CN108059186A - It is given up the method that zirconium prepares Zirconium powder as raw material hydro-thermal method using solid - Google Patents
It is given up the method that zirconium prepares Zirconium powder as raw material hydro-thermal method using solid Download PDFInfo
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Abstract
The invention belongs to technical field of chemical material preparation, and in particular to a kind of to be given up the method that zirconium prepares Zirconium powder as raw material hydro-thermal method using solid.This method be by solid give up zirconium by quaternization obtain alkalization material, alkalization material is first made the transition, again zirconium basic sulphate is obtained with sulfuric acid reaction, zirconium basic sulphate further obtains zirconium sulfate with sulfuric acid reaction, zirconium sulfate obtained is prepared into sulfuric acid zirconium solution, then Zirconium powder is obtained by hydro-thermal reaction.The present invention passes through two step acidification reactions so that the purity higher of zirconium sulfate is conducive to the hydro-thermal reaction of next step, further improves the content of zirconium oxide in Zirconium powder.Zirconium powder grain size is small in the present invention, purity is high, good dispersion, crystallinity are high, and hydrothermal synthesizing condition is mild, simple for process, not only avoids solid and gives up the disposal difficulties of zirconium, and realizes solid and give up the recycling of zirconium.
Description
Technical field
The invention belongs to technical field of chemical material preparation, and in particular to a kind of to give up zirconium as the preparation of raw material hydro-thermal method using solid
The method of Zirconium powder.
Background technology
It is continuously improved as society continues to develop with people's living standard, people are to electric light high-tech product and bullion
Demand it is more and more, photoelectric crystal, zirconium drill ornaments market are increasing.However the industries such as glass furnace, crystal growing furnace are replaced
The scrap feed material containing zirconium changed is more and more, and the leftover pieces that zirconium bores jewelry processing are also more and more.These solids zirconium that gives up is high temperature
Sintering is stablized or high-temperature fusion stablizes the tetragonal zircite or cubic zirconia to be formed, and materialization stability is good, can not be used common
Physical/chemical method is decomposed completely, can not further be recycled.
Zirconia ceramics is one of best structure/function ceramics of current comprehensive performance, is widely used in aerospace, passes
The technical fields such as sensor.As structural ceramics, zirconium oxide intensity height, good toughness, corrosion-resistant, high temperature resistant, for manufacturing jet hair
The critical components such as motivation, steam turbine；Zirconium oxide is nonmagnetic, non-conductive, wear-resistant, suitable for manufacture medical device, grinding and grinding
Component etc..As function ceramics, zirconium oxide can be used for manufacturing lambda sensor, solid oxide fuel cell element etc..With
The development of emerging high-tech industry, zirconia ceramics material application is more and more wider, if zirconia ceramics material is because its hardness is high, nothing
The advantages that signal shielding, thermal diffusivity are good, perception is strong becomes mobile fingerprint identification cover board, mobile phone backboard that annual value of production crosses hundred billion yuan
The preferred material of intelligent terminals component is waited, therefore high quality Zirconium powder has a vast market prospect.
High temperature and pressure, solvability be strong, reactant activity is changed and improves because its aqueous solution is in for hydrothermal synthesis method,
There is can to prepare solid phase reaction and be difficult to that the material prepared, product powder crystallinity are high, purity is high, pattern is easily-controllable, into
To prepare one of ideal methods of function powders such as Zirconium powder.
The method that Chinese patent CN105152211A discloses a kind of discarded object containing zirconium production zirconium oxychloride, this method be by containing
Zirconium is discarded makes zirconium oxide therein be converted into highly basic hydroxide, the neutralized reaction generation of highly basic hydroxide by alkali fusion reaction
Zirconium hydroxide, zirconium hydroxide is through the molten filtering and impurity removing of acid, clear liquid condensing crystallizing generation zirconium oxychloride.This method is traditional oxychlorination zirconium
Production line, there are problems that in the production process of zirconium oxychloride " three wastes " pollution, be unfavorable for environmental protection.
Chinese patent CN103193266A discloses a kind of refractory waste production zirconia-alumina composite oxide utilized containing zirconium
Method, this method be will contain zirconium waste material pass through 100 mesh sieve, sorting removal of impurities；Zirconium waste material will be contained to mix with alkaline matter
It is even, it at a temperature of 850 DEG C -1050 DEG C, carries out alkali and melts, when the time that alkali melts is 2-4 small；Topple over after material cooling after alkali is melted
Enter in water, when stirring at normal temperature leaching 1 is small, be then centrifuged for separating；It is carried out in the acid solution that concentration expressed in percentage by weight is 10-15%
Stirring leaching, when the time of acidleach is 2 small, the temperature of acidleach is 100-105 DEG C；The material of acidleach is centrifuged,
Washing, is then dried；Finally silica is sloughed in melting in electric smelter, and zirconia-alumina composite oxide is made through injection.The patent
It is that material after alkali is melted first leaches in water, then acidleach, the temperature of acidleach is 100-105 DEG C, and what is finally obtained is that zirconium aluminium is answered
Close oxide.
At present, it is the extraction route of zirconium and using the zirconium of extraction to be former based on the give up key of zirconium extraction Zirconium powder of solid
The method that material prepares high quality Zirconium powder.
The content of the invention
The object of the present invention is to provide it is a kind of it is simple for process, Zirconium powder purity is high gives up zirconium as raw material hydro-thermal using solid
The method that method prepares Zirconium powder.
It is of the present invention to prepare as raw material hydro-thermal method the method for Zirconium powder using the solid zirconium that gives up and be：The solid zirconium that gives up is led to
It crosses quaternization and obtains alkalization material, alkalization material is converted into zirconium sulfate by acidification reaction, then obtains zirconium oxide by hydro-thermal reaction
Powder.
Wherein：
The quaternization is to roast the solid zirconium that gives up with sodium hydroxide.
The give up mass ratio of zirconium and sodium hydroxide of the solid is 1:1.1-1.5.
The solid zirconium that gives up is selected from leftover pieces that the waste product, substandard products and zirconium of zirconia ceramics and refractory material bore etc..
The calcination temperature is 700-1000 DEG C, roasting time 2-5h.
The acidification reaction is that alkalization material first is obtained zirconium basic sulphate through being transferred in solution, then with sulfuric acid reaction,
Zirconium basic sulphate further obtains zirconium sulfate with sulfuric acid reaction.
The transition is using hydrochloric acid solution, and hydrochloric acid solution is for concentrated hydrochloric acid with water according to volume ratio 1:1-2 is made, the transition
Temperature is 60-80 DEG C, and the transition time is 2-4h.
Zirconium sulfate obtained is prepared into sulfuric acid zirconium solution, the wherein concentration of zirconium ion is 0.1-3.0mol/L.
The hydro-thermal reaction is to add in alkali, surfactant in sulfuric acid zirconium solution, and hydro-thermal reaction is dried to obtain zirconium oxide
Powder.
The alkali is Na2CO3、NaHCO3Or NaOH；The surfactant is sucrose, glucose, sodium gluconate, fruit
Sugar or polyethylene glycol.
The molar ratio of the alkali and zirconium ion in sulfuric acid zirconium solution is 1:In 0.5-1, surfactant and sulfuric acid zirconium solution
The molar ratio of zirconium ion is 0.1-0.5:1, the hydrothermal temperature is 150-250 DEG C, the hydro-thermal reaction time 1-10h.
The composition of Zirconium powder produced by the present invention is 90-100wt.% zirconium oxides and 0-10wt.% other elements oxygen
The zirconium oxide of compound, generally 92-97wt.%, the yttrium oxide of 3-8wt.%.
The particle size range of Zirconium powder produced by the present invention is 50-150nm, and it is total to account for zirconium oxide for wherein tetragonal phase zirconium oxide
The 80-100wt.% of amount.
It is of the present invention to prepare as raw material hydro-thermal method the method for Zirconium powder using the solid zirconium that gives up and specifically include following step
Suddenly：
(1) solid giving up, zirconium powder is broken to add in sodium hydroxide afterwards, and roasting makes zirconium oxide be converted into zirconates；
(2) by the zirconates that step (1) obtains through washing, hydrochloric acid solution be transferred in solution, then with sulfuric acid reaction, from
The heart, isolates zirconium basic sulphate, and zirconium basic sulphate further with sulfuric acid reaction, crystallizes, centrifugation, obtains zirconium sulfate, then by sulfuric acid
Zirconium is diluted to the sulfuric acid zirconium solution that zirconium ion concentration is 0.1-3.0mol/L；The transition refers to that zirconates is transferred to solution by solid
In.
(3) alkali, surfactant are added in the sulfuric acid zirconium solution that step (2) obtains and carry out hydro-thermal reaction, filtered, wash
It washs, is dried to obtain Zirconium powder.
If the present invention is without transition, directly by zirconates and sulfuric acid reaction, then impurity contained in zirconates can be directly entered
In solid sulphuric acid zirconium, the purity of zirconium sulfate is influenced.Therefore, first zirconates is entered by transition in solution, avoids impurity entrance
Solution.The present invention is according to a step acidification reaction also easily so that solid sulphuric acid zirconium is mingled with impurity.Therefore, it is acidified by two steps anti-
It should so that be not easy to be mingled with impurity in zirconium sulfate, be separated by two-step reaction, two steps so that the purity higher of zirconium sulfate.
Beneficial effects of the present invention are as follows：
Giving up the invention avoids solid, zirconium is traditional to recycle route and conventional oxidation zirconium production line.The present invention first will be solid
The body zirconium that gives up obtains alkalization material by quaternization, then alkalization material is transferred to through washing, making the transition in solution, and alkali is obtained with sulfuric acid reaction
Formula zirconium sulfate, zirconium basic sulphate further obtain zirconium sulfate with sulfuric acid reaction, and Zirconium powder is obtained finally by hydro-thermal reaction.
Solid is given up in zirconium zirconium successful conversion into zirconium sulfate by the present invention using the route of first quaternization two step acidification reactions again.
In fact, after the present invention washes alkalization material, and made the transition using hydrochloric acid solution, zirconium ion solution is formed, is first added in
A part of sulfuric acid, zirconium ion generate zirconium basic sulphate with sulfuric acid reaction, and zirconium basic sulphate with another part sulfuric acid reaction, generates again
Zirconium sulfate.Pass through two step acidification reactions so that be not easy to be mingled with impurity in zirconium sulfate, the purity higher of zirconium sulfate is conducive to next
The hydro-thermal reaction of step further improves the content of zirconium oxide in Zirconium powder.
Zirconium powder grain size is small in the present invention, purity is high, good dispersion, crystallinity are high, and hydrothermal synthesizing condition is mild, work
Skill is simple, not only avoids solid and gives up the disposal difficulties of zirconium, and realizes the recycling of solid waste.
Description of the drawings
Fig. 1 is the X-ray diffraction XRD diagram of 1 Zirconium powder of embodiment；
Fig. 2 is the scanning electron microscope sem figure of 1 Zirconium powder of embodiment.
Specific embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
Zirconia ceramics waste product is crushed into levigate, particle mean size 40nm, adds in piece alkali, zirconia ceramics waste product and piece alkali
Mass ratio be 1:1.2, it moves into after mixing in stainless-steel pan, zirconates is obtained when 800 DEG C of temperature calcinations 3 are small；
Zirconates is washed with deionized 3 times, adds in hydrochloric acid solution transition, hydrochloric acid solution is for concentrated hydrochloric acid with water according to volume ratio
1:1 is made, and the mass ratio of zirconates and hydrochloric acid solution is 1:2, be heated to 70 DEG C reaction 3 it is small when, be filtered to remove filter residue and made the transition
The mass ratio of liquid, transition liquid and sulfuric acid solution is 1:2.5, transition liquid is first reacted with the sulfuric acid solution of 1/2 mass, and centrifugation obtains alkali
Formula zirconium sulfate, zirconium basic sulphate are further reacted with remaining sulfuric acid solution, and crystallization, centrifugation obtains zirconium sulfate, then is diluted to zirconium
Ion concentration is the sulfuric acid zirconium solution of 0.25mol/L；
NaOH, sodium gluconate are added in sulfuric acid zirconium solution, the molar ratio of wherein NaOH and zirconium ion is 1:0.5, Portugal
The molar ratio of grape sodium saccharate and zirconium ion is 0.2:1, stirring 2 it is small when after be transferred in water heating kettle, at 180 DEG C react 2 it is small when, will produce
Object filters, and washes 3 times, then wash 1 time with absolute ethyl alcohol, obtains Zirconium powder after drying, average grain diameter 55nm, after testing
The content of zirconium oxide is 95.9wt.% in the Zirconium powder, and surplus is yttrium oxide.
Zirconium powder is subjected to X-ray diffraction, scanning electron microscope detection, X-ray diffraction XRD diagram is as shown in Figure 1, scanning
Electronic Speculum SEM schemes as shown in Fig. 2, the Zirconium powder that XRD analysis show to prepare is pure tetragonal phase zirconium oxide, and sem analysis shows to make
Standby Zirconium powder average grain diameter is small, is nanometer grade powder.
Embodiment 2
Zirconium is bored into leftover pieces and crushes levigate, particle mean size 60nm, adds in piece alkali, the matter of zirconia ceramics waste product and piece alkali
Amount is than being 1:1.1, it moves into after mixing in stainless-steel pan, zirconates is obtained when 700 DEG C of temperature calcinations 4 are small；
Zirconates is washed with deionized 3 times, adds in hydrochloric acid solution transition, hydrochloric acid solution is for concentrated hydrochloric acid with water according to volume ratio
1:1 is made, and the mass ratio of zirconates and hydrochloric acid solution is 1:2.5, be heated to 60 DEG C reaction 4 it is small when, be filtered to remove filter residue and turned
The mass ratio of type liquid, transition liquid and sulfuric acid solution is 1:1.5, transition liquid is first reacted with the sulfuric acid solution of 1/2 mass, and centrifugation obtains
Zirconium basic sulphate, zirconium basic sulphate are further reacted with remaining sulfuric acid solution, and crystallization, centrifugation obtains zirconium sulfate, then is diluted to
Zirconium ion concentration is the sulfuric acid zirconium solution of 0.5mol/L；
By Na2CO3, glucose add in sulfuric acid zirconium solution in, wherein Na2CO3Molar ratio with zirconium ion is 1:1, glucose
Molar ratio with zirconium ion is 0.1:1, stirring 2 it is small when after be transferred in water heating kettle, at 150 DEG C react 10 it is small when, product is filtered,
Washing 3 times, then washed 1 time with absolute ethyl alcohol, obtain Zirconium powder, average grain diameter 95nm, the after testing oxidation after dry
The content of zirconium oxide is 95.6wt.% in zirconium powder body, and surplus is yttrium oxide.
Zirconium powder is subjected to X-ray diffraction, scanning electron microscope detection, the Zirconium powder that XRD analysis show to prepare is
Pure tetragonal phase zirconium oxide, sem analysis show that the Zirconium powder average grain diameter prepared is small, are nanometer grade powder.
Embodiment 3
By zirconia refractory waste product crush levigate, particle mean size 50nm, add in piece alkali, zirconia ceramics waste product with
The mass ratio of piece alkali is 1:1.5, it moves into after mixing in stainless-steel pan, zirconates is obtained when 1000 DEG C of temperature calcinations 3 are small；
Zirconates is washed with deionized 3 times, adds in hydrochloric acid solution transition, hydrochloric acid solution is for concentrated hydrochloric acid with water according to volume ratio
1:1 is made, and the mass ratio of zirconates and hydrochloric acid solution is 1:3, be heated to 80 DEG C reaction 2 it is small when, be filtered to remove filter residue and made the transition
The mass ratio of liquid, transition liquid and sulfuric acid solution is 1:2, transition liquid is first reacted with the sulfuric acid solution of 1/2 mass, and centrifugation obtains alkali formula
Zirconium sulfate, zirconium basic sulphate further with remaining sulfuric acid solution react, crystallization, centrifugation obtain zirconium sulfate, then be diluted to zirconium from
Sub- concentration is the sulfuric acid zirconium solution of 3.0mol/L；
NaOH, polyethylene glycol are added in sulfuric acid zirconium solution, the molar ratio of wherein NaOH and zirconium ion is 1:0.8, poly- second
The molar ratio of glycol and zirconium ion is 0.5:1, stirring 2 it is small when after be transferred in water heating kettle, at 250 DEG C react 1 it is small when, by product mistake
Filter is washed 3 times, then wash 1 time with absolute ethyl alcohol, obtains Zirconium powder after drying, average grain diameter 70nm, after testing the oxygen
Change the content of zirconium oxide in zirconium powder body as 96.1wt.%, surplus is yttrium oxide.
Zirconium powder is subjected to X-ray diffraction, scanning electron microscope detection, the Zirconium powder that XRD analysis show to prepare is
Pure tetragonal phase zirconium oxide, sem analysis show that the Zirconium powder average grain diameter prepared is small, are nanometer grade powder.
Comparative example 1
After the zirconates washing in embodiment 1, without transition, it is directly added into sulfuric acid solution and reacts, remaining step is same
Embodiment 1, is as follows：
Zirconia ceramics waste product is crushed into levigate, particle mean size 40nm, adds in piece alkali, zirconia ceramics waste product and piece alkali
Mass ratio be 1:1.2, it moves into after mixing in stainless-steel pan, zirconates is obtained when 800 DEG C of temperature calcinations 3 are small；
The mass ratio of zirconates and sulfuric acid solution is 1:2.5, first zirconates and the sulfuric acid solution of 1/2 mass are reacted, centrifuged
To zirconium basic sulphate, zirconium basic sulphate is further reacted with remaining sulfuric acid solution, and crystallization, centrifugation obtains zirconium sulfate, then dilutes
Into the sulfuric acid zirconium solution that zirconium ion concentration is 0.25mol/L；
NaOH, sodium gluconate are added in sulfuric acid zirconium solution, the molar ratio of wherein NaOH and zirconium ion is 1:0.5, Portugal
The molar ratio of grape sodium saccharate and zirconium ion is 0.2:1, stirring 2 it is small when after be transferred in water heating kettle, at 180 DEG C react 2 it is small when, will produce
Object filters, and washes 3 times, then is washed 1 time with absolute ethyl alcohol, and Zirconium powder, average grain diameter 210nm, through inspection are obtained after dry
The content of zirconium oxide in the Zirconium powder is surveyed as 70.5wt.%, yttrium oxide 3.4wt.%, surplus is impurity.
Comparative example 2
A step acidifying will be carried out after zirconates transition in embodiment 1, remaining step is as follows with embodiment 1：
Zirconia ceramics waste product is crushed into levigate, particle mean size 40nm, adds in piece alkali, zirconia ceramics waste product and piece alkali
Mass ratio be 1:1.2, it moves into after mixing in stainless-steel pan, zirconates is obtained when 800 DEG C of temperature calcinations 3 are small；
Zirconates is washed with deionized 3 times, adds in hydrochloric acid solution transition, hydrochloric acid solution is for concentrated hydrochloric acid with water according to volume ratio
1:1 is made, and the mass ratio of zirconates and hydrochloric acid solution is 1:2, be heated to 70 DEG C reaction 3 it is small when, be filtered to remove filter residue and made the transition
The mass ratio of liquid, transition liquid and sulfuric acid solution is 1:2.5, transition liquid carries out single step reaction with sulfuric acid solution, and centrifugation obtains sulfuric acid
Zirconium, then it is diluted to the sulfuric acid zirconium solution that zirconium ion concentration is 0.25mol/L；
NaOH, sodium gluconate are added in sulfuric acid zirconium solution, the molar ratio of wherein NaOH and zirconium ion is 1:0.5, Portugal
The molar ratio of grape sodium saccharate and zirconium ion is 0.2:1, stirring 2 it is small when after be transferred in water heating kettle, at 180 DEG C react 2 it is small when, will produce
Object filters, and washes 3 times, then is washed 1 time with absolute ethyl alcohol, and Zirconium powder, average grain diameter 248nm, through inspection are obtained after dry
The content of zirconium oxide in the Zirconium powder is surveyed as 72.9wt.%, yttrium oxide 2.5wt.%, surplus is impurity.
By comparative example 1-2 compared with embodiment 1, the Zirconium powder average grain diameter that embodiment 1 obtains is small, zirconia powder
The content of zirconium oxide is high in body.In embodiment 1-3, the zirconia content of Zirconium powder is more than 95wt.%.
The present invention derives instrument using the Miniflex600 types X-ray of Rigaku companies and carries out XRD characterization analysis, utilizes
The S4800 types scanning electron microscope of Hitachi companies obtains SEM figures.Zirconia ceramics waste product of the present invention, zirconium bore leftover pieces,
Zirconia refractory waste product is commercial goods.
Claims (10)
1. a kind of given up the method that zirconium prepares Zirconium powder as raw material hydro-thermal method using solid, it is characterised in that：The solid zirconium that gives up is led to
It crosses quaternization and obtains alkalization material, alkalization material is converted into zirconium sulfate by acidification reaction, then obtains zirconium oxide by hydro-thermal reaction
Powder.
2. according to claim 1 given up the method that zirconium prepares Zirconium powder as raw material hydro-thermal method using solid, feature exists
In：The quaternization is to roast the solid zirconium that gives up with sodium hydroxide.
3. according to claim 2 given up the method that zirconium prepares Zirconium powder as raw material hydro-thermal method using solid, feature exists
In：The give up mass ratio of zirconium and sodium hydroxide of the solid is 1:1.1-1.5.
4. according to claim 2 given up the method that zirconium prepares Zirconium powder as raw material hydro-thermal method using solid, feature exists
In：The calcination temperature is 700-1000 DEG C, roasting time 2-5h.
5. according to claim 1 given up the method that zirconium prepares Zirconium powder as raw material hydro-thermal method using solid, feature exists
In：The acidification reaction is that alkalization material first is obtained zirconium basic sulphate, alkali formula sulphur through being transferred in solution, then with sulfuric acid reaction
Sour zirconium further obtains zirconium sulfate with sulfuric acid reaction.
6. according to claim 5 given up the method that zirconium prepares Zirconium powder as raw material hydro-thermal method using solid, feature exists
In：The transition is using hydrochloric acid solution, and hydrochloric acid solution is for concentrated hydrochloric acid with water according to volume ratio 1:1-2 is made, the transition temperature
For 60-80 DEG C, the transition time is 2-4h.
7. according to claim 5 given up the method that zirconium prepares Zirconium powder as raw material hydro-thermal method using solid, feature exists
In：Zirconium sulfate obtained is prepared into sulfuric acid zirconium solution, the wherein concentration of zirconium ion is 0.1-3.0mol/L.
8. according to claim 7 given up the method that zirconium prepares Zirconium powder as raw material hydro-thermal method using solid, feature exists
In：The hydro-thermal reaction is to add in alkali, surfactant in sulfuric acid zirconium solution, and hydro-thermal reaction is dried to obtain Zirconium powder.
9. according to claim 8 given up the method that zirconium prepares Zirconium powder as raw material hydro-thermal method using solid, feature exists
In：The alkali is Na2CO3、NaHCO3Or NaOH；The surfactant is sucrose, glucose, sodium gluconate, fructose or poly-
Ethylene glycol.
10. according to claim 8 given up the method that zirconium prepares Zirconium powder as raw material hydro-thermal method using solid, feature exists
In：The molar ratio of the alkali and zirconium ion in sulfuric acid zirconium solution is 1:0.5-1, surfactant and zirconium ion in sulfuric acid zirconium solution
Molar ratio be 0.1-0.5:1, the hydrothermal temperature is 150-250 DEG C, the hydro-thermal reaction time 1-10h.
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| CN110441123A (en) * | 2019-08-13 | 2019-11-12 | 湖北大学 | A kind of zirconio material digestion procedure |
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