CN109019682A - A kind of zirconium oxychloride and preparation method thereof - Google Patents
A kind of zirconium oxychloride and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of zirconium oxychlorides and preparation method thereof, method includes the following steps: 1) heating the thick zirconium chloride prepared by chloridising in a hydrogen atmosphere, the iron chloride in thick zirconium chloride is reacted with hydrogen generates frerrous chloride；2) it is heated under the first preset temperature, so that lower than the impurity gasification of the boiling point of zirconium chloride in thick zirconium chloride；3) it is heated under the second preset temperature, so that the zirconium chloride distillation in thick zirconium chloride, the zirconium chloride of distillation is hydrolyzed, zirconium oxychloride is generated.The preparation method of zirconium oxychloride in the present invention, impurity can effectively be removed, iron chloride in thick zirconium chloride is reduced into frerrous chloride, chlorination iron tramp is mixed into when can prevent zirconium chloride from distilling, and then the zirconium oxychloride product of high-purity is produced, the purity of zirconium oxychloride is not less than 95mas%.
Description
Technical field
The invention belongs to zirconium oxychloride production technical fields, and in particular to a kind of zirconium oxychloride and preparation method thereof.
Background technique
Hydration basic zirconium chloride is production other zirconium product such as zirconium dioxide, zirconium carbonate, zirconium sulfate, compound zirconia and zirconiums
The primary raw material of hafnium separation preparation metal zirconium hafnium, can be used for weaving, leather, rubber additive, metal conditioner, painting
Expect the products such as desiccant, refractory material, ceramics, catalyst, fireproof agent.
The method of zirconium oxychloride production can generally be divided into two kinds, another one is using alkali soluble solution zircon sand method
It is to be hydrolyzed using thick zirconium chloride, purify and obtain high-purity zirconium oxychloride.The technical process that alkali fusion prepares zirconium oxychloride is deposited
It is big in acid waste water yield, the problems such as environmental pollution is serious, therefore thick zirconium chloride is prepared by chloridising at present, then by four
It is the emphasis studied that zirconium chloride, which is hydrolyzed, purifies,.
Contain ZrCl in the thick zirconium chloride that chloridising obtains4、HfCl4、FeCl3、AlCl3、CaCl2、ZrSiO4、
HfSiO4、SiO2、Al2O3、Fe2O3、TiO2、UO2、ThO2、CaO、Y2O3, the impurity such as C, the oxygen chlorine obtained after thick zirconium chloride hydrolysis
The impurity content changed in zirconium is high, especially FeCl3、AlCl3Presence it is larger to the qualitative effects of zirconium oxychloride, cause
The quality of zirconium oxychloride is lower.
Summary of the invention
The technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide a kind of oxychlorination
Zirconium and preparation method thereof, the impurity content solved in the zirconium oxychloride obtained after thick zirconium chloride hydrolysis in the prior art are high
Technical problem.
It solves technical solution used by present invention problem and is to provide the preparation method of zirconium oxychloride a kind of, including with
Lower step:
1) the thick zirconium chloride prepared by chloridising is heated in a hydrogen atmosphere, iron chloride and hydrogen in thick zirconium chloride
Solid/liquid/gas reactions generate frerrous chloride；
2) it is heated under the first preset temperature, so that lower than the impurity gasification of the boiling point of zirconium chloride in thick zirconium chloride；
3) it is heated under the second preset temperature, so that the zirconium chloride distillation in thick zirconium chloride, by four chlorinations of distillation
Zirconium hydrolysis, generates zirconium oxychloride.
Chloridising prepares the specific method of thick zirconium chloride: zircon sand, carbonaceous reducing agent, chlorine are anti-at 1000~1200 DEG C
Zirconium chloride, silicon tetrachloride, hafnium tetrachloride, titanium tetrachloride and other metallic chloride impurities should be generated, while also generating an oxygen
Change carbon, carbon dioxide, is cooled to 120~150 DEG C and obtains thick zirconium chloride.
Thick zirconium chloride includes: 90-93mas%ZrCl4, 1-2mas%HfCl4, 1-3mas%ZrSiO4, 0-1mas%
HfSiO4, 0-1mas%SiO2, 1.5-3mas%C, 1.5-3mas%AlCl3, 0.5-1mas%FeCl3, 0-0.5mas%
CaCl2, 0-0.1mas%YCl3, 0-0.1mas%ThCl4, 0-0.2mas%Fe2O3, 0-0.2mas%Al2O3, 0-0.2mas%
CaO, 0-0.1mas%TiO2, 0-0.1mas%UO2, 0-0.1mas%ThO2, 0-0.1mas%Y2O3。
Preferably, thick zirconium chloride includes: 90-93mas%ZrCl4, 1-2mas%HfCl4, 1-3mas%ZrSiO4,
0.001-1mas%HfSiO4, 0.001-1mas%SiO2, 1.5-3mas%C, 2-3mas%AlCl3, 0.5-1mas%FeCl3,
0.001-0.5mas%CaCl2, 0.001-0.1mas%YCl3, 0.001-0.1mas%ThCl4, 0.001-0.2mas%Fe2O3,
0.001-0.2mas%Al2O3, 0.001-0.2mas%CaO, 0.001-0.1mas%TiO2, 0.001-0.1mas%UO2,
0.001-0.1mas%ThO2, 0.001-0.1mas%Y2O3。
Preferably, in the step 2), the 200 DEG C≤first preset temperature < 300 DEG C heat 1 under the first preset temperature
~3 hours.
Preferably, in the step 3), the second preset temperature is 300~400 DEG C, heats 5 under the second preset temperature
~8 hours.
Preferably, obtain hydrolyzate after the zirconium chloride hydrolysis to distil in the step 3), the method also includes with
Lower step: hydrolyzate being evaporated, is crystallized, and ZrOCl is precipitated in crystallization2·8H2O。
Preferably, evaporating temperature is 80~100 DEG C in the step 3), and crystallization temperature is 20~30 DEG C.
Preferably, the zirconium chloride of distillation is hydrolyzed in the step 3) method particularly includes: by four chlorinations of distillation
Zirconium is passed into eluting column and is eluted with water, and the zirconium chloride of distillation hydrolyzes to obtain hydrolyzate, by the water of the tower reactor of eluting column
Solution liquid is pumped into zirconium chloride of the tower top of eluting column as leacheate elution distillation by reflux pump, until the tower reactor of eluting column
In hydrolyzate in zirconium oxychloride concentration be 10~20mas%.
Preferably, residue is obtained after the zirconium chloride distillation in the step 3) in thick zirconium chloride, residue includes chlorine
Change ferrous iron, silica, chloridising prepare thick zirconium chloride reducing agent, zircon sand, metal oxide impurities, further include with
Lower step m):
Residue is used as the raw material that chloridising prepares thick zirconium chloride after acidleach, washing, drying.
Preferably, acid solution used in acidleach is hydrochloric acid solution, sulfuric acid solution, one in nitric acid solution in the step m)
Kind is several.
Preferably, mixed liquor of the acid solution used in acidleach for hydrochloric acid solution and sulfuric acid solution, acid solution in the step m)
Middle HCl and H2SO4Mass ratio be (3~5): 1.
Preferably, the concentration of acid solution used in acidleach is 18~40mas% in the step m).
The present invention also provides a kind of zirconium oxychlorides, are prepared by above-mentioned method.
The preparation method of zirconium oxychloride in the present invention can effectively remove impurity, by the chlorination in thick zirconium chloride
Iron is reduced into frerrous chloride, and chlorination iron tramp is mixed into when can prevent zirconium chloride from distilling, and then produces the oxygen chlorine of high-purity
Change zirconium product, the purity of zirconium oxychloride is not less than 95mas%.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the preparation facilities of the zirconium oxychloride in the embodiment of the present invention 2.
In figure: 1- reactive evaporation tank；2- eluting column；3- reflux pump；4- evaporator；5- cooler；6- crystallizer；7- first
Filter press；8- filtrate tanks；9- filtrate delivery pump；10- agitator tank；The second filter press of 11-；12- drying machine.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, with reference to the accompanying drawing and specific embodiment party
Present invention is further described in detail for formula.
Embodiment 1
The present embodiment provides a kind of preparation methods of zirconium oxychloride, comprising the following steps:
1) the thick zirconium chloride prepared by chloridising is heated in a hydrogen atmosphere, iron chloride and hydrogen in thick zirconium chloride
Solid/liquid/gas reactions generate frerrous chloride；
2) it is heated under the first preset temperature, so that lower than the impurity gasification of the boiling point of zirconium chloride in thick zirconium chloride；
3) it is heated under the second preset temperature, so that the zirconium chloride distillation in thick zirconium chloride, by four chlorinations of distillation
Zirconium hydrolysis, generates zirconium oxychloride.
The preparation method of zirconium oxychloride in the present embodiment can effectively remove impurity, by the chlorine in thick zirconium chloride
Change iron and be reduced into frerrous chloride, chlorination iron tramp is mixed into when can prevent zirconium chloride from distilling, and then produce the oxygen of high-purity
The purity of zirconium chloride product, zirconium oxychloride is not less than 95mas%.
Embodiment 2
As shown in Figure 1, the present embodiment provides a kind of preparation facilities of zirconium oxychloride, comprising:
Reactive evaporation tank 1 in a hydrogen atmosphere to add the thick zirconium chloride prepared by chloridising for being passed through hydrogen
Heat, the iron chloride in thick zirconium chloride is reacted with hydrogen generates frerrous chloride；Reactive evaporation tank 1 is also used in the first preset temperature
Lower heating, so that lower than the impurity gasification of the boiling point of zirconium chloride in thick zirconium chloride；Reactive evaporation tank 1 is also used to pre- second
It is heated at a temperature of if, so that the zirconium chloride distillation in thick zirconium chloride, the zirconium chloride of distillation is hydrolyzed, oxychlorination is generated
Zirconium.
Eluting column 2 is connect with reactive evaporation tank 1, and eluting column 2 is used for through water to the four of the distillation being passed through in eluting column 2
Zirconium chloride is eluted, and the zirconium chloride of distillation hydrolyzes to obtain hydrolyzate；
Reflux pump 3 is connect with eluting column 2, and reflux pump 3 is used to the hydrolyzate of the tower reactor of eluting column 2 being pumped into eluting column 2
Tower top as leacheate elution distillation zirconium chloride, until the zirconium oxychloride in the hydrolyzate in the tower reactor of eluting column 2
Concentration is preset concentration；
Evaporator 4 is connect with eluting column 2, and evaporator 4 from the tower bottoms that the tower reactor of eluting column 2 flows out for being heated
Evaporation；
Cooler 5 is connect with evaporator 4, and cooler 5 is obtained for being cooled down from the gas that the tower top of evaporator 4 flows out
To hydrochloric acid；
Crystallizer 6 is connect with evaporator 4, and crystallizer 6 from the liquid that the tower reactor of evaporator 4 flows out for being crystallized；
First filter press 7, connect with crystallizer 6, and the first filter press 7 is used to carry out the mixture flowed out from crystallizer 6
Filters pressing；
Filtrate tanks 8 are connect with the first filter press 7, and filtrate tanks 8 are for storing the filter that 7 filters pressing of the first filter press obtains
Liquid；
The entrance of filtrate delivery pump 9, filtrate delivery pump 9 is connect with filtrate tanks 8, the outlet and elution of filtrate delivery pump 9
The tower top of tower 2 connects, and filtrate delivery pump 9 is used to convey the filtrate in filtrate tanks 8 to eluting column 2 as leacheate；
Agitator tank 10 is connect with reactive evaporation tank 1, and agitator tank 10 is for stirring residue；
Second filter press 11, connect with agitator tank 10, and the second filter press 11 is used to carry out filters pressing to residue；
Drying machine 12 is connect with the second filter press 11, and drying machine 12 is for being dried residue.
The present embodiment provides a kind of methods for preparing zirconium oxychloride using above-mentioned apparatus, comprising the following steps:
1) it is passed through hydrogen into reactive evaporation tank 1, in reactive evaporation tank 1, the thick zirconium chloride that will be prepared by chloridising
It heats in a hydrogen atmosphere, the iron chloride in thick zirconium chloride is reacted with hydrogen generates frerrous chloride.The heating of reactive evaporation tank 1
Mode is inductive heating.Chloridising prepares the specific method of thick zirconium chloride: zircon sand, carbonaceous reducing agent, chlorine are at 1000 DEG C
Reaction generates zirconium chloride, silicon tetrachloride, hafnium tetrachloride, titanium tetrachloride and other metallic chloride impurities, while also generating one
Carbonoxide, carbon dioxide are cooled to 150 DEG C and obtain thick zirconium chloride.
Thick zirconium chloride includes: 91mas%ZrCl4, 1.50mas%HfCl4, 2.0mas%ZrSiO4, 0.05mas%
HfSiO4, 0.03mas%SiO2, 3.0mas%C, 1.6mas%AlCl3, 0.5mas%FeCl3, remaining is other impurities,
Its impurity includes CaCl2, YCl3, ThCl4, Fe2O3, Al2O3, CaO, TiO2, UO2, ThO2, Y2O3。
Product after thick zirconium chloride is reacted with hydrogen includes: 91.00mas%ZrCl4, 1.50mas%HfCl4,
2.00mas%ZrSiO4, 0.05mas%HfSiO4, 0.03mas%SiO2, 3.00mas%C, 1.60mas%AlCl3,
0.49mas%FeCl2, 0.01mas%FeCl3, remaining is other impurities, and other impurity include CaCl2, YCl3, ThCl4,
Fe2O3, Al2O3, CaO, TiO2, UO2, ThO2, Y2O3。
2) reactive evaporation tank 1 heats under the first preset temperature, and the first preset temperature is 200 DEG C, in the first preset temperature
Lower heating 3 hours, so that lower than the impurity gasification of the boiling point of zirconium chloride, the outlet of reacted evaporator 1 in thick zirconium chloride
It is emitted into tail gas absorbing system, the FeCl in thick zirconium chloride3Reduction reaction occurs with hydrogen, generates FeCl2And gaseous state HCl, gas
State HCl is together with low boiling impurity to exhaust system；Wherein, the aluminum chloride sublimation in thick zirconium chloride becomes gaseous state.Reaction is steamed
The tail gas for sending out tank 1 passes through the outlet drain of reactive evaporation tank 1 to tail gas absorbing system.
Thick zirconium chloride after the heating of the first preset temperature includes: 92.09%ZrCl4, 1.52mas%HfCl4,
2.02mas%ZrSiO4, 0.05mas%HfSiO4, 0.03mas%SiO2, 3.04mas%C, 0.05mas%AlCl3,
0.49mas%FeCl2, 0.01mas%FeCl3, remainder is other impurity.It can be seen that major part AlCl therein3Pass through evaporation to remove
It goes.
3) reactive evaporation tank 1 heats under the second preset temperature, and the second preset temperature is 350 DEG C, in the second preset temperature
Lower heating 7 hours, so that the zirconium chloride distillation in thick zirconium chloride, and collect.Step 2), 3) in by collect different boiling
The component of evaporation realizes the purification of thick zirconium chloride.The boiling point of iron chloride is 315 DEG C, and the boiling point of zirconium chloride is 331 DEG C, chlorine
Changing ferrous boiling point is 700 DEG C, after iron chloride is transformed into frerrous chloride, since the boiling point of frerrous chloride is significantly larger than four chlorinations
The boiling point of zirconium, so avoiding frerrous chloride impurity when heating is so that zirconium chloride distils under the second preset temperature and being mixed into liter
In the zirconium chloride of China, the purification of thick zirconium chloride is realized.
The zirconium chloride of distillation, which is passed into eluting column 2, uses water to elute as leacheate, specifically, the present embodiment
In for the water of leacheate be desalted water, the zirconium chloride of distillation is passed into the movement in eluting column 2 from bottom to top from lower part, drenches
The leacheate washed in tower 2 is passed through top-down movement in eluting column 2 from top, and zirconium chloride and the leacheate adverse current of distillation connect
The zirconium chloride hydrolysis of touching, distillation generates zirconium oxychloride, obtains hydrolyzate, the hydrolyzate of the tower reactor of eluting column 2 is passed through reflux
Pump 3 is pumped into zirconium chloride of the tower top of eluting column 2 as leacheate elution distillation, the hydrolysis in the tower reactor of eluting column 2
The concentration of zirconium oxychloride in liquid is 10mas%, and hydrolyzate is sent into evaporator 4 and carries out heating evaporation, and evaporating temperature is 95 DEG C,
Evaporation removes part water and hydrogen chloride gas, and the concentration for obtaining the zirconium oxychloride in hydrolyzate is 15mas%.Non-leaching tower
The concentration of zirconium oxychloride in hydrolyzate in 2 tower reactor, reduces the energy consumption in evaporation process.
Hydrolyzate is sent to crystallizer 6 again to crystallize, crystallization temperature is 30 DEG C, and ZrOCl is precipitated in crystallization2·8H2O is brilliant
Body, ZrOCl2·8H2The purity of O crystal is 97mas%, ZrOCl2·8H2AlCl in O crystal3Content is less than 50ppm, FeCl3
Content is less than 20ppm.Residue is obtained after zirconium chloride distillation in thick zirconium chloride.
Residue includes: 7.80mas%FeCl2, 31.82mas%ZrSiO4, 0.80mas%HfSiO4, 0.48mas%
SiO2, 47.73mas%C, remainder is other impurity, and other impurity include CaCl2, ThCl4, YCl3, Al2O3, Fe2O3, TiO2,
UO2, ThO2, CaO, Y2O3。FeCl2It has stayed in residue.
4) mixture in crystallizer 6 is sent in the first filter press 7 and carries out filters pressing, filtrate is passed into filtrate tanks
In 8, when the liquid level in filtrate tanks 8 is more than 1/3, filtrate is delivered to as leacheate by eluting column 2 by filtrate delivery pump 9
Carry out cycling and reutilization.
5) residue is added in agitator tank 10, while the acid solution that concentration is 18mas% is added into agitator tank 10 and carries out acid
Leaching, acid solution are the mixed liquor of hydrochloric acid solution and sulfuric acid solution, HCl and H in acid solution2SO4Mass ratio be 3:1.Metal in residue
Oxide reacts with acid solution generates corresponding salt, while the FeCl in residue2It is dissolved in acid solution, what is obtained after reaction is mixed
Conjunction object, which enters in the second filter press 11, carries out filters pressing, is washed in pressure-filtering process, obtains filter cake, filter cake includes: ZrSiO4、
HfSiO4, chloridising preparation thick zirconium chloride reducing agent, soild oxide impurity.Wherein, soild oxide impurity includes:
SiO2.Filter cake is passed into drying machine 12 and is dried, the raw material progress that chloridising prepares thick zirconium chloride is used as after dry
Recycling, filtered filtrate return into agitator tank 10 and are recycled.
The present embodiment also provides a kind of zirconium oxychloride, is prepared by above-mentioned method.
The preparation method of zirconium oxychloride in the present embodiment can effectively remove impurity, by the chlorine in thick zirconium chloride
Change iron and be reduced into frerrous chloride, chlorination iron tramp is mixed into when can prevent zirconium chloride from distilling, and then produce the oxygen of high-purity
The purity of zirconium chloride product, zirconium oxychloride is not less than 95mas%.
Embodiment 3
The present embodiment provides a kind of method that the preparation facilities using the zirconium oxychloride in embodiment 2 prepares zirconium oxychloride,
With the difference of the method in embodiment 2 are as follows:
In step 1), chloridising prepares the specific method of thick zirconium chloride: zircon sand, carbonaceous reducing agent, chlorine are at 1200 DEG C
Lower reaction generates zirconium chloride, silicon tetrachloride, hafnium tetrachloride, titanium tetrachloride and other metallic chloride impurities, while also generating
Carbon monoxide, carbon dioxide are cooled to 120 DEG C and obtain thick zirconium chloride.
Thick zirconium chloride includes: 90-93mas%ZrCl4, 1-2mas%HfCl4, 1-3mas%ZrSiO4, 0-1mas%
HfSiO4, 0-1mas%SiO2, 1.5-3mas%C, 1.5-2.5mas%AlCl3, 0.5-0.8mas%FeCl3, 0-0.5mas%
CaCl2, 0-0.1mas%YCl3, 0-0.1mas%ThCl4, 0-0.2mas%Fe2O3, 0-0.2mas%Al2O3, 0-0.2mas%
CaO, 0-0.1mas%TiO2, 0-0.1mas%UO2, 0-0.1mas%ThO2, 0-0.1mas%Y2O3。
In step 2), the first preset temperature is 295 DEG C, is heated 2 hours under the first preset temperature.By the first default temperature
Thick zirconium chloride after degree heating includes: 92-94mas%ZrCl4, 1.5-2.5mas%HfCl4, 1-3mas%ZrSiO4, 0-
1mas%HfSiO4, 0-1mas%SiO2, 2-4mas%C, 0-0.02mas%AlCl3, 0.45-0.75mas%FeCl2, 0.01-
0.05masFeCl3, 0-0.5mas%CaCl2, 0-0.1mas%YCl3, 0-0.1mas%ThCl3, 0-0.2mas%Fe2O3, 0-
0.2mas%Al2O3, 0-0.2mas%CaO, 0-0.1mas%TiO2, 0-0.1mas%UO2, 0-0.1mas%ThO2, 0-
0.1mas%Y2O3.It can be seen that AlCl therein3Almost evaporate.
In step 3), the second preset temperature is 300 DEG C, is heated 8 hours under the second preset temperature.Residue includes: 3-7%
FeCl2, 1-3%ThCl4, 0-1%CaCl2, 5-8%YCl3, 30-40%ZrSiO4, 0.5-1%HfSiO4, 0.5-1%SiO2,
0-1%Al2O3, 0-1%Fe2O3, 0-0.5%TiO2, 0-0.1%UO2, 0-0.1%ThO2, 0-0.1%CaO, 0-0.1%Y2O3,
40-50%C.
Until the concentration of the zirconium oxychloride in the hydrolyzate in the tower reactor of eluting column is 15mas%, by hydrolyzate feeding steaming
It sends out device and carries out heating evaporation, evaporating temperature is 80 DEG C, and evaporation removes part water and hydrogen chloride gas, obtains the oxygen in hydrolyzate
The concentration of zirconium chloride is 20mas%.
Hydrolyzate is sent to crystallizer again to crystallize, crystallization temperature is 25 DEG C, and ZrOCl is precipitated in crystallization2·8H2O is brilliant
Body, ZrOCl2·8H2The purity of O crystal is 95mas%.
In step 5), residue is added in agitator tank, while the acid solution that concentration is 30mas% is added into agitator tank and carries out
Acidleach, acid solution are the mixed liquor of hydrochloric acid solution and sulfuric acid solution, HCl and H in acid solution2SO4Mass ratio be 5:1.
Embodiment 4
The present embodiment provides a kind of method that the preparation facilities using the zirconium oxychloride in embodiment 2 prepares zirconium oxychloride,
With the difference of the method in embodiment 2 are as follows:
In step 1), chloridising prepares the specific method of thick zirconium chloride: zircon sand, carbonaceous reducing agent, chlorine are at 1100 DEG C
Lower reaction generates zirconium chloride, silicon tetrachloride, hafnium tetrachloride, titanium tetrachloride and other metallic chloride impurities, while also generating
Carbon monoxide, carbon dioxide are cooled to 135 DEG C and obtain thick zirconium chloride.
Thick zirconium chloride includes: 90-93mas%ZrCl4, 1-2mas%HfCl4, 1-3mas%ZrSiO4, 0-1mas%
HfSiO4, 0-1mas%SiO2, 1.5-3mas%C, 1.6-2.8mas%AlCl3, 0.5-1mas%FeCl3, 0-0.5mas%
CaCl2, 0-0.1mas%YCl3, 0-0.1mas%ThCl4, 0-0.2mas%Fe2O3, 0-0.2mas%Al2O3, 0-0.2mas%
CaO, 0-0.1mas%TiO2, 0-0.1mas%UO2, 0-0.1mas%ThO2, 0-0.1mas%Y2O3。
In step 2), the first preset temperature is 250 DEG C, is heated 1 hour under the first preset temperature.By the first default temperature
Thick zirconium chloride after degree heating includes: 92-94mas%ZrCl4, 1.5-2.5mas%HfCl4, 1-3mas%ZrSiO4, 0-
1mas%HfSiO4, 0-1mas%SiO2, 2-4mas%C, 0-0.03mas%AlCl3, 0.45-0.95mas%FeCl2, 0-
0.05masFeCl3, 0-0.5mas%CaCl2, 0-0.1mas%YCl3, 0-0.1mas%ThCl3, 0-0.2mas%Fe2O3, 0-
0.2mas%Al2O3, 0-0.2mas%CaO, 0-0.1mas%TiO2, 0-0.1mas%UO2, 0-0.1mas%ThO2, 0-
0.1mas%Y2O3.It can be seen that AlCl therein3Almost evaporate.
In step 3), the second preset temperature is 400 DEG C, is heated 5 hours under the second preset temperature.Residue includes: 3-7%
FeCl2, 1-3%ThCl4, 0-1%CaCl2, 5-8%YCl3, 30-40%ZrSiO4, 0.5-1%HfSiO4, 0.5-1%SiO2,
0-1%Al2O3, 0-1%Fe2O3, 0-0.5%TiO2, 0-0.1%UO2, 0-0.1%ThO2, 0-0.1%CaO, 0-0.1%Y2O3,
40-50%C.
Until the concentration of the zirconium oxychloride in the hydrolyzate in the tower reactor of eluting column is 20mas%, by hydrolyzate feeding steaming
It sends out device and carries out heating evaporation, evaporating temperature is 100 DEG C, and evaporation removes part water and hydrogen chloride gas, obtains in hydrolyzate
The concentration of zirconium oxychloride is 25mas%.
Hydrolyzate is sent to crystallizer again to crystallize, crystallization temperature is 20 DEG C, and ZrOCl is precipitated in crystallization2·8H2O is brilliant
Body, ZrOCl2·8H2The purity of O crystal is 96mas%.
In step 5), residue is added in agitator tank, while the acid solution that concentration is 40mas% is added into agitator tank and carries out
Acidleach, acid solution are the mixed liquor of hydrochloric acid solution and sulfuric acid solution, HCl and H in acid solution2SO4Mass ratio be 4:1.
Embodiment 5
The present embodiment provides the sides that a kind of preparation facilities using eight water oxygen zirconium chlorides in embodiment 2 prepares zirconium oxychloride
The difference of method in method, with embodiment 2 are as follows:
In step 1), chloridising prepares the specific method of thick zirconium chloride: zircon sand, carbonaceous reducing agent, chlorine are at 1100 DEG C
Lower reaction generates zirconium chloride, silicon tetrachloride, hafnium tetrachloride, titanium tetrachloride and other metallic chloride impurities, while also generating
Carbon monoxide, carbon dioxide are cooled to 140 DEG C and obtain thick zirconium chloride.
Thick zirconium chloride includes: 90-93mas%ZrCl4, 1-2mas%HfCl4, 1-3mas%ZrSiO4, 0-1mas%
HfSiO4, 0-1mas%SiO2, 1.5-3mas%C, 1.6-2.8mas%AlCl3, 0.5-0.8mas%FeCl3, 0-
0.5mas%CaCl2, 0-0.1mas%YCl3, 0-0.1mas%ThCl4, 0-0.2mas%Fe2O3, 0-0.2mas%Al2O3, 0-
0.2mas%CaO, 0-0.1mas%TiO2, 0-0.1mas%UO2, 0-0.1mas%ThO2, 0-0.1mas%Y2O3。
Thick zirconium chloride in step 2) after the heating of the first preset temperature includes: 92-94mas%ZrCl4, 1.5-
2.5mas%HfCl4, 1-3mas%ZrSiO4, 0-1mas%HfSiO4, 0-1mas%SiO2, 2-4mas%C, 0-0.05mas%
AlCl3, 0.45-0.75mas%FeCl3, 0-0.5mas%CaCl2, 0-0.1mas%YCl3, 0-0.1mas%ThCl3, 0-
0.2mas%Fe2O3, 0-0.2mas%Al2O3, 0-0.2mas%CaO, 0-0.1mas%TiO2, 0-0.1mas%UO2, 0-
0.1mas%ThO2, 0-0.1mas%Y2O3.It can be seen that AlCl therein3Almost evaporate.
In step 3), residue includes: 3-7%FeCl2, 1-3%ThCl4, 0-1%CaCl2, 5-8%YCl3, 30-40%
ZrSiO4, 0.5-1%HfSiO4, 0.5-1%SiO2, 0-1%Al2O3, 0-1%Fe2O3, 0-0.5%TiO2, 0-0.1%UO2, 0-
0.1%ThO2, 0-0.1%CaO, 0-0.1%Y2O3, 40-50%C.
Acid solution in step 5) is nitric acid solution, and the concentration of nitric acid solution is 18mas%, ZrOCl2·8H2O crystal it is pure
Degree is 97mas%.
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, essence of the invention is not being departed from
In the case where mind 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 (10)
1. a kind of preparation method of zirconium oxychloride, which comprises the following steps:
1) the thick zirconium chloride prepared by chloridising is heated in a hydrogen atmosphere, the iron chloride in thick zirconium chloride and hydrogen are anti-
Frerrous chloride should be generated；
2) it is heated under the first preset temperature, so that lower than the impurity gasification of the boiling point of zirconium chloride in thick zirconium chloride；
3) it is heated under the second preset temperature, so that the zirconium chloride distillation in thick zirconium chloride, by the zirconium chloride water of distillation
Solution generates zirconium oxychloride.
2. the preparation method of zirconium oxychloride according to claim 1, which is characterized in that in the step 2), 200 DEG C≤the
One preset temperature < 300 DEG C are heated 1~3 hour under the first preset temperature.
3. the preparation method of zirconium oxychloride according to claim 1, which is characterized in that in the step 3), second is default
Temperature is 300~400 DEG C, is heated 5~8 hours under the second preset temperature.
4. the preparation method of zirconium oxychloride according to claim 1, which is characterized in that the tetrachloro to distil in the step 3)
Hydrolyzate is obtained after changing zirconium hydrolysis, the method also includes following steps: hydrolyzate being evaporated, is crystallized, crystallization is precipitated
ZrOCl2·8H2O。
5. the preparation method of zirconium oxychloride according to claim 4, which is characterized in that evaporating temperature is in the step 3)
80~100 DEG C, crystallization temperature is 20~30 DEG C.
6. the preparation method of zirconium oxychloride described in any one according to claim 1~5, which is characterized in that the step 3)
What the middle zirconium chloride by distillation hydrolyzed method particularly includes: the zirconium chloride of distillation is passed into eluting column and is drenched with water
It washes, the zirconium chloride of distillation hydrolyzes to obtain hydrolyzate, and the hydrolyzate of the tower reactor of eluting column is pumped into eluting column by reflux pump
Zirconium chloride of the tower top as leacheate elution distillation, it is dense until the zirconium oxychloride in the hydrolyzate in the tower reactor of eluting column
Degree is 10~20mas%.
7. the preparation method of zirconium oxychloride described in any one according to claim 1~5, which is characterized in that the step 3)
In obtain residue after zirconium chloride distillation in thick zirconium chloride, it is further comprising the steps of m): residue by acidleach, washing, do
The raw material of thick zirconium chloride is prepared after dry as chloridising.
8. the preparation method of zirconium oxychloride according to claim 7, which is characterized in that in the step m) used in acidleach
Acid solution is one or more of hydrochloric acid solution, sulfuric acid solution, nitric acid solution.
9. the preparation method of zirconium oxychloride according to claim 7, which is characterized in that in the step m) used in acidleach
The concentration of acid solution is 18~40mas%.
10. a kind of zirconium oxychloride, which is characterized in that it is prepared by method described in any one of claim 1 to 9.
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