CN109019682B - Zirconium oxychloride and preparation method thereof - Google Patents
Zirconium oxychloride and preparation method thereof Download PDFInfo
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- CN109019682B CN109019682B CN201810947672.1A CN201810947672A CN109019682B CN 109019682 B CN109019682 B CN 109019682B CN 201810947672 A CN201810947672 A CN 201810947672A CN 109019682 B CN109019682 B CN 109019682B
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Abstract
The invention discloses zirconium oxychloride and a preparation method thereof, and the method comprises the following steps: 1) heating crude zirconium tetrachloride prepared by a chlorination method in a hydrogen atmosphere, and reacting ferric chloride in the crude zirconium tetrachloride with hydrogen to generate ferrous chloride; 2) heating at a first preset temperature to gasify impurities in the crude zirconium tetrachloride, which are lower than the boiling point of the zirconium tetrachloride; 3) heating at a second preset temperature to sublimate zirconium tetrachloride in the crude zirconium tetrachloride and hydrolyze the sublimated zirconium tetrachloride to generate zirconium oxychloride. The preparation method of zirconium oxychloride can effectively remove impurities, reduce ferric chloride in the crude zirconium tetrachloride into ferrous chloride, prevent ferric chloride impurities from being mixed in when the zirconium tetrachloride is sublimated, and further produce a high-purity zirconium oxychloride product, wherein the purity of the zirconium oxychloride is not lower than 95 mas%.
Description
Technical Field
The invention belongs to the technical field of zirconium oxychloride production, and particularly relates to zirconium oxychloride and a preparation method thereof.
Background
The hydrous zirconium oxychloride is a main raw material for producing other zirconium products such as zirconium dioxide, zirconium carbonate, zirconium sulfate, composite zirconium oxide and zirconium hafnium separation to prepare metal zirconium hafnium, and can also be used for products such as textiles, leather, rubber additives, metal surface treatment agents, coating drying agents, refractory materials, ceramics, catalysts, fire retardants and the like.
The method for producing zirconium oxychloride can be roughly divided into two methods, one is a method of dissolving zircon sand by using alkali, and the other is a method of hydrolyzing and purifying crude zirconium tetrachloride to obtain high-purity zirconium oxychloride. The technical process for preparing zirconium oxychloride by an alkali fusion method has the problems of large generation amount of acidic wastewater, serious environmental pollution and the like, so that the research of preparing crude zirconium tetrachloride by a chlorination method, and then hydrolyzing and purifying the zirconium tetrachloride is the key point of the research at present.
ZrCl is contained in the crude zirconium tetrachloride obtained by the chlorination process4、HfCl4、FeCl3、AlCl3、CaCl2、ZrSiO4、HfSiO4、SiO2、Al2O3、Fe2O3、TiO2、UO2、ThO2、CaO、Y2O3C, etc., and the content of impurities in the zirconium oxychloride obtained after the hydrolysis of the crude zirconium tetrachloride is high, particularly FeCl3、AlCl3The presence of (b) has a greater impact on the quality of the zirconium oxychloride, resulting in a lower quality of the zirconium oxychloride obtained.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art, provides zirconium oxychloride and a preparation method thereof, and solves the technical problem of high impurity content in the zirconium oxychloride obtained by hydrolyzing crude zirconium tetrachloride in the prior art.
The technical scheme adopted for solving the technical problem of the invention is to provide a preparation method of zirconium oxychloride, which comprises the following steps:
1) heating crude zirconium tetrachloride prepared by a chlorination method in a hydrogen atmosphere, and reacting ferric chloride in the crude zirconium tetrachloride with hydrogen to generate ferrous chloride;
2) heating at a first preset temperature to gasify impurities in the crude zirconium tetrachloride, which are lower than the boiling point of the zirconium tetrachloride;
3) heating at a second preset temperature to sublimate zirconium tetrachloride in the crude zirconium tetrachloride and hydrolyze the sublimated zirconium tetrachloride to generate zirconium oxychloride.
The specific method for preparing the crude zirconium tetrachloride by the chlorination method comprises the following steps: reacting zircon sand, a carbon reducing agent and chlorine at 1000-1200 ℃ to generate zirconium tetrachloride, silicon tetrachloride, hafnium tetrachloride, titanium tetrachloride and other metal chloride impurities, simultaneously generating carbon monoxide and carbon dioxide, and cooling to 120-150 ℃ to obtain crude zirconium tetrachloride.
The crude zirconium tetrachloride comprises: 90-93 mas% 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, the crude zirconium tetrachloride comprises: 90-93 mas% 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 first preset temperature is not lower than 200 ℃ and less than 300 ℃, and the heating is carried out for 1-3 hours at the first preset temperature.
Preferably, in the step 3), the second preset temperature is 300-400 ℃, and the heating is carried out for 5-8 hours at the second preset temperature.
It is preferable thatHydrolysis liquid is obtained after the zirconium tetrachloride sublimated in the step 3) is hydrolyzed, and the method further comprises the following steps: evaporating and crystallizing the hydrolysate to separate ZrOCl2·8H2O。
Preferably, the evaporation temperature in the step 3) is 80-100 ℃, and the crystallization temperature is 20-30 ℃.
Preferably, the specific method for hydrolyzing the sublimed zirconium tetrachloride in the step 3) is as follows: and introducing the sublimated zirconium tetrachloride into an elution tower to be eluted by water, hydrolyzing the sublimated zirconium tetrachloride to obtain a hydrolysate, pumping the hydrolysate in the tower kettle of the elution tower into the tower top of the elution tower through a reflux pump to be used as an eluent to elute the sublimated zirconium tetrachloride until the concentration of zirconium oxychloride in the hydrolysate in the tower kettle of the elution tower is 10-20 mas%.
Preferably, in the step 3), the residue is obtained after sublimation of zirconium tetrachloride in the crude zirconium tetrachloride, and the residue comprises ferrous chloride, silica, a reducing agent of the crude zirconium tetrachloride prepared by a chlorination method, zircon sand and metal oxide impurities, and further comprises the following step m):
the residue is used as a raw material for preparing crude zirconium tetrachloride by a chlorination method after acid leaching, water washing and drying.
Preferably, the acid solution used in the acid leaching in step m) is one or more of a hydrochloric acid solution, a sulfuric acid solution and a nitric acid solution.
Preferably, the acid solution used in the acid leaching in the step m) is a mixed solution of a hydrochloric acid solution and a sulfuric acid solution, and HCl and H in the acid solution2SO4The mass ratio of (3-5): 1.
preferably, the concentration of the acid solution used for acid leaching in the step m) is 18-40 mas%.
The invention also provides zirconium oxychloride prepared by the method.
The preparation method of zirconium oxychloride can effectively remove impurities, reduce ferric chloride in the crude zirconium tetrachloride into ferrous chloride, prevent ferric chloride impurities from being mixed in when the zirconium tetrachloride is sublimated, and further produce a high-purity zirconium oxychloride product, wherein the purity of the zirconium oxychloride is not lower than 95 mas%.
Drawings
FIG. 1 is a schematic view of the structure of an apparatus for producing zirconium oxychloride in example 2 of the present invention.
In the figure: 1-a reaction evaporation tank; 2-leaching the tower; 3-a reflux pump; 4-an evaporator; 5-a cooler; 6-a crystallizer; 7-a first filter press; 8-a filtrate storage tank; 9-filtrate delivery pump; 10-a stirring tank; 11-a second filter press; 12-a dryer.
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 oxychloride, which comprises the following steps:
1) heating crude zirconium tetrachloride prepared by a chlorination method in a hydrogen atmosphere, and reacting ferric chloride in the crude zirconium tetrachloride with hydrogen to generate ferrous chloride;
2) heating at a first preset temperature to gasify impurities in the crude zirconium tetrachloride, which are lower than the boiling point of the zirconium tetrachloride;
3) heating at a second preset temperature to sublimate zirconium tetrachloride in the crude zirconium tetrachloride and hydrolyze the sublimated zirconium tetrachloride to generate zirconium oxychloride.
The preparation method of zirconium oxychloride in the embodiment can effectively remove impurities, reduce ferric chloride in crude zirconium tetrachloride into ferrous chloride, and prevent ferric chloride impurities from being mixed in when the zirconium tetrachloride is sublimated, so that a high-purity zirconium oxychloride product is produced, wherein the purity of the zirconium oxychloride is not lower than 95 mas%.
Example 2
As shown in fig. 1, the present embodiment provides a zirconium oxychloride preparation apparatus, including:
a reaction evaporation tank 1 for introducing hydrogen gas to heat the crude zirconium tetrachloride prepared by the chlorination process in a hydrogen gas atmosphere, and reacting ferric chloride in the crude zirconium tetrachloride with the hydrogen gas to generate ferrous chloride; the reaction evaporation tank 1 is also used for heating at a first preset temperature so as to gasify impurities in the crude zirconium tetrachloride, wherein the impurities are lower than the boiling point of the zirconium tetrachloride; the reactive evaporation tank 1 is also used for heating at a second preset temperature, so that zirconium tetrachloride in the crude zirconium tetrachloride is sublimated, and the sublimated zirconium tetrachloride is hydrolyzed to generate zirconium oxychloride.
The leaching tower 2 is connected with the reaction evaporation tank 1, the leaching tower 2 is used for leaching the sublimed zirconium tetrachloride introduced into the leaching tower 2 through water, and the sublimed zirconium tetrachloride is hydrolyzed to obtain hydrolysate;
the reflux pump 3 is connected with the leaching tower 2, and the reflux pump 3 is used for pumping the hydrolysate in the tower kettle of the leaching tower 2 to the tower top of the leaching tower 2 to be used as leaching liquid to leach the sublimated zirconium tetrachloride until the concentration of the zirconium oxychloride in the hydrolysate in the tower kettle of the leaching tower 2 is a preset concentration;
the evaporator 4 is connected with the leaching tower 2, and the evaporator 4 is used for heating and evaporating tower bottom liquid flowing out of a tower bottom of the leaching tower 2;
a cooler 5 connected to the evaporator 4, the cooler 5 being configured to cool the gas flowing out of the top of the evaporator 4 to obtain hydrochloric acid;
the crystallizer 6 is connected with the evaporator 4, and the crystallizer 6 is used for crystallizing liquid flowing out of a tower kettle of the evaporator 4;
the first filter press 7 is connected with the crystallizer 6, and the first filter press 7 is used for filter pressing the mixture flowing out of the crystallizer 6;
the filtrate storage tank 8 is connected with the first filter press 7, and the filtrate storage tank 8 is used for storing filtrate obtained by filter pressing of the first filter press 7;
the inlet of the filtrate delivery pump 9 is connected with the filtrate storage tank 8, the outlet of the filtrate delivery pump 9 is connected with the top of the leaching tower 2, and the filtrate delivery pump 9 is used for delivering the filtrate in the filtrate storage tank 8 to the leaching tower 2 as the leaching solution;
the stirring tank 10 is connected with the reaction evaporation tank 1, and the stirring tank 10 is used for stirring residues;
the second filter press 11 is connected with the stirring tank 10, and the second filter press 11 is used for carrying out filter pressing on the residues;
the dryer 12 is connected to the second filter press 11, and the dryer 12 is used for drying the residue.
The embodiment provides a method for preparing zirconium oxychloride by using the device, which comprises the following steps:
1) introducing hydrogen into the reaction evaporation tank 1, heating the crude zirconium tetrachloride prepared by the chlorination method in the reaction evaporation tank 1 under the hydrogen atmosphere, and reacting ferric chloride in the crude zirconium tetrachloride with the hydrogen to generate ferrous chloride. The heating mode of the reaction evaporation tank 1 is inductive heating. The specific method for preparing the crude zirconium tetrachloride by the chlorination method comprises the following steps: zircon sand, carbon reducing agent and chlorine react at 1000 ℃ to generate zirconium tetrachloride, silicon tetrachloride, hafnium tetrachloride, titanium tetrachloride and other metal chloride impurities, and simultaneously generate carbon monoxide and carbon dioxide, and the crude zirconium tetrachloride is obtained after cooling to 150 ℃.
The crude zirconium tetrachloride comprises: 91 mas% ZrCl4，1.50mas％HfCl4，2.0mas％ZrSiO4，0.05mas％HfSiO4，0.03mas％SiO2，3.0mas％C，1.6mas％AlCl3，0.5mas％FeCl3The balance being other impurities including CaCl2，YCl3，ThCl4，Fe2O3，Al2O3，CaO，TiO2，UO2，ThO2，Y2O3。
The product of the reaction of crude zirconium tetrachloride with hydrogen comprises: 91.00 mas% ZrCl4，1.50mas％HfCl4，2.00mas％ZrSiO4，0.05mas％HfSiO4，0.03mas％SiO2，3.00mas％C，1.60mas％AlCl3，0.49mas％FeCl2，0.01mas％FeCl3The balance being other impurities including CaCl2，YCl3，ThCl4，Fe2O3，Al2O3，CaO，TiO2，UO2，ThO2，Y2O3。
2) The reaction evaporation tank 1 is heated at a first preset temperature of 200 ℃ for 3 hours, so that impurities in the crude zirconium tetrachloride, which are lower than the boiling point of the zirconium tetrachloride, are gasified and discharged to tail gas through an outlet of the reaction evaporation tank 1Absorption system, FeCl in crude zirconium tetrachloride3Carrying out reduction reaction with hydrogen to generate FeCl2And gaseous HCl, the gaseous HCl and low boiling point impurities are sent to a tail gas system together; wherein aluminum chloride in the crude zirconium tetrachloride sublimes to become gaseous. And the tail gas of the reaction evaporation tank 1 is discharged to a tail gas absorption system through an outlet of the reaction evaporation tank 1.
The crude zirconium tetrachloride after being heated at the first preset temperature comprises: 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％FeCl3The remainder is other impurities. Most of which can be seen in AlCl3Has been removed by evaporation.
3) The reaction evaporation tank 1 is heated at a second preset temperature of 350 ℃ for 7 hours, so that the zirconium tetrachloride in the crude zirconium tetrachloride is sublimated and collected. And in the steps 2) and 3), the purification of the crude zirconium tetrachloride is realized by collecting evaporated components with different boiling points. The boiling point of ferric chloride is 315 ℃, the boiling point of zirconium tetrachloride is 331 ℃, the boiling point of ferrous chloride is 700 ℃, after the ferric chloride is converted into the ferrous chloride, because the boiling point of the ferrous chloride is far higher than the boiling point of the zirconium tetrachloride, when the zirconium chloride is sublimated by heating at the second preset temperature, ferrous chloride impurities are prevented from being mixed into the sublimated zirconium chloride, and the purification of the crude zirconium tetrachloride is realized.
The method comprises the following steps of introducing sublimed zirconium tetrachloride into an elution tower 2, and eluting the zirconium tetrachloride by using water as eluent, wherein in the embodiment, the water used for the eluent is desalted water, the sublimed zirconium tetrachloride is introduced into the elution tower 2 from the lower part and moves from bottom to top, the eluent in the elution tower 2 is introduced into the elution tower 2 from the upper part and moves from top to bottom, the sublimed zirconium tetrachloride is in countercurrent contact with the eluent, the sublimed zirconium tetrachloride is hydrolyzed to generate zirconium oxychloride, a hydrolysate is obtained, the hydrolysate in the tower bottom of the elution tower 2 is pumped into the tower top of the elution tower 2 by a reflux pump 3 to be used as the eluent to elute the sublimed zirconium tetrachloride until the concentration of the zirconium oxychloride in the hydrolysate in the tower bottom of the elution tower 2 is 10 mas%, the hydrolysate is sent into an evaporator 4 to be heated and evaporated, the evaporation temperature is 95 ℃, and part of water and hydrogen chloride gas are evaporated, so that the concentration of the zirconium oxychloride in the hydrolysate is 15 mas. The concentration of zirconium oxychloride in the hydrolysate in the tower kettle of the leaching tower 2 is controlled, and the energy consumption in the evaporation process is reduced.
Then the hydrolysate is sent into a crystallizer 6 for crystallization, the crystallization temperature is 30 ℃, ZrOCl is crystallized and separated out2·8H2Crystal of O, ZrOCl2·8H2The purity of the O crystal is 97 mas%, ZrOCl2·8H2AlCl in O crystal3Less than 50ppm, FeCl3The content is less than 20 ppm. The residue is obtained after sublimation of zirconium tetrachloride in the crude zirconium tetrachloride.
The residue comprises: 7.80 mas% FeCl2，31.82mas％ZrSiO4，0.80mas％HfSiO4，0.48mas％SiO247.73 mas% C, the remainder being other impurities including CaCl2，ThCl4，YCl3，Al2O3，Fe2O3，TiO2，UO2，ThO2,CaO，Y2O3。FeCl2And remain in the residue.
4) And (3) feeding the mixture in the crystallizer 6 into a first filter press 7 for filter pressing, introducing the filtrate into a filtrate storage tank 8, and when the liquid level in the filtrate storage tank 8 exceeds 1/3, conveying the filtrate to the leaching tower 2 through a filtrate conveying pump 9 to be used as leaching liquid for recycling.
5) Adding the residue into a stirring tank 10, and simultaneously adding 18 mas% acid solution into the stirring tank 10 for acid leaching, wherein the acid solution is a mixed solution of hydrochloric acid solution and sulfuric acid solution, and HCl and H in the acid solution2SO4The mass ratio of (A) to (B) is 3: 1. the metal oxide in the residue reacts with the acid liquor to generate corresponding salts, and FeCl in the residue2Dissolving in acid liquor, carrying out filter pressing in a second filter press 11 on the mixture obtained after the reaction, and washing in the filter pressing process to obtain a filter cake, wherein the filter cake comprises: ZrSiO4、HfSiO4Reducing agent of crude zirconium tetrachloride prepared by chlorination method and solid oxide impurity.Wherein the solid oxide impurities comprise: SiO 22. And (3) introducing the filter cake into a dryer 12 for drying, recycling the dried filter cake used as a raw material for preparing the crude zirconium tetrachloride by a chlorination method, and returning the filtered filtrate to the stirring tank 10 for recycling.
The embodiment also provides zirconium oxychloride, which is prepared by the method.
The preparation method of zirconium oxychloride in the embodiment can effectively remove impurities, reduce ferric chloride in crude zirconium tetrachloride into ferrous chloride, and prevent ferric chloride impurities from being mixed in when the zirconium tetrachloride is sublimated, so that a high-purity zirconium oxychloride product is produced, wherein the purity of the zirconium oxychloride is not lower than 95 mas%.
Example 3
This example provides a method for preparing zirconium oxychloride using the apparatus for preparing zirconium oxychloride of example 2, which is different from the method of example 2 in that:
in the step 1), the specific method for preparing the crude zirconium tetrachloride by the chlorination method comprises the following steps: zircon sand, carbon reducing agent and chlorine react at 1200 ℃ to generate zirconium tetrachloride, silicon tetrachloride, hafnium tetrachloride, titanium tetrachloride and other metal chloride impurities, and simultaneously generate carbon monoxide and carbon dioxide, and the crude zirconium tetrachloride is obtained after the reaction is cooled to 120 ℃.
The crude zirconium tetrachloride comprises: 90-93 mas% 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 ℃, and the heating is carried out for 2 hours at the first preset temperature. The crude zirconium tetrachloride after being heated at the first preset temperature comprises: 92-94 mas% 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. Can see AlCl therein3Almost evaporated off.
In step 3), the second preset temperature is 300 ℃, and the heating is carried out for 8 hours at the second preset temperature. The residue comprises: 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 zirconium oxychloride in the hydrolysate in the tower kettle of the leaching tower is 15 mas%, feeding the hydrolysate into an evaporator for heating and evaporation, wherein the evaporation temperature is 80 ℃, and evaporating to remove part of water and hydrogen chloride gas to obtain the concentration of the zirconium oxychloride in the hydrolysate of 20 mas%.
Then the hydrolysate is sent into a crystallizer for crystallization, the crystallization temperature is 25 ℃, and ZrOCl is crystallized and precipitated2·8H2Crystal of O, ZrOCl2·8H2The purity of the O crystals was 95 mas%.
Step 5), adding the residues into a stirring tank, and simultaneously adding acid liquor with the concentration of 30 mas% into the stirring tank for acid leaching, wherein the acid liquor is mixed liquor of hydrochloric acid solution and sulfuric acid solution, and HCl and H in the acid liquor2SO4The mass ratio of (A) to (B) is 5: 1.
example 4
This example provides a method for preparing zirconium oxychloride using the apparatus for preparing zirconium oxychloride of example 2, which is different from the method of example 2 in that:
in the step 1), the specific method for preparing the crude zirconium tetrachloride by the chlorination method comprises the following steps: zircon sand, carbon reducing agent and chlorine react at 1100 ℃ to generate zirconium tetrachloride, silicon tetrachloride, hafnium tetrachloride, titanium tetrachloride and other metal chloride impurities, and simultaneously generate carbon monoxide and carbon dioxide, and the crude zirconium tetrachloride is obtained after the reaction product is cooled to 135 ℃.
The crude zirconium tetrachloride comprises: 90-93 mas% 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 ℃, and the heating is carried out for 1 hour at the first preset temperature. The crude zirconium tetrachloride after being heated at the first preset temperature comprises: 92-94 mas% 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. Can see AlCl therein3Almost evaporated off.
In step 3), the second preset temperature is 400 ℃, and the heating is carried out for 5 hours at the second preset temperature. The residue comprises: 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。
And (3) until the concentration of zirconium oxychloride in the hydrolysate in the tower kettle of the leaching tower is 20 mas%, feeding the hydrolysate into an evaporator for heating and evaporation, wherein the evaporation temperature is 100 ℃, and evaporating to remove part of water and hydrogen chloride gas to obtain the zirconium oxychloride with the concentration of 25mas in the hydrolysate.
Then the hydrolysate is sent into a crystallizer for crystallization, the crystallization temperature is 20 ℃, and ZrOCl is crystallized and precipitated2·8H2Crystal of O, ZrOCl2·8H2The purity of the O crystals was 96 mas%.
Step 5), adding the residues into a stirring tank, and simultaneously adding acid liquor with the concentration of 40 mas% into the stirring tank for acid leaching, wherein the acid liquor is mixed liquor of hydrochloric acid solution and sulfuric acid solution, and HCl and H in the acid liquor2SO4The mass ratio of (A) to (B) is 4: 1.
example 5
This example provides a method for preparing zirconium oxychloride using the apparatus for preparing zirconium oxychloride octahydrate of example 2, which differs from the method of example 2 in that:
in the step 1), the specific method for preparing the crude zirconium tetrachloride by the chlorination method comprises the following steps: zircon sand, carbon reducing agent and chlorine react at 1100 ℃ to generate zirconium tetrachloride, silicon tetrachloride, hafnium tetrachloride, titanium tetrachloride and other metal chloride impurities, and simultaneously generate carbon monoxide and carbon dioxide, and the mixture is cooled to 140 ℃ to obtain crude zirconium tetrachloride.
The crude zirconium tetrachloride comprises: 90-93 mas% 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。
The crude zirconium tetrachloride heated at the first preset temperature in the step 2) comprises: 92-94 mas% 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. Can see AlCl therein3Almost evaporated off.
In step 3), the residue comprises: 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。
The acid solution in the step 5) is nitric acid solution, the concentration of the nitric acid solution is 18mas percent, ZrOCl2·8H2The purity of the O crystals was 97 mas%.
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 (9)
1. The preparation method of zirconium oxychloride is characterized by comprising the following steps:
1) heating crude zirconium tetrachloride prepared by a chlorination method in a hydrogen atmosphere, and reacting ferric chloride in the crude zirconium tetrachloride with hydrogen to generate ferrous chloride;
2) heating at a first preset temperature to gasify impurities in the crude zirconium tetrachloride, which are lower than the boiling point of the zirconium tetrachloride;
3) heating at a second preset temperature to sublimate zirconium tetrachloride in the crude zirconium tetrachloride and hydrolyze the sublimated zirconium tetrachloride to generate zirconium oxychloride,
the specific method for hydrolyzing the sublimed zirconium tetrachloride in the step 3) comprises the following steps: and introducing the sublimated zirconium tetrachloride into an elution tower to be eluted by water, hydrolyzing the sublimated zirconium tetrachloride to obtain a hydrolysate, pumping the hydrolysate in the tower kettle of the elution tower into the tower top of the elution tower through a reflux pump to be used as an eluent to elute the sublimated zirconium tetrachloride until the concentration of zirconium oxychloride in the hydrolysate in the tower kettle of the elution tower is 10-20 mas%.
2. The method for preparing zirconium oxychloride as claimed in claim 1, wherein the step 2) is performed by heating at a first preset temperature of 200 ℃ or more and less than 300 ℃ for 1 to 3 hours.
3. The method for preparing zirconium oxychloride as claimed in claim 1, wherein the second predetermined temperature in the step 3) is 350 to 400 ℃ and the heating is performed at the second predetermined temperature for 5 to 8 hours.
4. The method for preparing zirconium oxychloride as claimed in claim 1, wherein the zirconium tetrachloride sublimate in the step 3) is hydrolyzed to obtain a hydrolysate, and the method further comprises the steps of: evaporating and crystallizing the hydrolysate to separate ZrOCl2·8H2O。
5. The method for preparing zirconium oxychloride as claimed in claim 4, wherein the evaporation temperature in the step 3) is 80 to 100 ℃ and the crystallization temperature is 20 to 30 ℃.
6. The method for producing zirconium oxychloride as claimed in any one of claims 1 to 5, wherein the step 3) comprises sublimating zirconium tetrachloride in the crude zirconium tetrachloride to obtain a residue, and further comprises the step m) of: the residue is used as a raw material for preparing crude zirconium tetrachloride by a chlorination method after acid leaching, water washing and drying.
7. The method for preparing zirconium oxychloride as claimed in claim 6, wherein the acid solution used in the acid leaching in step m) is one or more of a hydrochloric acid solution, a sulfuric acid solution and a nitric acid solution.
8. The method for preparing zirconium oxychloride as claimed in claim 6, wherein the acid solution used in the acid leaching in step m) has a concentration of 18 to 40 mass%.
9. Zirconium oxychloride produced by the process according to any one of claims 1 to 8.
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