the tower top of the absorption tower, and emptying the tail gas of the absorption tower; the first dust removal tail gas comprises: hydrogen chloride, nitrogen, oxygen, trace water vapor and trace hydrogen.
The tail gas of the absorption tower comprises: nitrogen, oxygen, trace moisture and trace hydrogen.
5) And introducing the tower bottom liquid of the absorption tower into an analytic tower to analyze hydrogen chloride, and obtaining tail gas of the analytic tower at the top of the analytic tower, wherein the tail gas of the analytic tower comprises hydrogen chloride. The tail gas of the desorption tower comprises: hydrogen chloride and water.
Preferably, the step 5) is followed by the following steps:
6) and introducing the tower bottom liquid of the desorption tower and/or the tower bottom liquid of the absorption tower to the top of the absorption tower to be used as the leacheate of the absorption tower.
The invention also provides a preparation device of zirconium dioxide, comprising:
the evaporator is used for heating and sublimating the solid zirconium tetrachloride into gaseous zirconium tetrachloride;
the combustor is connected with the evaporator and used for igniting gaseous zirconium tetrachloride and hydrogen, oxygen or air in the combustor, the gaseous zirconium tetrachloride and the hydrogen, the oxygen or the air are subjected to combustion reaction to generate solid zirconium dioxide and hydrogen chloride, and a first mixture is obtained after the reaction.
Preferably, the apparatus for preparing zirconium dioxide further comprises:
and the mixer is arranged between the evaporator and the combustor and is respectively connected with the evaporator and the combustor, and the mixer is used for mixing the gaseous zirconium tetrachloride with the hydrogen introduced into the mixer.
Preferably, a gas distributor for introducing the material into the burner is arranged in the burner, and the gas distributor comprises: the inner ring channel is used for introducing mixed gas of gaseous zirconium tetrachloride and hydrogen, the middle ring channel is used for introducing oxygen or air, and the outer ring channel is used for introducing mixed gas of gaseous zirconium tetrachloride and hydrogen.
Preferably, the apparatus for preparing zirconium dioxide further comprises:
the first dust remover is connected with the combustor and used for removing dust of the first mixture introduced into the first dust remover, separating solid zirconium dioxide in the first mixture and obtaining separated first dust removal tail gas.
Preferably, the apparatus for preparing zirconium dioxide further comprises:
the cooler is connected with the first dust remover and used for cooling the first dust removal tail gas and cooling the gaseous zirconium tetrachloride into solid zirconium tetrachloride to obtain a cooled mixture;
the second dust remover is connected with the cooler and is used for removing dust from the cooled mixture, separating solid zirconium tetrachloride in the cooled mixture and obtaining separated second dust-removing tail gas;
and the deaerator is connected with the second dust remover and used for deaerating the second dust removal tail gas to obtain deaerator tail gas, and the deaerator tail gas comprises hydrogen chloride and hydrogen.
Preferably, the apparatus for preparing zirconium dioxide further comprises:
the absorption tower is connected with the first dust remover and used for adsorbing hydrogen chloride on the first dust removal tail gas, tower bottom liquid of the absorption tower is obtained at a tower bottom of the absorption tower, the tail gas of the absorption tower is obtained at the tower top of the absorption tower, and the tail gas of the absorption tower is discharged;
and the desorption tower is connected with the absorption tower and is used for desorbing hydrogen chloride from the tower bottom liquid of the absorption tower, and desorption tower tail gas is obtained at the tower top of the desorption tower and comprises hydrogen chloride.
Preferably, the tower kettle of the desorption tower is connected with the tower top of the absorption tower, and tower kettle liquid of the desorption tower is introduced to the tower top of the absorption tower to be used as eluent of the absorption tower; and/or the presence of a gas in the gas,
the tower kettle of the absorption tower is connected with the tower top of the absorption tower, and tower kettle liquid of the absorption tower is introduced to the tower top of the absorption tower to be used as leacheate of the absorption tower.
According to the preparation method of zirconium dioxide, solid zirconium dioxide is prepared through ignition combustion reaction, so that self-supply of heat in a combustor is realized, energy is saved, and production cost is reduced.
Drawings
FIG. 1 is a schematic structural view of an apparatus for preparing zirconium dioxide in example 2 of the present invention;
FIG. 2 is a schematic structural view of an apparatus for preparing zirconium dioxide in example 5 of the present invention;
FIG. 3 is a front view of a gas distributor in examples 2 and 5 of the present invention;
FIG. 4 is a plan view of a gas distributor in examples 2 and 5 of the present invention.
In the figure: 1-an evaporator; 2-a mixer; 3-a burner; 4-a gas distributor; 5-inner ring channel; 6-medium ring channel; 7-outer ring channel; 8-a first dust remover; 9-a cooler; 10-a second dust remover; 11-a deaerator; 12-an absorption column; 13-a tower bottom acid liquor circulating pump; 14-overhead reflux sprayer; 15-a resolution column; 16-heater.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Example 1
The embodiment provides a preparation method of zirconium dioxide, which comprises the following steps:
1) heating and sublimating solid zirconium tetrachloride into gaseous zirconium tetrachloride in an evaporator;
2) igniting gaseous zirconium tetrachloride and hydrogen, oxygen or air in a combustor, carrying out combustion reaction to generate solid zirconium dioxide and hydrogen chloride, and obtaining a first mixture after the reaction.
The embodiment also provides a preparation apparatus of zirconium dioxide, including:
the evaporator is used for heating and sublimating the solid zirconium tetrachloride into gaseous zirconium tetrachloride;
the combustor is connected with the evaporator and used for igniting gaseous zirconium tetrachloride and hydrogen, oxygen or air in the combustor, the gaseous zirconium tetrachloride and the hydrogen, the oxygen or the air are subjected to combustion reaction to generate solid zirconium dioxide and hydrogen chloride, and a first mixture is obtained after the reaction.
According to the preparation method of zirconium dioxide in the embodiment, solid zirconium dioxide is prepared through ignition combustion reaction, so that self-supply of heat in a combustor is realized, energy is saved, and production cost is reduced.
Example 2
As shown in fig. 1, this embodiment further provides an apparatus for preparing zirconium dioxide, including:
an evaporator 1 for heating and sublimating solid zirconium tetrachloride into gaseous zirconium tetrachloride; specifically, the main body of the evaporator 1 in this embodiment is made of carbon steel or stainless steel, a wear-resistant and high-temperature-resistant ceramic lining made of silicon nitride, zirconium oxide, aluminum oxide or a mixture thereof is disposed inside the evaporator 1, and a heating mechanism is disposed outside the evaporator 1, and the heating mode is one of resistance heating, radiation heating and induction heating. The pipeline between the evaporator 1 and the combustor 3 is internally provided with a wear-resistant and high-temperature-resistant ceramic lining formed by silicon nitride, zirconia, alumina or a mixture thereof, and is also provided with electric heat tracing and heat preservation.
The mixer 2 is connected with the evaporator 1 and is respectively connected with the evaporator 1 and the burner 3, and the mixer 2 is used for mixing gaseous zirconium tetrachloride with hydrogen introduced into the mixer;
the combustor 3 is connected with the mixer 2, and the combustor 3 is used for igniting the mixed gaseous zirconium tetrachloride and hydrogen introduced into the combustor and oxygen introduced into the combustor, carrying out combustion reaction to generate solid zirconium dioxide and hydrogen chloride, and obtaining a first mixture after the reaction; a gas distributor 4 for introducing the material into the burner 3 is provided in the burner 3, and as shown in fig. 3 and 4, the gas distributor 4 includes: the gas-liquid separation device comprises an inner ring channel 5 positioned in the center, a middle ring channel 6 wrapping the inner ring channel 5 and presenting an annular shape, and an outer ring channel 7 wrapping the middle ring channel 6 and presenting an annular shape, wherein the inner ring channel 5 is used for introducing mixed gas of gaseous zirconium tetrachloride and hydrogen, the middle ring channel 6 is used for introducing oxygen, and the outer ring channel 7 is used for introducing mixed gas of gaseous zirconium tetrachloride and hydrogen. The main body of the combustor 3 is made of 800H steel high-temperature resistant material, a wear-resistant high-temperature resistant ceramic lining made of silicon nitride, zirconium oxide, aluminum oxide or composite materials of the silicon nitride, the zirconium oxide and the aluminum oxide is arranged inside the combustor, and a gas distributor 4 is arranged at the bottom of the combustion reactor to form reaction conditions of combustible gas hydrogen wrapping oxidant oxygen, so that complete reaction of the oxidant in the reaction process is ensured.
The first dust remover 8 is connected with the combustor 3, the first dust remover 8 is used for removing dust of the first mixture introduced into the first dust remover, solid zirconium dioxide in the first mixture is separated, and separated first dust removal tail gas is obtained; preferably, the first dust collector 8 is a bag type dust collector, and the filter element is a metal sintered filter element or a cloth bag type filter element.
The cooler 9 is connected with the first dust remover 8, and the cooler 9 is used for cooling the first dust removal tail gas and cooling the gaseous zirconium tetrachloride into solid zirconium tetrachloride to obtain a cooled mixture; preferably, the cooler 9 is a tubular heat exchanger, and the adopted refrigerant is circulating water or steam condensate.
The second dust remover 10 is connected with the cooler 9, the second dust remover 10 is used for removing dust from the cooled mixture, solid zirconium tetrachloride in the cooled mixture is separated, and separated second dust-removing tail gas is obtained;
the deaerator 11 is connected with the second dust remover 10, and the deaerator 11 is used for deoxidizing the second dust removal tail gas to obtain deaerator tail gas, and the deaerator tail gas comprises hydrogen chloride and hydrogen. The deaerator 11 uses silica gel and/or molecular sieve as an adsorbent, and removes oxygen in the second dust removal tail gas in a temperature swing adsorption or pressure swing adsorption mode.
The embodiment provides a method for preparing zirconium dioxide by using the device, which comprises the following steps:
1) refined solid zirconium tetrachloride is used as a raw material, the solid zirconium tetrachloride is heated and sublimated in an evaporator 1 to gaseous zirconium tetrachloride, and the heating temperature in the evaporator 1 is 480 ℃.
2) Gaseous zirconium tetrachloride and excessive hydrogen are mixed in the mixer 2, then enter the combustion reactor through the gas distributor 4, and are uniformly mixed with oxygen at the outlet of the gas distributor 4, and the mole number of the hydrogen is as follows: molar number of oxygen: igniting zirconium tetrachloride with the molar number of 2.5:1:1.15, reacting to generate zirconium dioxide powder and hydrogen chloride gas, reacting to obtain a first mixture, igniting and reacting, and releasing heat to keep the temperature in the combustor 3 at 500-1000 ℃. The temperature in the combustor 3 is controlled to be 500-1000 ℃ by adjusting the air inflow of oxygen in the combustion reactor. In the reaction process, the zirconium tetrachloride is slightly excessive, the hydrogen is excessive, and the oxygen completely reacts. The first mixture includes: zirconium dioxide content 15-20 mol% (solid), hydrogen chloride content 65-75 mol%, zirconium tetrachloride content 1-5 mol%, hydrogen content 5-10 mol%, oxygen content less than 0.1 mol%, water vapor content less than 0.1 mol%.
3) And introducing zirconium dioxide powder in the first mixture into the first dust remover 8 for dust removal under the action of the airflow, wherein the boiling point of zirconium tetrachloride is lower than the temperature in the first dust remover 8 and lower than the boiling point of zirconium dioxide, the solid zirconium dioxide in the first mixture is separated, and the separated first dust removal tail gas is obtained. Specifically, the temperature in the first dust collector 8 in this embodiment is 400 to 1000 ℃. The solid zirconium dioxide is discharged through a slag discharge pipeline connected to the bottom of the first dust collector 8. The first dust removal tail gas comprises: the zirconium dioxide content is less than 0.1 mol%, the hydrogen chloride content is 75-90 mol%, the zirconium tetrachloride content is 2-5 mol%, the hydrogen content is 10-15 mol%, the oxygen content is less than 0.1 mol%, and the water vapor content is less than 0.1 mol%.
4) And (3) introducing the first dedusting tail gas into a cooler 9 for cooling, wherein the cooling temperature of the cooler 9 is 180-220 ℃. Unreacted zirconium tetrachloride vapor in the first dedusting tail gas is cooled to solid zirconium tetrachloride, and a cooled mixture is obtained. The cooling process does not change the amount of the substance, and the cooling mixture comprises: the zirconium dioxide content is less than 0.1 mol%, the hydrogen chloride content is 75-90 mol%, the zirconium tetrachloride content is 2-5 mol%, the hydrogen content is 10-15 mol%, the oxygen content is less than 0.1 mol%, and the water vapor content is less than 0.1 mol%.
5) Introducing the cooled mixture into a second dust remover 10 for dust removal, separating solid zirconium tetrachloride in the cooled mixture, and obtaining separated second dust removal tail gas; the solid zirconium tetrachloride was discharged through a slag discharge line connected to the bottom of the second dust collector 10. The second dust removal tail gas comprises: 85-90 mol% of hydrogen chloride, 10-15 mol% of hydrogen and less than 0.1 mol% of oxygen.
6) And introducing the second dedusting tail gas into a deaerator 11 for deaerating to obtain deaerator tail gas, wherein the deaerator tail gas comprises hydrogen chloride and hydrogen. The deaerator tail gas comprises a mixed gas of hydrogen chloride and hydrogen with high purity, and can be used as a chlorinating agent in the production process of trichlorosilane. In the embodiment, the chlorine element is fully recycled in the reaction process, the problem of environmental pollution is solved, and the economic benefit is improved. The deaerator tail gas includes: the hydrogen chloride content is 85-90 mol%, and the hydrogen content is 10-15 mol%.
In the preparation method of zirconium dioxide in the embodiment, solid zirconium dioxide is prepared through ignition combustion reaction, so that self-supply of heat in the combustor 3 is realized, energy is saved, and production cost is reduced. The hydrogen chloride generated in the ignition combustion reaction is fully recovered, the problem of environmental pollution is solved, and the economic benefit is improved.
Example 3
This example provides a method for preparing zirconium dioxide, using the apparatus for preparing zirconium dioxide in example 2, the difference between the method in this example and the method in example 2 is:
in the step 1), the heating temperature in the evaporator 1 is 420 ℃;
in step 2), the molar number of hydrogen: molar number of oxygen: the molar number of zirconium tetrachloride was 2.3:1: 1.1.
Example 4
This example provides a method for preparing zirconium dioxide, using the apparatus for preparing zirconium dioxide in example 2, the difference between the method in this example and the method in example 2 is:
in the step 1), the heating temperature in the evaporator 1 is 530 ℃;
in step 2), the molar number of hydrogen: molar number of oxygen: the molar number of zirconium tetrachloride was 2.2:1: 1.2.
Example 5
As shown in fig. 2, this embodiment further provides an apparatus for preparing zirconium dioxide, including:
an evaporator 1 for heating and sublimating solid zirconium tetrachloride into gaseous zirconium tetrachloride;
the mixer 2 is connected with the evaporator 1 and is respectively connected with the evaporator 1 and the burner 3, and the mixer 2 is used for mixing gaseous zirconium tetrachloride with hydrogen introduced into the mixer;
the combustor 3 is connected with the mixer 2, and the combustor 3 is used for igniting the mixed gaseous zirconium tetrachloride and hydrogen introduced into the combustor and air introduced into the combustor, carrying out combustion reaction to generate solid zirconium dioxide and hydrogen chloride, and obtaining a first mixture after the reaction; a gas distributor 4 for introducing the material into the burner 3 is provided in the burner 3, and as shown in fig. 3 and 4, the gas distributor 4 includes: the gas turbine comprises an inner ring channel 5 positioned in the center, a middle ring channel 6 which is wrapped outside the inner ring channel 5 and is annular, and an outer ring channel 7 which is wrapped outside the middle ring channel 6 and is annular, wherein the inner ring channel 5 is used for introducing mixed gas of gaseous zirconium tetrachloride and hydrogen, the middle ring channel 6 is used for introducing oxygen or air, and the outer ring channel 7 is used for introducing mixed gas of gaseous zirconium tetrachloride and hydrogen.
The first dust remover 8 is connected with the combustor 3, the first dust remover 8 is used for removing dust of the first mixture introduced into the first dust remover, solid zirconium dioxide in the first mixture is separated, and separated first dust removal tail gas is obtained;
the absorption tower 12 is connected with the first dust remover 8, the absorption tower 12 is used for adsorbing hydrogen chloride on the first dust removal tail gas, tower bottom liquid of the absorption tower 12 is obtained at a tower bottom of the absorption tower 12, the absorption tower tail gas is obtained at the tower top of the absorption tower 12, and the absorption tower tail gas is discharged; the absorption tower 12 includes: the tower bottom acid liquid circulating pump 13 is used for pumping the tower bottom liquid of the absorption tower 12 into the analysis tower 15 for analysis, and the tower top reflux liquid sprayer 14 is used for spraying the liquid at the top of the absorption tower 12.
The desorption tower 15 is connected with the absorption tower 12, the desorption tower 15 is used for desorbing hydrogen chloride from the tower bottom liquid of the absorption tower 12, desorption tower tail gas is obtained at the tower top of the desorption tower 15, the desorption tower tail gas comprises hydrogen chloride, the tower bottom of the desorption tower 15 is connected with the tower top of the absorption tower 12, and the tower bottom liquid of the desorption tower 15 is introduced to the tower top of the absorption tower 12 and is used as leacheate of the absorption tower 12; the bottom of the absorption tower 12 is connected to the top of the absorption tower 12, and the bottom acid circulation pump 13 is further configured to pump the bottom of the absorption tower 12 to the top of the absorption tower 12 as an eluent of the absorption tower 12. The bottom of the desorption tower 15 is provided with a heater 16 for heating.
The embodiment provides a method for preparing zirconium dioxide by using the device, which comprises the following steps:
1) refined solid zirconium tetrachloride is used as a raw material, the solid zirconium tetrachloride is heated and sublimated in an evaporator 1 to be gaseous zirconium tetrachloride, and the heating temperature in the evaporator 1 is 400 ℃.
2) Gaseous zirconium tetrachloride and excessive hydrogen are mixed in the mixer 2, then enter the combustion reactor through the gas distributor 4, and are uniformly mixed with oxygen at the outlet of the gas distributor 4, and the mole number of the hydrogen is as follows: number of moles of oxygen in air: the molar number of zirconium tetrachloride is 2.1: 1.3: 1, igniting, reacting to generate solid zirconium dioxide and hydrogen chloride, reacting to obtain a first mixture, and after the ignition reaction, releasing heat in the reaction to keep the temperature in the combustor 3 at 500-1000 ℃. In the reaction process, hydrogen and air are excessive, and the zirconium tetrachloride completely reacts. The first mixture includes: 35-45 mol% of hydrogen chloride, 45-55 mol% of nitrogen, 5-15 mol% (solid) of zirconium dioxide, 0-5 mol% of oxygen, 0-1 mol% of water vapor and less than 0.1 mol% of hydrogen.
3) And (3) introducing the first mixture into a first dust remover 8 for dust removal, separating solid zirconium dioxide in the first mixture, and obtaining separated first dust removal tail gas. The first dust removal tail gas comprises: 40-45 mol% of hydrogen chloride, 50-55 mol% of nitrogen, 1-5 mol% of oxygen, 0-1 mol% of water vapor and less than 0.1 mol% of hydrogen.
4) Introducing the first dedusting tail gas into the absorption tower 12 to adsorb hydrogen chloride, obtaining tower bottom liquid of the absorption tower 12 at the tower bottom of the absorption tower 12, obtaining absorption tower tail gas at the tower top of the absorption tower 12, and emptying the absorption tower tail gas. The absorption tower 12 takes dilute hydrochloric acid as an absorbent, the first dust removal tail gas enters the absorption tower 12 from the bottom of the absorption tower 12, and is in gas-liquid contact with acid liquor sprayed from the top of the absorption tower 12 in the upward moving process in the absorption tower 12, hydrogen chloride in the first dust removal tail gas is absorbed, the tail gas of the absorption tower obtained from the top of the absorption tower 12 comprises nitrogen and oxygen, and can be directly discharged, and tower bottom liquid of the absorption tower 12 is high-concentration hydrochloric acid. The tail gas of the absorption tower comprises: 90-98 mol% of nitrogen, 2-5 mol% of oxygen, 0-1 mol% of water and less than 0.1 mol% of hydrogen.
5) Introducing the tower bottom liquid of the absorption tower 12 into an analytical tower 15 to analyze hydrogen chloride, and obtaining analytical tower tail gas at the top of the analytical tower 15, wherein the analytical tower tail gas comprises hydrogen chloride. The bottom of the analysis tower 15 is provided with a heater 16, the heater 16 heats the bottom of the analysis tower 15 to 70-85 ℃, hydrogen chloride gas in the acid liquid in the analysis tower 15 is transferred from the liquid phase to the gas phase, the analyzed hydrogen chloride gas is discharged from the top of the analysis tower 15, and tail gas of the analysis tower is discharged from the top of the analysis tower 15 and can be used as a chlorinating agent in a trichlorosilane synthesis process. In the embodiment, the chlorine element is fully recycled in the reaction process, the problem of environmental pollution is solved, and the economic benefit is improved. The tail gas of the desorption tower comprises: 99 vol% hydrogen chloride, 1 vol% water.
6) The bottom liquid of the desorption tower 15 and/or the bottom liquid of the absorption tower 12 is introduced to the top of the absorption tower 12 to be used as the eluent of the absorption tower 12. The bottom liquid of the low-concentration stripping column 15 obtained by stripping in the stripping column 15 is introduced into the top of the absorption column 12.
In the preparation method of zirconium dioxide in the embodiment, solid zirconium dioxide is prepared through ignition combustion reaction, so that self-supply of heat in the combustor 3 is realized, energy is saved, and production cost is reduced. The hydrogen chloride generated in the ignition combustion reaction is fully recovered, the problem of environmental pollution is solved, and the economic benefit is improved.
Example 6
This example provides a method for preparing zirconium dioxide, using the apparatus for preparing zirconium dioxide in example 5, the difference between the method in this example and the method in example 5 is:
in the step 1), the heating temperature in the evaporator 1 is 500 ℃;
in step 2), the molar number of hydrogen: molar number of oxygen: molar number of zirconium tetrachloride 2.15: 1.1: 1.
example 7
This example provides a method for preparing zirconium dioxide, using the apparatus for preparing zirconium dioxide in example 5, the difference between the method in this example and the method in example 5 is:
in the step 1), the heating temperature in the evaporator 1 is 550 ℃;
in step 2), the molar number of hydrogen: molar number of oxygen: molar number of zirconium tetrachloride 2.2: 1.5: 1.
it will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.
Claims (7)
1. The preparation method of zirconium dioxide is characterized by comprising the following steps:
1) heating and sublimating solid zirconium tetrachloride into gaseous zirconium tetrachloride in an evaporator;
2) igniting gaseous zirconium tetrachloride with hydrogen, oxygen or air in a burner, the molar number of hydrogen being: molar number of oxygen: the molar number of zirconium tetrachloride is (2.2 to 2.5) 1 (1.1 to 1.2), or the molar number of hydrogen gas: number of moles of oxygen in air: the molar number of zirconium tetrachloride is (2.1 to 2.2): (1.1-1.5): 1, generating solid zirconium dioxide and hydrogen chloride through a combustion reaction, obtaining a first mixture after the reaction, and preparing the solid zirconium dioxide through an ignition combustion reaction, thereby realizing self-sufficiency of heat in a combustor;
3) and introducing the first mixture into a first dust remover for dust removal, separating solid zirconium dioxide in the first mixture, and obtaining separated first dust removal tail gas.
2. The method for producing zirconium dioxide as claimed in claim 1, wherein the temperature in the burner in step 2) is 500 to 1000 ℃.
3. The method for producing zirconium dioxide as claimed in claim 1, wherein the boiling point of zirconium tetrachloride < the temperature in the first dust collector < the boiling point of zirconium dioxide.
4. The method for preparing zirconium dioxide according to claim 1 or 3, characterized in that the step 3) is followed by the following steps:
4) introducing the first dedusting tail gas into a cooler for cooling, and cooling gaseous zirconium tetrachloride in the first dedusting tail gas into solid zirconium tetrachloride to obtain a cooled mixture;
5) introducing the cooled mixture into a second dust remover for dust removal, separating solid zirconium tetrachloride in the cooled mixture, and obtaining separated second dust removal tail gas;
6) and introducing the second dedusting tail gas into a deaerator for deaerating to obtain deaerator tail gas, wherein the deaerator tail gas comprises hydrogen chloride and hydrogen.
5. The method for preparing zirconium dioxide according to claim 4, wherein the temperature of cooling in the cooler in step 4) is 150 to 220 ℃.
6. The method for preparing zirconium dioxide according to claim 1, characterized in that the method further comprises the following steps after step 3):
4) introducing the first dust removal tail gas into an absorption tower to adsorb hydrogen chloride, obtaining tower bottom liquid of the absorption tower at a tower bottom of the absorption tower, obtaining tail gas of the absorption tower at the tower top of the absorption tower, and emptying the tail gas of the absorption tower;
5) and introducing the tower bottom liquid of the absorption tower into an analytic tower to analyze hydrogen chloride, and obtaining tail gas of the analytic tower at the top of the analytic tower, wherein the tail gas of the analytic tower comprises hydrogen chloride.
7. The method according to claim 6, characterized in that step 5) is followed by the following steps:
6) and introducing the tower bottom liquid of the desorption tower and/or the tower bottom liquid of the absorption tower to the top of the absorption tower to be used as the leacheate of the absorption tower.
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