CN108083333A - It is a kind of to be given up the method that zirconium prepares zirconium aluminium composite granule using solid - Google Patents
It is a kind of to be given up the method that zirconium prepares zirconium aluminium composite granule using solid Download PDFInfo
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Abstract
It is given up the method that zirconium prepares zirconium aluminium composite granule, comprised the following steps with solid the present invention relates to a kind of：(1) alkalize：Solid is given up and NaOH is added in after zirconium powder breakdown mill roasts, obtains zirconates；(2) intermediate is prepared：After the zirconates is carried out washing impurity elimination, pickling transformation, filtering and removing slag, must make the transition liquid, the transition liquid is obtained into the first sediment with sulfuric acid first set reaction, by first sediment and sulfuric acid, zirconium sulfate is precipitated in reactive crystallization again, by the zirconium sulfate be formulated as 0.25 3mol/L sulfuric acid zirconium solution in case with；(3) silicon source is added in into the sulfuric acid zirconium solution and stirs 2 6h, obtain zirconium aluminum solutions；(4) precipitating reagent is instilled into the zirconium aluminum solutions to be reacted, obtain the second sediment；(5) by second sediment it is washed, it is dry, calcining and post processing after to get zirconium aluminium composite granule.This method equipment requirement is low, simple for process, powder quality is high, realizes the recycling of the solid waste containing zirconium.
Description
Technical field
The present invention relates to environmental protection technical fields.More particularly, to it is a kind of using solid give up zirconium prepare high quality zirconium
Aluminium composite granule realizes the method that solid waste resource recovery utilizes.
Background technology
China is at present 30-40wt/ with zirconium ore amount, becomes the first in the world zirconium ore resources consumption big country.But due to China
The limitation of zirconium resource, self-produced zirconium ore only account for the 2/5 of aggregate consumption, calculate by existing GDP development speeds and the percentage of import, as nothing is new
Zirconium ore source can about ensure that China uses for 40 years, such as be estimated by radix of zero import, then degree of protection is only 20 years or so.
Chinese zirconium ore resource requirement at present largely relies on foreign countries, and import zircon sand price is left by the 3000 yuan/t of early 1990s
Upper right increases to the 10000 yuan/t of highest price of 2005.Since zirconium is important strategic materials, once external perform limitation outlet political affairs
Plan, Zirconium of China industry will be in semiparalysis situation, will generate significant impact to the Chinese national economic development and national defense construction.
As Chinese Resources comprehensively utilize, the reinforcement of environmental protection dynamics, zirconium waste material utilization of resources technical research is increasingly
To the attention of people, the larger zirconium waste material varieties of resources of quantity have at present：The acid white residue containing zirconium of basic zirconium chloride production discharge, dioxy
Change zirconium synthetic cut stone processing grinding slag, zirconium dioxide composite refractory waste material etc..Various zirconium waste resource recoveries study a point such as table
1。
1 zirconium waste resource recovery of table studies a point w/%
Zirconium synthetic cut stone is using high-purity ZrO2Add Y2O3High temperature crystallizations is waited to draw.China is zirconium synthetic cut stone weight
The production and processing state, artificial zirconium jewel yield wanted rank the first in the world.But zirconium gem crystal be processed into jewel into
Product rate is low, amount of waste is big.For zirconium gem crystal be processed into the waste material, refractory material that jewel cuts, polishes with
And being discarded containing zirconium for brick of displacing of the industries such as the glass furnaces such as photoelectric crystal, crystal growing furnace, their main component is
High temperature sintering is stable or high-temperature fusion is stablized to form tetragonal zircite or cubic zirconia, and materialization stability is good, it is difficult to using general
Logical physical/chemical method is decomposed completely, realizes further efficiently utilization.Traditional processing method is by the mill of zirconium gem processing
It cuts slag etc. and substitutes zircon sand alkali fusion production basic zirconium chloride, while the Y of high added value is recycled in zirconium, silicon separation process2O3.However
Grinding slag can still generate zirconium white residue waste material during basic zirconium chloride is produced, and the zirconium white residue in China still mainly uses heap at present
Processing is deposited, the zirconium white residue largely stored up has become the serious problems for restricting enterprise development.
And aluminium oxide ceramics is one of ceramics being most widely used at present, with high temperature resistant, mechanical strength is good, is electrically insulated
Good, the more low many excellent properties of cost of property.However in the fields such as abrasive media, ceramic valve plate, joint prosthesis, aluminium oxide ceramics
Because the reasons such as brittleness are it is impossible to meet usage requirement, it is necessary to develop with the more preferable performance such as high tenacity, high rigidity, wear-resistant
Aluminium oxide ceramics.In order to improve the mechanical property of aluminium oxide ceramics, people using zirconium oxide transformation toughening, it is dispersed particle-strengthened or
The methods of fiber and crystal whisker excess weld metal, is improved.Wherein using zirconium oxide transformation toughening method improve performance significantly, using compared with
To be extensive.Zirconia-alumina composite ceramic becomes the research hotspot of advanced ceramics material.Zirconia-alumina composite ceramic
Performance mainly determine that and microstructure is mainly determined by material powder state by its microstructure, therefore high quality zirconium aluminium
Composite granule is the premise of the excellent zirconia-alumina composite ceramic of processability.
Therefore, how to discard brick by what the industries such as glass furnace, crystal growing furnace were displaced containing zirconium and be efficiently converted to zirconium aluminium
Composite granule is the research purpose of the present invention.
The content of the invention
It is given up the method that zirconium prepares zirconium aluminium composite granule using solid the technical problem to be solved in the present invention is to provide a kind of.This
Invention directly prepares zirconium oxide using the solid zirconium that gives up as raw material, overcomes in traditional route and produces zirconium oxide by raw material of zirconium oxychloride
" three wastes " problem of environmental pollution present in powder, realizes the recycling of solid waste, and the present invention prepares zirconium oxide
The method production cost of powder is low, simple for process, equipment requirement is low, and zirconium aluminium uniform component distribution is high in obtained product.
The technical scheme is that：
It is a kind of to be given up the method that zirconium prepares zirconium aluminium composite granule with solid, which is characterized in that comprise the following steps：
(1) alkalize：Solid is given up and NaOH is added in after zirconium powder breakdown mill roasts, obtains zirconates；
(2) intermediate is prepared：After the zirconates is carried out washing impurity elimination, pickling transformation, filtering and removing slag, transition liquid is obtained, it will
The transition liquid obtains the first sediment with sulfuric acid first set reaction, and by first sediment, sulphur is precipitated in reactive crystallization again with sulfuric acid
Sour zirconium, by the zirconium sulfate be formulated as 0.25-3mol/L sulfuric acid zirconium solution in case with；
(3) silicon source stirring 2-6h is added in into the sulfuric acid zirconium solution, obtains zirconium aluminum solutions；
(4) precipitating reagent is instilled into the zirconium aluminum solutions to be reacted, obtain the second sediment；
(5) by second sediment it is washed, it is dry, calcining and post processing after to get zirconium aluminium composite granule.
Involved chemical formula is in step (1)：
Chemical formula in step (2) involved by pickling transformation is：
Na2ZrO3+2H+=ZrO (OH)2+2Na+
Na2FeO2+H2O=Fe (OH)2+2NaOH
Fe(OH)2+2H+=Fe2++2H2O
The chemical formula prepared in step (2) involved by zirconium sulfate is：
ZrO(OH)2+H2SO4=ZrOSO4+2H2O
ZrOSO4+H2SO4=Zr (SO4)2+H2O
Y2O3+3H2SO4=Y2(SO4)3+3H2O
Involved chemical formula is in step (4)：
Zr(SO4)2+4OH-=Zr (OH)4↓+2SO42-
Al3++3OH-=Al (OH)3↓
Or Zr (SO4)2+2(CO3)2-+2H2O=Zr (OH)4↓+2SO4 2-+2CO2↑
2Al3++3(CO3)2-+3H2O=2Al (OH)3↓+3CO2↑
Or Zr (SO4)2+4(HCO3)-=Zr (OH)4↓+2SO42-+4CO2↑
Al3++3(HCO3)-=Al (OH)3↓+3CO2↑
Chemical formula involved by step (5) is：
Preferably：Solid described in step (1) gives up zirconium as zirconia ceramics waste material, zirconium dioxide composite refractory waste material
And one or more of zirconium dioxide synthetic cut stone processing grinding slag.
Preferably：The give up mass ratio of zirconium and the alkaline material of solid described in step (1) is 1:1.1~1.5, the roasting
The temperature of burning is 700-1000 DEG C.
When the give up mass ratio of zirconium and alkaline material of solid is 1:Can give up solid when 1.1~1.5 the complete alkali fusion of zirconium and reality
The efficient utilization of existing material.
Preferably：Be transformed into using described in step (2) mass fraction for 21~24% hydrochloric acid to washing impurity elimination after
Zirconates carries out heating reaction.
Preferably：Silicon source described in step (3) is aluminum nitrate solution, liquor alumini chloridi, aluminum sulfate solution and aluminum acetate are molten
It is one or more of in liquid.
Preferably：The additive amount of silicon source described in step (3) is Al3+：Zr4+=(0.5-2)：1.
Preferably：Precipitating reagent described in step (3) is Na2CO3Solution, NaHCO3One kind in solution or NaOH solution or
It is several.
The present invention does not select ammonium hydroxide as precipitating reagent, and using Na2CO3Solution, NaHCO3One in solution or NaOH solution
Kind is several, not only avoids the pollution of volatile ammonia, and reduces equipment tight requirements, so as to simplify equipment, reduces into
This.
Further：Precipitating reagent described in step (4) is Na2CO3Solution or NaHCO3Solution.
The present invention uses Na2CO3Solution or NaHCO3Solution is as precipitating reagent and then generates carbonate, and carbonate is rear
It can be decomposed during continuous Calcination: Calcination and generate a large amount of gases, form the effect of loose product, the finished product zirconium oxide formed is
Superfine powder between nanometer and sub-micron.Superfine powder has that large specific surface area, fusing point be low, magnetic strong, active good, light
The good excellent performance of good absorbing, thermal conductivity.
Preferably：The molar concentration of precipitating reagent described in step (4) be 0.25~0.5mol/L, the precipitating reagent anion
Molar concentration and zirconium ion molar concentration rate be 1:0.5~1.
Preferably：Calcining heat is 800~1200 DEG C in step (4), and calcination time is 2~6h.
Preferably：Calcining heat is 800~1200 DEG C in step (5), the Ball-milling Time for 5~for 24 hours, the zirconium oxide
The grain size of powder is 50~250nm.
Beneficial effects of the present invention are as follows：
(1) present invention prepares zirconium aluminium composite granule using coprecipitation, specifically gives up zirconium as raw material using solid, carries out letter successively
Change, extract to concentrate and prepare sulfuric acid zirconium solution as intermediate, while add in a certain amount of silicon source and stir and evenly mix, add precipitation
Agent carries out coprecipitation reaction, and so as to prepare zirconium aluminium presoma, zirconium aluminium presoma can obtain subsphaeroidal ultra-fine after high-temperature calcination
Zirconium aluminium composite granule.The advantages of preparation method, is：First, the intermediate prepared by this method is sulfuric acid zirconium solution, is distinguished
In the production line of conventional oxidation zirconium, zirconium oxychloride is not generated during preparation, avoids and is given birth to by raw material of zirconium oxychloride
Calcining leads to the problem of such as volatility HCl " three wastes " pollutions when producing zirconium oxide, is conducive to environmental protection；Secondly, it is being co-precipitated
Shi Caiyong Na2CO3Solution or NaHCO3Solution etc. is reacted as precipitating reagent, is decomposed during subsequent calcination and is generated dioxy
Change the innocuous gas such as carbon, will not etching apparatus and pollution environment, and generate a large amount of gases due to that can be decomposed during Calcination: Calcination,
The effect of loose product is formed, and then improves the distributing homogeneity and composite effect of zirconium aluminium component, is formed between nanometer and Asia
Zirconium aluminium composite granule between micron；This method raw material is easy to get, and inexpensive, equipment is conventional, simple for process, production cost is low, is to prepare
The ideal method of composite granule.
(2) coprecipitation prepares that zirconium aluminium composite granule is simple for process, equipment requirement is low, powder quality is high, using this hair
The composition of Zirconium powder made from bright method is usually 90~100wt% zirconium oxides and 0~10wt% other elements oxides,
Further, composition is usually the zirconium oxide of 92~97wt%, the yttrium oxide of 3~8wt%, in obtained Zirconium powder
Tetragonal phase zirconium oxide accounts for the 88~100% of zirconium oxide total amount；
(3) present invention is reacted using the sulfuric acid zirconium solution of 0.25-3mol/L with precipitating reagent, can avoid zirconium sulfate solution concentration
When excessive, precipitation is too fast, reunites serious, particle size becomes larger extremely；And concentration it is too low when solubility product is not achieved, it is heavy to generate
It forms sediment.
(4) it is of the invention that zirconium is given up as raw material using solid, and then the Zirconium powder of wide market is prepared, not only keep away
Exempt from solid to give up the disposal difficulties of zirconium, and realize the recycling of solid waste.
Description of the drawings
It in order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention, for those of ordinary skill in the art, without creative efforts, can be with
Other attached drawings are obtained according to these attached drawings.
Fig. 1 is the X-ray diffraction XRD spectrums of zirconium aluminium composite granule prepared by present application example 1.
Fig. 2 is the scanning electron microscope sem figure of zirconium aluminium composite granule prepared by present application example 1.
Specific embodiment
Technical scheme is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation
Example is part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
Personnel's all other embodiments obtained without making creative work, belong to the scope of protection of the invention.
Unless otherwise instructed, the raw material in embodiments herein is bought by commercial sources.It should be noted that following embodiments
Middle XRD characterization analysis derives instrument using the Miniflex600 types X-ray of Rigaku companies, and SEM figures are using Hitachi companies
The scanning of S4800 types scanning electron microscope obtains.
Embodiment 1
It is a kind of to be given up the method that zirconium prepares zirconium oxide with solid, comprise the following steps：
(1) it is zirconia ceramics waste material pulverising mill is thin, and press 1 with NaOH:1.2 quality is moved into not after mixing than mixing
It becomes rusty in steel pot, roasts 3h at 800 DEG C, obtain zirconates；
(2) zirconates with deionized water is cleaned, is then added in the hydrochloric acid that concentration is 21wt% and heats instead
3h is answered, obtains reaction product, the reaction product is subjected to separation of solid and liquid, obtains transition liquid, sulfuric acid is added in into the transition liquid
Carry out first set reaction, obtain zirconium basic sulphate as the first sediment, by first sediment further with sulfuric acid reaction knot
Crystalline substance obtains zirconium sulfate, by the zirconium sulfate be formulated as 0.25mol/L sulfuric acid zirconium solution in case with；
(3) aluminum sulfate that 0.25mol/L is added in into the sulfuric acid zirconium solution is stirred 2h, and wherein additive amount is Al3+：
Zr4+=1:1, presoma zirconium aluminum solutions are obtained after stirring；
(4) NaOH solution that 0.25mol/L is instilled into the zirconium aluminum solutions is reacted, wherein OH-With Zr4+Mole
Concentration ratio is 1:0.5, after reacting 2h, obtain the second sediment；
(5) second sediment is filtered successively, deionized water wash 3 times, absolute ethyl alcohol washed once, then
It is dried and calcines, wherein calcining is to calcine 12h at 1200 DEG C, then ball milling 12h, dried 150 mesh sieve obtain zirconium aluminium and answer again
Close powder.
Zirconium powder obtained by embodiment 1 is after XRD analysis it can be seen that it is cubic phase oxidation to prepare products obtained therefrom
Zirconium and alumina composite powders, sem analysis show the zirconium aluminium composite granule prepared to be subsphaeroidal, and average grain diameter is nanoscale
(90nm)。
Embodiment 2
It is a kind of to be given up the method that zirconium prepares zirconium oxide with solid, comprise the following steps：
(1) it is zirconium dioxide synthetic cut stone processing grinding ground-slag comminution is thin, and press 1 with NaOH:1.5 quality than mixing,
It is moved into after mixing in stainless-steel pan, roasts 3h at 700 DEG C, obtain zirconates；
(2) zirconates with deionized water is cleaned, is then added in the hydrochloric acid that concentration is 22wt% and heats instead
3h is answered, obtains reaction product, the reaction product is subjected to separation of solid and liquid, obtains transition liquid, sulfuric acid is added in into the transition liquid
Carry out first set reaction, obtain zirconium basic sulphate as the first sediment, by first sediment further with sulfuric acid reaction knot
Crystalline substance obtains zirconium sulfate, by the zirconium sulfate be formulated as 0.5mol/L sulfuric acid zirconium solution in case with；
(3) aluminum acetate that 0.5mol/L is added in into the sulfuric acid zirconium solution is stirred 4h, and wherein additive amount is Al3+：
Zr4+=2:1, presoma zirconium aluminum solutions are obtained after stirring；
(4) NaHCO of 0.5mol/L is instilled into the zirconium aluminum solutions3Solution is reacted, wherein (HCO3)-With Zr4+'s
Molar concentration rate is 1:0.8, after reacting 4h, obtain the second sediment；
(5) second sediment is filtered successively, deionized water wash 3 times, absolute ethyl alcohol washed once, then
It is dried and calcines, wherein calcining is to calcine 3h at 800 DEG C, then it is compound to obtain zirconium aluminium for ball milling 5h, dried 150 mesh sieve again
Powder.
Zirconium powder obtained by embodiment 2 is after XRD analysis it can be seen that it is cubic phase oxidation to prepare products obtained therefrom
Zirconium and alumina composite powders, sem analysis show the zirconium aluminium composite granule prepared to be subsphaeroidal, and average grain diameter is nanoscale
(130nm)。
Embodiment 3
It is a kind of to be given up the method that zirconium prepares zirconium oxide with solid, comprise the following steps：
(1) it is zirconium dioxide composite refractory waste material pulverising mill is thin, and press 1 with NaOH:1.1 quality is mixed than mixing
It is moved into after even in stainless-steel pan, roasts 3h at 1000 DEG C, obtain zirconates；
(2) zirconates with deionized water is cleaned, is then added in the hydrochloric acid that concentration is 23wt% and heats instead
3h is answered, obtains reaction product, the reaction product is subjected to separation of solid and liquid, obtains transition liquid, sulfuric acid is added in into the transition liquid
Carry out first set reaction, obtain zirconium basic sulphate as the first sediment, by first sediment further with sulfuric acid reaction knot
Crystalline substance obtains zirconium sulfate, by the zirconium sulfate be formulated as 3.0mol/L sulfuric acid zirconium solution in case with；
(3) aluminum nitrate that 6.0mol/L is added in into the sulfuric acid zirconium solution is stirred 4h, and wherein additive amount is Al3+：
Zr4+=4:1, presoma zirconium aluminum solutions are obtained after stirring；
(4) NaOH solution that 0.25mol/L is instilled into the zirconium aluminum solutions is reacted, wherein OH-With Zr4+Mole
Concentration ratio is 1:1, after reacting 4h, obtain the second sediment；
(5) second sediment is filtered successively, deionized water wash 3 times, absolute ethyl alcohol washed once, then
It is dried and calcines, wherein calcining is to calcine 2h at 1000 DEG C, then for 24 hours, dried 150 mesh sieve obtains zirconium aluminium and answers ball milling again
Close powder.
Zirconium powder obtained by embodiment 3 is after XRD analysis it can be seen that it is cubic phase oxidation to prepare products obtained therefrom
Zirconium and alumina composite powders, sem analysis show the zirconium aluminium composite granule prepared to be subsphaeroidal, and average grain diameter is nanoscale
(300nm)。
Embodiment 4
It is a kind of to be given up the method that zirconium prepares zirconium oxide with solid, comprise the following steps：
(1) it is zirconia ceramics waste material pulverising mill is thin, and press 1 with NaOH:1.5 quality is moved into not after mixing than mixing
It becomes rusty in steel pot, roasts 3h at 800 DEG C, obtain zirconates；
(2) zirconates with deionized water is cleaned, is then added in the hydrochloric acid that concentration is 24wt% and heats instead
3h is answered, obtains reaction product, the reaction product is subjected to separation of solid and liquid, obtains transition liquid, sulfuric acid is added in into the transition liquid
Carry out first set reaction, obtain zirconium basic sulphate as the first sediment, by first sediment further with sulfuric acid reaction knot
Crystalline substance obtains zirconium sulfate, by the zirconium sulfate be formulated as 0.5mol/L sulfuric acid zirconium solution in case with；
(3) aluminium chloride that 0.5mol/L is added in into the sulfuric acid zirconium solution is stirred 2h, and wherein additive amount is Al3+：
Zr4+=1:2, presoma zirconium aluminum solutions are obtained after stirring；
(4) Na of 1.0mol/L is instilled into the zirconium aluminum solutions2CO3Solution is reacted, wherein CO3 2-With Zr4+Rub
Your concentration ratio is 1:0.5, after reacting 6h, obtain the second sediment；
(5) second sediment is filtered successively, deionized water wash 3 times, absolute ethyl alcohol washed once, then
It is dried and calcines, wherein calcining is to calcine 2h at 900 DEG C, then it is compound to obtain zirconium aluminium for ball milling 12h, dried 150 mesh sieve again
Powder.
Zirconium powder obtained by embodiment 4 is after XRD analysis it can be seen that it is cubic phase oxidation to prepare products obtained therefrom
Zirconium and alumina composite powders, sem analysis show the zirconium aluminium composite granule prepared to be subsphaeroidal, and average grain diameter is nanoscale
(210nm)。
Embodiment 5
It is a kind of to be given up the method that zirconium prepares zirconium oxide with solid, comprise the following steps：
(1) it is zirconium dioxide composite refractory waste material pulverising mill is thin, and press 1 with NaOH:1.3 quality is mixed than mixing
It is moved into after even in stainless-steel pan, roasts 3h at 1000 DEG C, obtain zirconates；
(2) zirconates with deionized water is cleaned, is then added in the hydrochloric acid that concentration is 24wt% and heats instead
3h is answered, obtains reaction product, the reaction product is subjected to separation of solid and liquid, obtains transition liquid, sulfuric acid is added in into the transition liquid
Carry out first set reaction, obtain zirconium basic sulphate as the first sediment, by first sediment further with sulfuric acid reaction knot
Crystalline substance obtains zirconium sulfate, by the zirconium sulfate be formulated as 1.0mol/L sulfuric acid zirconium solution in case with；
(3) aluminum nitrate that 1.0mol/L is added in into the sulfuric acid zirconium solution is stirred 4h, and wherein additive amount is Al3+：
Zr4+=2:1, presoma zirconium aluminum solutions are obtained after stirring；
(4) NaHCO of 0.5mol/L is instilled into the zirconium aluminum solutions3Solution is reacted, wherein (HCO3)-With Zr4+'s
Molar concentration rate is 1:0.8, after reacting 4h, obtain the second sediment；
(5) second sediment is filtered successively, deionized water wash 3 times, absolute ethyl alcohol washed once, then
It is dried and calcines, wherein calcining is to calcine 2h at 800 DEG C, then for 24 hours, it is compound to obtain zirconium aluminium to ball milling for dried 150 mesh sieve again
Powder.
Zirconium powder obtained by embodiment 5 is after XRD analysis it can be seen that it is cubic phase oxidation to prepare products obtained therefrom
Zirconium and alumina composite powders, sem analysis show the zirconium aluminium composite granule prepared to be subsphaeroidal, and average grain diameter is nanoscale
(180nm)。
The foregoing is merely the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, all should by the change or replacement that can be readily occurred in
It is included within the scope of the present invention.Therefore, protection scope of the present invention should using the scope of the claims as
It is accurate.
Claims (10)
1. a kind of given up the method that zirconium prepares zirconium aluminium composite granule with solid, which is characterized in that is comprised the following steps：
(1) alkalize：Solid is given up and NaOH is added in after zirconium powder breakdown mill roasts, obtains zirconates；
(2) intermediate is prepared：After the zirconates is carried out washing impurity elimination, pickling transformation, filtering and removing slag, transition liquid is obtained, by described in
Transition liquid obtains the first sediment with sulfuric acid first set reaction, and by first sediment, sulfuric acid is precipitated in reactive crystallization again with sulfuric acid
Zirconium, by the zirconium sulfate be formulated as 0.25-3mol/L sulfuric acid zirconium solution in case with；
(3) silicon source stirring 2-6h is added in into the sulfuric acid zirconium solution, obtains zirconium aluminum solutions；
(4) precipitating reagent is instilled into the zirconium aluminum solutions to be reacted, obtain the second sediment；
(5) by second sediment it is washed, it is dry, calcining and post processing after to get zirconium aluminium composite granule.
2. according to the method described in claim 1, zirconium gives up for zirconia ceramics it is characterized in that, solid described in step (1) gives up
One or more of material, zirconium dioxide composite refractory waste material and zirconium dioxide synthetic cut stone processing grinding slag.
3. according to the method described in claim 1, zirconium and the alkaline material it is characterized in that, solid described in step (1) gives up
Mass ratio be 1:1.1~1.5, the temperature of the roasting is 700-1000 DEG C.
4. according to the method described in claim 1, it is characterized in that, it is transformed into using mass fraction described in step (2) as 21
~24% hydrochloric acid carries out heating reaction to the zirconates after washing impurity elimination.
5. according to the method described in claim 1, it is characterized in that, silicon source described in step (3) is aluminum nitrate solution, aluminium chloride
It is one or more of in solution, aluminum sulfate solution and Burow's Solution.
6. according to the method described in claim 1, it is characterized in that, the additive amount of silicon source described in step (3) is Al3+：Zr4+=
(0.5-2)：1.
7. according to the method described in claim 1, it is characterized in that, precipitating reagent described in step (4) is Na2CO3Solution,
NaHCO3One or more of solution or NaOH solution.
8. the method according to the description of claim 7 is characterized in that the molar concentration of precipitating reagent described in step (4) is 0.25
~0.5mol/L, the molar concentration of the precipitating reagent anion and the molar concentration rate of zirconium ion are 1:0.5~1.
9. according to the method described in claim 1, it is characterized in that, in step (4) calcining heat be 800~1200 DEG C, calcining
Time is 2~6h.
10. according to the method described in claim 1, it is characterized in that, in step (5) calcining heat be 800~1200 DEG C, it is described
Ball-milling Time for 5~for 24 hours, the grain size of the Zirconium powder is 50~250nm.
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