CN109626424A - A kind of method that zirconium nitrate thermal denitration prepares zirconium dioxide - Google Patents
A kind of method that zirconium nitrate thermal denitration prepares zirconium dioxide Download PDFInfo
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- CN109626424A CN109626424A CN201811376118.9A CN201811376118A CN109626424A CN 109626424 A CN109626424 A CN 109626424A CN 201811376118 A CN201811376118 A CN 201811376118A CN 109626424 A CN109626424 A CN 109626424A
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Abstract
The invention belongs to zirconium dioxide preparation technical fields, and in particular to a kind of method that zirconium nitrate thermal denitration prepares zirconium dioxide.Include the following steps: that zirconium nitrate solution is evaporated concentration by (1), the zirconium nitrate solution after being concentrated；(2) zirconium nitrate solution after concentration is delivered in cooler crystallizer, crystallisation by cooling is carried out at a temperature of being cooled to 40 DEG C, generate Zr (NO3)4·5H2O crystal, in the evaporation concentration equipment of saturated solution return step (1)；(3) Zr (NO for obtaining step (2)3)4·5H2O crystal is dehydrated using microwave drying, by Zr (NO3)4·5H2O crystal transformation is Zr (NO3)4Powder, the chemical reaction of generation are Zr (NO3)4·5H2O→Zr(NO3)4+6H2O↑；(4) by Zr (NO obtained in step (3)3)4Powder generates ZrO by the way of microwave heating in a fluidized bed2Product, the chemical reaction of generation are Zr (NO3)4→ZrO2+4NO2↑+O2↑.This method have process flow it is short, without using sodium hydroxide pellets agent, do not increase waste water, ZrO2The advantages that product uniformity is good.
Description
Technical field
The invention belongs to zirconium dioxide preparation technical fields, and in particular to a kind of zirconium nitrate thermal denitration prepares zirconium dioxide
Method.
Background technique
Zirconium dioxide is a kind of excellent nonmetallic materials, and because having high rigidity, high tenacity, thermal conductivity is low, corrosion-resistant, high
The characteristics such as intermediary warm conductive and as subsequent production sponge zirconium, are widely used.Especially space flight, aviation,
It is occupied an important position in the industries such as electronics and nuclear industry.
Currently, the method for denitration both at home and abroad is prepared with there are mainly three types of oxides, it is AUC thermal decomposition and reduction method, ADU respectively
Thermal decomposition and reduction method, UNH denitration reduction method.Wherein, anti-stripping agent makes uranyl nitrate decompose three oxygen of acquisition using the method for heating
Changing uranium is UNH method, i.e. thermal denitration method.Ammonium diuranate is obtained using ammonia precipitation process and realizes that nitrate anion removal is ADU method, is flowed in ADU
It carries out carbonic acid crystalline ammonium after journey and obtains ammonium uranyl tricarbonate to be AUC method.
Currently used zirconium dioxide preparation method mainly has the precipitation method and hydrothermal synthesis method.The ratio that the precipitation method are applied at present
It is wide, sediment high-temperature calcination will be obtained into product after precipitating reagent and zirconium salt solution hybrid reaction, feature is easy to operate, but
It is to be easily introduced impurity, consumes precipitating reagent, and product is easy agglomeration；Hydrothermal synthesis method applies in general to zirconium oxychloride, zirconium oxychloride
Through hydrolysis obtain zirconium hydroxide, reaction kettle then is added together with a certain amount of water, through high temperature and pressure (100~300 DEG C ,~
It 15Mpa) reacts and is dried to obtain product after crystal is made.
Therefore, it researches and develops, design a kind of method that zirconium nitrate thermal denitration prepares zirconium dioxide, provided for the preparation of zirconium dioxide
A kind of new preparation method.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of methods that zirconium nitrate thermal denitration prepares zirconium dioxide.
In order to realize the purpose, the technical solution adopted by the present invention is that:
A kind of method that zirconium nitrate thermal denitration prepares zirconium dioxide, includes the following steps:
(1) zirconium nitrate solution is evaporated concentration, the zirconium nitrate solution after being concentrated；
(2) zirconium nitrate solution after concentration is delivered in cooler crystallizer, is cooled down at a temperature of being cooled to 40 DEG C
Crystallization generates Zr (NO3)4·5H2O crystal, in the evaporation concentration equipment of saturated solution return step (1)；
(3) Zr (NO for obtaining step (2)3)4·5H2O crystal is dehydrated using microwave drying, by Zr (NO3)4·5H2O is brilliant
Body is converted into Zr (NO3)4Powder, the chemical reaction of generation are Zr (NO3)4·5H2O→Zr(NO3)4+6H2O↑；
(4) by Zr (NO obtained in step (3)3)4Powder generates ZrO by the way of microwave heating in a fluidized bed2It produces
Product, the chemical reaction of generation are Zr (NO3)4→ZrO2+4NO2↑+O2↑。
Further, a kind of method that zirconium nitrate thermal denitration prepares hafnium oxide as described above, in step (1), nitric acid
[Zr]=60~90g/L, [HNO in zirconium solution3]=4~5mol/L.
Further, a kind of method that zirconium nitrate thermal denitration prepares hafnium oxide as described above, in step (1), by nitre
The temperature that sour zirconium solution is evaporated concentration is 85~100 DEG C.
Further, a kind of method that zirconium nitrate thermal denitration prepares hafnium oxide as described above, in step (1), by nitre
The equipment that sour zirconium solution is evaporated concentration is MVR evaporator.
Further, a kind of method that zirconium nitrate thermal denitration prepares hafnium oxide as described above in step (1), obtains
Concentration after zirconium nitrate solution in zirconium nitrate concentration be 550-650g/L.
Further, a kind of method that zirconium nitrate thermal denitration prepares hafnium oxide as described above in step (1), obtains
Concentration after zirconium nitrate solution in zirconium nitrate concentration be 600g/L.
Further, a kind of method that zirconium nitrate thermal denitration prepares hafnium oxide as described above, in step (2), control
Rate of temperature fall is 2 DEG C/min.
Further, a kind of method that zirconium nitrate thermal denitration prepares hafnium oxide as described above, in step (3), control
Dehydration temperaturre is at 150~200 DEG C.
Further, a kind of method that zirconium nitrate thermal denitration prepares hafnium oxide as described above, in step (4), Zr
(NO3)4The reaction temperature control of powder in a fluidized bed is at 800~900 DEG C, Zr (NO3)4When powder stop in a fluidized bed
Between be 2min.
The beneficial effect of technical solution of the present invention is: this method is short with process flow, does not use sodium hydroxide pellets
Agent does not increase waste water, ZrO2The advantages that product uniformity is good.
Detailed description of the invention
Fig. 1 is that a kind of zirconium nitrate solution thermal denitration of the present invention prepares zirconium dioxide process flow chart.
Specific embodiment
Technical solution of the present invention is described in detail in the following with reference to the drawings and specific embodiments.
As shown in Figure 1, a kind of method that zirconium nitrate thermal denitration prepares zirconium dioxide of the present invention, includes the following steps:
(1) zirconium nitrate solution is evaporated concentration, the zirconium nitrate solution after being concentrated；
[Zr]=60~90g/L, [HNO in zirconium nitrate solution3]=4~5mol/L；
It is 85~100 DEG C by the temperature that zirconium nitrate solution is evaporated concentration；
It is MVR evaporator by the equipment that zirconium nitrate solution is evaporated concentration；
The concentration of zirconium nitrate is 550-650g/L in zirconium nitrate solution after obtained concentration.
(2) zirconium nitrate solution after concentration is delivered in cooler crystallizer, is cooled down at a temperature of being cooled to 40 DEG C
Crystallization generates Zr (NO3)4·5H2O crystal, in the evaporation concentration equipment of saturated solution return step (1)；
Control rate of temperature fall is 2 DEG C/min when cooling.
(3) Zr (NO for obtaining step (2)3)4·5H2O crystal is dehydrated using microwave drying, by Zr (NO3)4·5H2O is brilliant
Body is converted into Zr (NO3)4Powder, the chemical reaction of generation are Zr (NO3)4·5H2O→Zr(NO3)4+6H2O↑；
Dehydration temperaturre is controlled at 150~200 DEG C.
(4) by Zr (NO obtained in step (3)3)4Powder generates ZrO by the way of microwave heating in a fluidized bed2It produces
Product, the chemical reaction of generation are Zr (NO3)4→ZrO2+4NO2↑+O2↑；Zr(NO3)4The reaction temperature control of powder in a fluidized bed
System is at 800~900 DEG C, Zr (NO3)4The residence time of powder in a fluidized bed is 2min.
Embodiment 1
(1) by uranyl nitrate solution ([Zr]=85g/l, [HNO3]=4mol/l, with 2.0m3/ h flow inputs MVR evaporation
In device, 88 DEG C of temperature of control, the zirconium nitrate solution after being concentrated, solubility 580g/l；
(2) in the zirconium nitrate solution input cooler crystallizer after being concentrated, stirring frequency 50r/min, rate of temperature fall 2 are controlled
DEG C/min, final 40 DEG C/min of crystallization temperature, 1.5h complete crystallization, generate Zr (NO3)4·5H2O；
(3)Zr(NO3)4·5H2O crystal inputs in microwave dryer, feed paddle frequency 20Hz, controls dehydration temperaturre 170
DEG C, generate Zr (NO3)4Powder；
(4)Zr(NO3)4Control calcination temperature generates ZrO at 820 DEG C in a fluidized bed2Product, product are qualified.
Embodiment 2
(1) by uranyl nitrate solution ([Zr]=78g/l, [HNO3]=4.5mol/l, with 2.5m3/ h flow inputs MVR and steams
It sends out in device, 90 DEG C of temperature of control, the zirconium nitrate solution after being concentrated, solubility 570g/l；
(2) in the zirconium nitrate solution input cooler crystallizer after being concentrated, stirring frequency 50r/min, rate of temperature fall 2 are controlled
DEG C/min, final 40 DEG C/min of crystallization temperature, 1.5h complete crystallization, generate Zr (NO3)4·5H2O；
(3)Zr(NO3)4·5H2O crystal inputs in microwave dryer, feed paddle frequency 20Hz, controls dehydration temperaturre 170
DEG C, generate Zr (NO3)4Powder；
(4)Zr(NO3)4Control calcination temperature generates ZrO at 830 DEG C in a fluidized bed2Product, product are qualified.
Claims (10)
1. a kind of method that zirconium nitrate thermal denitration prepares zirconium dioxide, it is characterised in that: include the following steps:
(1) zirconium nitrate solution is evaporated concentration, the zirconium nitrate solution after being concentrated；
(2) zirconium nitrate solution after concentration is delivered in cooler crystallizer, carries out crystallisation by cooling at a temperature of being cooled to 40 DEG C,
Generate Zr (NO3)4·5H2O crystal, in the evaporation concentration equipment of saturated solution return step (1)；
(3) Zr (NO for obtaining step (2)3)4·5H2O crystal is dehydrated using microwave drying, by Zr (NO3)4·5H2O crystal turns
Turn to Zr (NO3)4Powder, the chemical reaction of generation are Zr (NO3)4·5H2O→Zr(NO3)4+6H2O↑；
(4) by Zr (NO obtained in step (3)3)4Powder generates ZrO by the way of microwave heating in a fluidized bed2Product,
The chemical reaction of generation is Zr (NO3)4→ZrO2+4NO2↑+O2↑。
2. a kind of method that zirconium nitrate thermal denitration prepares hafnium oxide as described in claim 1, it is characterised in that: step (1)
In, [Zr]=60~90g/L, [HNO in zirconium nitrate solution3]=4~5mol/L.
3. a kind of method that zirconium nitrate thermal denitration prepares hafnium oxide as described in claim 1, it is characterised in that: step (1)
In, it is 85~100 DEG C by the temperature that zirconium nitrate solution is evaporated concentration.
4. a kind of method that zirconium nitrate thermal denitration prepares hafnium oxide as described in claim 1, it is characterised in that: step (1)
In, it is MVR evaporator by the equipment that zirconium nitrate solution is evaporated concentration.
5. a kind of method that zirconium nitrate thermal denitration prepares hafnium oxide as described in claim 1, it is characterised in that: step (1)
In, the concentration of zirconium nitrate is 550-650g/L in the zirconium nitrate solution after obtained concentration.
6. a kind of method that zirconium nitrate thermal denitration prepares hafnium oxide as claimed in claim 5, it is characterised in that: step (1)
In, the concentration of zirconium nitrate is 600g/L in the zirconium nitrate solution after obtained concentration.
7. a kind of method that zirconium nitrate thermal denitration prepares hafnium oxide as described in claim 1, it is characterised in that: step (2)
In, control rate of temperature fall is 2 DEG C/min.
8. a kind of method that zirconium nitrate thermal denitration prepares hafnium oxide as described in claim 1, it is characterised in that: step (3)
In, dehydration temperaturre is controlled at 150~200 DEG C.
9. a kind of method that zirconium nitrate thermal denitration prepares hafnium oxide as described in claim 1, it is characterised in that: step (4)
In, Zr (NO3)4The reaction temperature control of powder in a fluidized bed is at 800~900 DEG C, Zr (NO3)4Powder stopping in a fluidized bed
Staying the time is 2min.
10. a kind of method that zirconium nitrate thermal denitration prepares hafnium oxide as described in claim 1, it is characterised in that: step (1)
In, [Zr]=60~90g/L, [HNO in zirconium nitrate solution3]=4~5mol/L；Zirconium nitrate solution is evaporated to the temperature of concentration
Degree is 85~100 DEG C；It is MVR evaporator by the equipment that zirconium nitrate solution is evaporated concentration；Zirconium nitrate after obtained concentration
The concentration of zirconium nitrate is 600g/L in solution；
In step (2), control rate of temperature fall is 2 DEG C/min；
In step (3), dehydration temperaturre is controlled at 150~200 DEG C；
In step (4), Zr (NO3)4The reaction temperature control of powder in a fluidized bed is at 800~900 DEG C, Zr (NO3)4Powder is flowing
Changing the residence time in bed is 2min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4563335A (en) * | 1982-12-21 | 1986-01-07 | Doryokuro Kakunenryo Kaihatsu Jigyodan | Apparatus for continuously concentrating and denitrating nitrate solution by microwave |
| JP2004012166A (en) * | 2002-06-04 | 2004-01-15 | Japan Nuclear Cycle Development Inst States Of Projects | Reprocessing method for spent nuclear fuel |
| CN106629854A (en) * | 2016-10-20 | 2017-05-10 | 核工业理化工程研究院 | Method for producing uranium trioxide by heating uranyl nitrate solution in microwave manner |
-
2018
- 2018-11-19 CN CN201811376118.9A patent/CN109626424A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4563335A (en) * | 1982-12-21 | 1986-01-07 | Doryokuro Kakunenryo Kaihatsu Jigyodan | Apparatus for continuously concentrating and denitrating nitrate solution by microwave |
| JP2004012166A (en) * | 2002-06-04 | 2004-01-15 | Japan Nuclear Cycle Development Inst States Of Projects | Reprocessing method for spent nuclear fuel |
| CN106629854A (en) * | 2016-10-20 | 2017-05-10 | 核工业理化工程研究院 | Method for producing uranium trioxide by heating uranyl nitrate solution in microwave manner |
Non-Patent Citations (5)
| Title |
|---|
| GORAN STEFANIC: "Formation of ZrO2 by the Thermal Decomposition of Zirconium Salts", 《CROATICA CHEMICA ACTA》 * |
| 朱洪法: "《无机化工产品手册》", 31 December 2008, 金盾出版社 * |
| 沈朝纯: "《铀及其化合物的化学与工艺学》", 30 June 1991 * |
| 蒋东民等: "《氧氯化锆制备工艺与应用》", 31 August 2012, 冶金工业出版社 * |
| 达维多夫: "《制取稀有和放射性金属氧化物的热过程与设备》", 31 August 1984 * |
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