CN107915255A - The preparation method of nano zircite and its nano zircite of preparation - Google Patents
The preparation method of nano zircite and its nano zircite of preparation Download PDFInfo
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- CN107915255A CN107915255A CN201610882966.1A CN201610882966A CN107915255A CN 107915255 A CN107915255 A CN 107915255A CN 201610882966 A CN201610882966 A CN 201610882966A CN 107915255 A CN107915255 A CN 107915255A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
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Abstract
The present invention relates to a kind of preparation method of nano zircite and its nano zircite of preparation, mainly solves the problems, such as that nano zircite specific surface area prepared by the prior art is small.The present invention by using including with alkali precipitation zirconates obtain precursor, and by the precursor pH value be 7~12 under the conditions of flow back the step of technical solution preferably solve the problems, such as this, available in the industrial production of nano zircite.
Description
Technical field
The present invention relates to a kind of preparation method of nano zircite and its nano zircite of preparation.
Background technology
ZrO2There are three kinds of stable crystal forms:Room temperature to 1170 DEG C be monoclinic phase, 1170 DEG C~2370 DEG C are Tetragonal, are higher than
2370 DEG C are Emission in Cubic, the physics and differing chemical properties of the zirconium dioxide of different phase.Meanwhile nanoscale zirconia is a kind of
There is acid, alkalescence and oxidation, the metal oxide nano-material of reproducibility at the same time, and be P-type semiconductor again, be also easy to produce sky
Cave, can produce stronger interaction with active component, excellent catalytic performance is often shown in some catalytic reactions.
Traditional method for preparing zirconium oxide includes the precipitation method, hydro-thermal method, sol-gal process etc., and basic ideas are will be solvable
Property raw material reacts after being sufficiently mixed, and prepares the product of uniformity, size tunable.But due to the atom of Zr atoms in itself
Measure it is bigger, cause synthesis after nanometer zirconium oxide specific surface area it is less than normal, be generally less than 50m2g-1, this is largely
On limit application of the zirconium oxide as catalyst or catalyst carrier.
Document CN103523830A discloses a kind of monoclinic phase zirconia nanocrystals raw powder's production technology, and this method exists
After the long period acid solution containing zirconium ion of the heating pH value less than 5 above-mentioned monoclinic phase two is deposited using water-soluble flocculant
Zirconium oxide micelle or fine solid particle.The high specific surface zirconium that this method obtains is pure monoclinic phase.Due to different phase oxidations
The physicochemical properties of zirconium are variant, its application receives certain limitation.
The content of the invention
The technical problems to be solved by the invention are the problem of nano zircite specific surface area of prior art preparation are small, are carried
For a kind of preparation method of new nano zircite.Nano zircite prepared by this method has the characteristics that specific surface area is big.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of preparation method of nano zircite,
Including obtaining precursor with alkali precipitation zirconates, and
The step of flowing back under the conditions of being 7~12 in pH value by the precursor.
In above-mentioned technical proposal, reflux temperature is 0~150 DEG C, preferably 80~100 DEG C.
In above-mentioned technical proposal, return time for 1~60 it is small when, preferably 24~48 it is small when.
In above-mentioned technical proposal, the zirconates is the soluble nitrate of zirconium, carbonate, villaumite, oxalates, formates,
At least one of acetate and ammonium salt；It is preferred that at least one of zirconium nitrate, zirconyl nitrate, zirconium oxychloride and zirconium chloride.
In above-mentioned technical proposal, the alkali is at least one of potassium hydroxide, sodium hydroxide and ammonium hydroxide.
The present invention also provides a kind of nano zircite prepared according to the preparation method of the nano zircite.
In above-mentioned technical proposal, the specific surface area of the nano zircite is more than 100 centimetres2/ gram, preferably 120~160 lis
Rice2/ gram.
In above-mentioned technical proposal, the crystal form of the nano zircite is Tetragonal.
The present invention also provides a kind of nano zircite prepared according to the preparation method of the nano zircite in water-gas
Application in conversion and decarboxylation of fatty acids reaction.
The nano zircite can be used as catalyst when being used for water gas shift reaction.Reaction condition includes：Temperature 100~
300 DEG C, pressure normal pressure, when the volume space velocity of water-gas is 1000~60000 small-1。
When the nano zircite is used for decarboxylation of fatty acids reaction, catalyst carrier can be used as, load is selected from Pt, Pd and Ru
At least one of active component.Reaction condition includes：100~400 DEG C of temperature, pressure normal pressure, the mass space velocity 0.1 of aliphatic acid
~50 it is small when-1。
The method of the present invention adds aqueous slkali reflux course, that is, uses alkali soluble during prepared by Conventional nano zirconium oxide
Zirconium salt solution is subject to precipitation and forms sediment presoma by liquid, is flowed back in aqueous slkali, has been obtained specific surface area and be up to 152
Centimetre2/ gram tetragonal phase zirconium oxide, achieve preferable technique effect.
Brief description of the drawings
Fig. 1 is【Embodiment 1~4】The XRD diffraction patterns of the nano zircite of preparation.
Fig. 1 shows, according to zirconium oxide XRD standard spectrums, the nano zircite of preparation is tetragonal phase, according to Scherrer formula meter
Obtained zirconium oxide particle diameter is about 4~8 nanometers.
Embodiment
Nano zircite preparation method provided by the invention, comprises the following steps that：
A) zirconates is dissolved in water, is configured to solution, preferably in zirconium nitrate, zirconyl nitrate, zirconium oxychloride and zirconium chloride extremely
Few one kind；
B) aqueous slkali is added under agitation to the pH value specified is reached, and the scope of endpoint pH is 7-12；
C) adjusting ambient degree is to 0~150 DEG C, is allowed plus reflux when being deposited in that reflux 1~60 is small in aqueous slkali, whole
Keep mother liquor pH value constant in a reflux course；
(4) precipitation filtered, washed to free from admixture ion, dry, roasting.Drying temperature is 60~150 DEG C, dry
When time 4~48 is small, calcination temperature is 200~800 DEG C, when roasting time is 1~12 small.
Below by embodiment, the invention will be further elaborated.
【Embodiment 1~4】
Zirconium nitrate, zirconium oxychloride, Nitric Acid Oxidation and zirconium chloride are dissolved in deionized water, are configured to 0.5mol L-1Solution, beat
Stirring is opened, concentrated ammonia liquor (mass fraction 37%) is added dropwise under the mixing speed of 300rpm to pH=9, plus reflux,
100 DEG C of solution temperature value is raised, when reflux 48 is small.By precipitation filtering, wash to free from admixture ion, 120 DEG C dry, at 500 DEG C
Roast 4 it is small when, obtain nano zircite.Its structural characterization is as shown in table 1.
【Embodiment 5~6】
Zirconium oxychloride is dissolved in deionized water, is configured to 0.5mol L-1Solution, open stirring, in the stirring of 300rpm
NaOH (2mol L are added dropwise under speed respectively-1) and KOH (2mol L-1) solution is molten plus reflux, rise to pH=9
100 DEG C of liquid temperature angle value, when reflux 48 is small.By precipitation filtering, wash to free from admixture ion, 120 DEG C dry, and roasting 4 is small at 500 DEG C
When, obtain nano zircite.Its structural characterization is as shown in table 1.
【Embodiment 7~9】
Zirconium oxychloride is dissolved in deionized water, is configured to 0.5mol L-1Solution, open stirring, in the stirring of 300rpm
Concentrated ammonia liquor (mass fraction 37%) is added dropwise under speed respectively to pH=9, plus reflux, rise solution temperature value 100
DEG C, when reflux 48 is small.By precipitation filtering, wash to free from admixture ion, 120 DEG C of drying, respectively at 300 DEG C, 400 DEG C and 600 DEG C
It is lower roasting 4 it is small when, obtain nano zircite.Its structural characterization is as shown in table 1.
【Comparative example 1~2】
Zirconium nitrate is dissolved in deionized water, is configured to 0.5mol L-1Solution, open stirring, 300rpm stirring speed
NaOH (2mol L are added dropwise under degree respectively-1) solution and concentrated ammonia liquor to pH=9, do not flow back.By precipitation filtering, washing to without miscellaneous
Matter ion, 120 DEG C dry, when roasting 4 is small at 500 DEG C.Its structural characterization is as shown in table 1.
Table 1
| Sample | Specific surface area (m2g-1) |
| Embodiment 1 | 124 |
| Embodiment 2 | 145 |
| Embodiment 3 | 137 |
| Embodiment 4 | 152 |
| Embodiment 5 | 124 |
| Embodiment 6 | 112 |
| Embodiment 7 | 105 |
| Embodiment 8 | 135 |
| Embodiment 9 | 122 |
| Comparative example 1 | 78 |
| Comparative example 2 | 62 |
【Embodiment 10】The zirconia catalyst of Au loads
By 2g【Embodiment 2】The Zirconium oxide powder of preparation, adds in urea liquid (0.28M), stirs 1h at room temperature.Then
By HAuCl4Solution (0.024mol L-1) be added dropwise in suspension, the ratio between amount of material of urea and Au is at 100,80 DEG C
Stir 8h.Filter, the precipitation of gained is washed with deionized 6 times, the dry 12h at 100 DEG C, and 300 DEG C of roasting 4h in air, obtain
To the zirconia catalyst of Au loads.
【Embodiment 11】The zirconia catalyst of Pt loads
Weigh 0.5g【Embodiment 2】The Zirconium oxide powder of preparation, adds platinum acid chloride solution 10mL, ultrasonic 0.5h and promotes oxidation
Zirconium it is scattered, then boil off solvent in 60 DEG C of water-baths, 120 DEG C of dry 12h, roast 4h, obtained catalyst for 300 DEG C in air
Presoma uses 5%H in tube furnace2/ Ar is reduced, 300 DEG C, retention time 4h of reduction temperature, and the zirconium oxide for obtaining Pt loads is urged
Agent.
【Comparative example 3】The zirconia catalyst of Au loads
By 2g【Comparative example 2】The Zirconium oxide powder of preparation, adds in urea liquid (0.28M), stirs 1h at room temperature.Then
By HAuCl4Solution (0.024mol L-1) be added dropwise in suspension, the ratio between amount of material of urea and Au is at 100,80 DEG C
Stir 8h.Filter, the precipitation of gained is washed with deionized 6 times, the dry 12h at 100 DEG C, and 300 DEG C of roasting 4h in air, obtain
To the zirconia catalyst of Au loads.
【Comparative example 4】The zirconia catalyst of Pt loads
Weigh 0.5g【Comparative example 2】The Zirconium oxide powder of preparation, adds platinum acid chloride solution 10mL, ultrasonic 0.5h and promotes ZrO2
It is scattered, then boil off solvent in 60 DEG C of water-baths, 120 DEG C of dry 12h, roast 4h under proper temperature, before obtained catalyst
Drive body and 5%H is used in tube furnace2/ Ar is reduced, 300 DEG C, retention time 4h of reduction temperature, obtains the zirconium oxide catalysis of Pt loads
Agent.
Will【Embodiment 10】With【Comparative example 3】Carry out water gas shift reaction.As a result such as table 2.
Reaction condition：Catalyst 0.2g, reacting gas composition is 13%CO, 13% vapor, 74%N2, GHSV=
30000h-1。
Table 2
Will【Embodiment 11】With【Comparative example 4】For laurate decarboxylic reaction, as a result such as table 3.
Reaction condition：It is Ar, catalyst 1g, gas flow rate 50mL min to be passed through gas-1, 300 DEG C of reaction temperature, laurate
WHSV be 0.5min-1。
Table 3
Claims (13)
1. a kind of preparation method of nano zircite, including precursor is obtained with alkali precipitation zirconates, and by the precursor in pH
The step of being worth to flow back under the conditions of 7~12.
2. the preparation method of nano zircite according to claim 1, it is characterised in that reflux temperature is 0~150 DEG C.
3. the preparation method of nano zircite according to claim 2, it is characterised in that reflux temperature is 80~100 DEG C.
4. the preparation method of nano zircite according to claim 1, it is characterised in that when return time is 1~60 small.
5. the preparation method of nano zircite according to claim 4, it is characterised in that when return time is 24~48 small.
6. the preparation method of nano zircite according to claim 1, it is characterised in that the zirconates is the soluble nitre of zirconium
At least one of hydrochlorate, carbonate, villaumite, oxalates, formates, acetate and ammonium salt.
7. the preparation method of nano zircite according to claim 6, it is characterised in that the zirconates is zirconium nitrate, nitric acid
At least one of oxygen zirconium, zirconium oxychloride and zirconium chloride.
8. the preparation method of nano zircite according to claim 1, it is characterised in that the alkali is potassium hydroxide, hydrogen-oxygen
Change at least one of sodium and ammonium hydroxide.
9. nano zircite prepared by the preparation method of any nano zircite of claim 1~8.
10. nano zircite according to claim 9, it is characterised in that the specific surface area of the nano zircite is more than 100
Centimetre2/ gram.
11. nano zircite according to claim 10, it is characterised in that the specific surface area of the nano zircite is 120
~160 centimetres2/ gram.
12. nano zircite according to claim 10, it is characterised in that the crystal form of the nano zircite is Tetragonal.
13. nano zircite prepared by the preparation method of any nano zircite of claim 1~8 in Water gas shift/WGS and
Application in decarboxylation of fatty acids reaction.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107915563A (en) * | 2016-10-10 | 2018-04-17 | 中国石油化工股份有限公司 | The method of decarboxylation of fatty acids |
| CN112429771A (en) * | 2020-11-23 | 2021-03-02 | 山东国瓷功能材料股份有限公司 | Nano zirconium oxide powder, preparation method thereof, dispersion liquid obtained by preparation method and optical film |
| CN115259217A (en) * | 2022-07-26 | 2022-11-01 | 宣城晶瑞新材料有限公司 | Preparation method of metal-doped nano zirconium dioxide |
| CN116023133A (en) * | 2021-10-26 | 2023-04-28 | 国家能源投资集团有限责任公司 | Composite zirconia powder and preparation method thereof |
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| CN105218289A (en) * | 2015-10-15 | 2016-01-06 | 浙江大学 | The method of long chain alkane is prepared in the decarboxylation of a kind of unsaturated fatty acids original position hydrogenation |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107915563A (en) * | 2016-10-10 | 2018-04-17 | 中国石油化工股份有限公司 | The method of decarboxylation of fatty acids |
| CN107915563B (en) * | 2016-10-10 | 2021-12-28 | 中国石油化工股份有限公司 | Method for decarboxylation of fatty acids |
| CN112429771A (en) * | 2020-11-23 | 2021-03-02 | 山东国瓷功能材料股份有限公司 | Nano zirconium oxide powder, preparation method thereof, dispersion liquid obtained by preparation method and optical film |
| CN112429771B (en) * | 2020-11-23 | 2021-06-11 | 山东国瓷功能材料股份有限公司 | Nano zirconium oxide powder, preparation method thereof, dispersion liquid obtained by preparation method and optical film |
| CN116023133A (en) * | 2021-10-26 | 2023-04-28 | 国家能源投资集团有限责任公司 | Composite zirconia powder and preparation method thereof |
| CN116023133B (en) * | 2021-10-26 | 2024-04-05 | 国家能源投资集团有限责任公司 | Composite zirconia powder and preparation method thereof |
| CN115259217A (en) * | 2022-07-26 | 2022-11-01 | 宣城晶瑞新材料有限公司 | Preparation method of metal-doped nano zirconium dioxide |
| CN115259217B (en) * | 2022-07-26 | 2023-12-01 | 宣城晶瑞新材料有限公司 | Preparation method of metal doped nano zirconium dioxide |
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