CN103934468B - The supercritical water process for thermosynthesizing of nano metal or metal oxide nano particles - Google Patents
The supercritical water process for thermosynthesizing of nano metal or metal oxide nano particles Download PDFInfo
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- CN103934468B CN103934468B CN201410131897.1A CN201410131897A CN103934468B CN 103934468 B CN103934468 B CN 103934468B CN 201410131897 A CN201410131897 A CN 201410131897A CN 103934468 B CN103934468 B CN 103934468B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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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
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses the supercritical water process for thermosynthesizing of a kind of nano metal or metal oxide nano particles, comprise the steps: soluble metal salt solution to carry out fully mixing the pre-reaction material as supercritical water thermal synthesis with alkali lye (or mixture of alkali lye, reductant solution and organic ligand); Adopt high-pressure pump respectively by this pre-reaction material with after the supercritical water of preheating pressurizes, pump into blender, carry out supercritical water thermal synthesis reaction after being heated up by the mode directly mixed; After reaction certain hour, by the product that obtains after cooling, centrifugal, drying, nano metal or metal oxide nano particles can be obtained.The nano metal that the present invention prepares or metal oxide nano particles have that particle diameter is little, favorable dispersibility, purity advantages of higher.
Description
[technical field]
The present invention relates to a kind of preparation method of nano particle, particularly relate to the supercritical water process for thermosynthesizing of a kind of nano metal or metal oxide nano particles.
[background technology]
Nano metal or metal oxide nano particles are important industrial products, compared with common metal or metal-oxide powder, there is more superior performance, as large specific area, interfacial effect, quantum effect and quantum tunneling effect etc., impart its various special performance being different from traditional material and special electricity, calorifics, magnetics, optics and mechanical property, be widely used in every field, as being used as catalyst, have the features such as particle diameter is little, specific surface large, the activated centre number of particle surface is many, catalytic efficiency is high, by force selective; In sensor, as the coating film of sensor, can greatly improve the selective of sensor and sensitivity; At battery industry, be expected to the negative material for high-performance chemical battery; For the colouring agent, tail gas clean-up material, slider material etc. of glass, pottery.
Traditional nanometer grain preparation method is divided into Physical and the large class of chemical method two.Physical comprises mechanical milling method and physical vaporous deposition, and its shortcoming is complex process equipment, yields poorly, and large-scale production difficulty is larger.Microemulsion method and spray pyrolysis etc. generally all will, through high-temperature heat treatment, cause particle easily to be reunited, and occur particle misgrowth phenomenon.And the hydro-thermal method of routine is longer for reaction time, usually need several hours, even reaction time a couple of days, the problem that unavoidable germination is larger.Chemical electrolysis method is prepared nano-metal particle and is a kind of comparative maturity and industrial process, but the metal dust obtained needs just finally to obtain ultra-fine metallic particles through the technique such as ball milling, sub-sieve more usually, and containing a large amount of metal ions in electrolysis waste solution, any discharge can cause the pollution of the wasting of resources and environment, thus constrains the large-scale application of the method.Liquid phase reduction is the nanometer grain preparation method comparatively enlivened in recent years, but the method need adopt a large amount of organic solvents or the additive component of severe toxicity usually, causes severe contamination aborning, and its application is very limited.Therefore, explore with water is that green, efficiently the nano particle technology of preparing of reaction medium is significant.
Supercritical water (Supercriticalwater is called for short SCW) refers to temperature and pressure all higher than the water of the special state of its critical point (T=374.15 DEG C, P=22.12MPa).Supercritical water has character that is liquid and vaporous water concurrently, and only have a small amount of hydrogen bond to exist in the water under this state, dielectric constant is similar to organic solvent, has high diffusion coefficient and low viscosity.Overcritical hydrothermal synthesis reaction refers in airtight high-pressure reactor, using supercritical water as reaction medium, make that slaine is hydrolyzed in hydro-thermal medium, dehydration, and then nucleation, growth, finally form the reaction with the nanocrystal of certain particle size and crystal habit.In supercritical water, reductive organic matter or hydrogen etc. are nonpolarity gas can formation homogeneous reaction system miscible with supercritical water, realizes metal oxide and efficiently reduces, generate highly purified metal nanoparticle.Because reaction medium is supercritical water, course of reaction is carried out in airtight high-pressure bottle, thus can not introduce other pollutant in course of reaction, is considered to a kind of nano fabrication technique of environmental protection.
[summary of the invention]
The object of this invention is to provide the supercritical water process for thermosynthesizing of a kind of nano metal or metal oxide nano particles, nano metal prepared by the method or nano-metal-oxide composition granule have that particle diameter is little, favorable dispersibility, purity advantages of higher.
For achieving the above object, the present invention is achieved by the following technical solutions:
The supercritical water process for thermosynthesizing of nano metal or metal oxide nano particles, comprises the steps:
1) adopt pure water to dissolve soluble metallic salt, obtain soluble metal salt solution;
2) respectively the mixture of the soluble metal salt solution obtained and alkali lye or alkali lye, reducing agent and organic ligand is forced into supercritical pressure, and at normal temperatures both is carried out premixed, obtain the pre-reaction material for overcritical hydrothermal synthesis reaction;
3) by step 2) pre-reaction material that obtains directly mixes with the supercritical water through preheating, be heated to supercriticality, and enter in supercritical water thermal synthesis reactor and carry out overcritical hydrothermal synthesis reaction, after question response completes, product is cooled, step-down and collection, obtain product sample;
4) the product sample of gained is carried out centrifugation, washing, dry, nano metal or metal oxide nano particles product can be obtained.
The present invention improves further and is: soluble metallic salt is sulfate, nitrate or chlorate.
The present invention improves further and is: when preparing soluble metal salt solution, carry out preheating to improve the solubility of soluble metallic salt to it.
The present invention improves further and is: the addition of the mixture of alkali lye or alkali lye, reducing agent and organic ligand should make pre-reaction material be neutral.
The present invention improves further and is: reducing agent is hydrogen or formic acid, and it is for reducing to the metal ion of high-valence state.
The present invention improves further and is: the carboxyl containing polar functional group in the molecule of organic ligand or amido, and it has heat endurance in supercritical water simultaneously.
The present invention improves further and is: organic ligand is ethylenediamine tetra-acetic acid.
The present invention improves further and is: supercritical water thermal synthesis reactor is batch (-type) supercritical water thermal synthesis reactor or continuous supercritical water thermal synthesis reactor.
The present invention improves further and is: in step 4), after pure water and absolute ethanol washing, at 60 DEG C, carries out vacuum drying again.
Compared with prior art, advantage of the present invention is:
Nano metal prepared by the present invention or metal oxide nano particles have that particle diameter is little, good dispersion and purity high, and the nano metal obtained or nano-metal-oxide can be used for the additive or electrode material etc. of effective catalyst, coloring agent.
[accompanying drawing explanation]
Fig. 1 is the FB(flow block) of the supercritical water process for thermosynthesizing of nano metal of the present invention or metal oxide nano particles.
Fig. 2 is the TEM figure of the nano oxidized copper products of gained in the invention process case 1.
Fig. 3 is the XRD figure of the nano oxidized copper products of gained in the embodiment of the present invention 1.
Fig. 4 is the TEM figure of gained Nanometer Copper product in the embodiment of the present invention 2.
Fig. 5 is the XRD figure of gained Nanometer Copper product in the embodiment of the present invention 2.
[detailed description of the invention]
Below in conjunction with the drawings and specific embodiments, the present invention is described in further details.
See Fig. 1, the supercritical water process for thermosynthesizing of nano metal of the present invention or metal oxide nano particles, comprises the steps:
1) adopting pure water to dissolve soluble metallic salt, obtain soluble metal salt solution, when preparing soluble metal salt solution, preheating can be carried out to improve the solubility of soluble metallic salt to it.
2) respectively the mixture of the soluble metal salt solution obtained and alkali lye or alkali lye, reducing agent and organic ligand is forced into supercritical pressure, and at normal temperatures both is carried out premixed, obtain the pre-reaction material for overcritical hydrothermal synthesis reaction; Wherein, the addition of the mixture of alkali lye or alkali lye, reducing agent and organic ligand should make pre-reaction material be neutral, reducing agent can be hydrogen or formic acid, it is for reducing to the metal ion of high-valence state, carboxyl containing polar functional group in the molecule of organic ligand or amido, it has heat endurance, such as ethylenediamine tetra-acetic acid in supercritical water simultaneously.
3) by step 2) pre-reaction material that obtains directly mixes with the supercritical water through preheating, be heated to supercriticality, and enter in supercritical water thermal synthesis reactor and carry out overcritical hydrothermal synthesis reaction, after question response completes, product is cooled, step-down and collection, obtain product sample; Wherein, supercritical water thermal synthesis reactor is batch (-type) supercritical water thermal synthesis reactor or continuous supercritical water thermal synthesis reactor.
4) the product sample of gained is carried out centrifugation, after pure water and absolute ethanol washing, at 60 DEG C, carry out vacuum drying again, nano metal or metal oxide nano particles product can be obtained.
Wherein, above-mentioned soluble metallic salt is sulfate, nitrate or chlorate.
Embodiment 1:
The present embodiment prepares nano cupric oxide to adopt the thermal synthesis of copper sulphate supercritical water, is described, comprises the following steps the inventive method:
1) by CuSO
45H
2o crystal (Cu (NO
3)
2crystal or CuCl
2crystal) be dissolved in pure water, obtain copper sulphate (copper nitrate or the copper chloride) solution of 0.5mol/L;
2) employing NaOH solution regulates the pH value of copper sulphate (copper nitrate or copper chloride) solution to close to neutral, using the pre-reaction material of the mixture of acquisition as overcritical hydrothermal synthesis reaction;
3) high-pressure pump is adopted respectively by step 2) pre-reaction material that generates directly is mixed into supercritical water thermal synthesis reactor with the pure water being preheated to supercritical temperature, (usually 1min is less than) after a period of time in reaction time, collect the product through cooling, step-down, centrifugal separator is adopted to be separated nano cupric oxide product, again through pure water and absolute ethyl alcohol cyclic washing, at 60 DEG C, carry out vacuum drying again after, nano cupric oxide product can be obtained.
After testing, the granularity of the nano cupric oxide product obtained is 20 ~ 100nm, and particle size usually increases with reactant concentration and increases, and increases with NaOH addition and reduce.
See the TEM figure that Fig. 2 and Fig. 3, Fig. 2 are the nano oxidized copper products of gained in the invention process case 1; Fig. 3 is the XRD figure of the nano oxidized copper products of gained in the embodiment of the present invention 1.As can be seen from Figures 2 and 3, the nano cupric oxide particle adopting supercritical water thermal synthesis technology to prepare is uniform elliposoidal structure; As can be seen from XRD analysis collection of illustrative plates, product is made up of cupric oxide completely, there is not other impurity component.
Embodiment 2:
The present embodiment prepares Nanometer Copper to adopt the thermal synthesis of soluble copper salt supercritical water, is described, comprises the following steps the inventive method:
1) by CuSO
45H
2o crystal (Cu (NO
3)
2crystal or CuCl
2crystal) be dissolved in pure water, obtain copper sulphate (copper nitrate or the copper chloride) solution of 0.5mol/L;
2) copper sulphate (copper nitrate or the copper chloride) solution obtained fully is mixed with the mixture of NaOH solution, formic acid solution and ethylenediamine tetra-acetic acid, as the pre-reaction material of overcritical hydrothermal synthesis reaction;
3) high-pressure pump is adopted respectively by step 2) after the pre-reaction material that generates directly mixes with the pure water being preheated to supercritical temperature, enter supercritical water thermal synthesis reactor, after a period of time in reaction time, collect the product through cooling, step-down, centrifugal separator is adopted to be separated Nanometer Copper product, again through pure water and absolute ethyl alcohol cyclic washing, at 60 DEG C, carry out vacuum drying again after, Nanometer Copper product can be obtained.
After testing, the granularity of the Nanometer Copper product obtained is 15 ~ 80nm, and particle size usually increases with reactant concentration and increases, and increases and reduce with NaOH addition; Products therefrom is highly purified nano copper particle, oxygen-freeization copper or cuprous oxide impurity.
See the TEM figure that Fig. 4 and Fig. 5, Fig. 4 are gained Nanometer Copper products in the embodiment of the present invention 2; Fig. 5 is the XRD figure of gained Nanometer Copper product in the embodiment of the present invention 2.As can be seen from Figure 4 and Figure 5, adopt nano copper particle even particle size distribution prepared by supercritical water thermal synthesis technology, particle dispersion is good.As can be seen from XRD analysis collection of illustrative plates, product is made up of cupric oxide completely, there is not other impurity component; As can be seen from XRD analysis collection of illustrative plates, product is made up of pure Nanometer Copper, very high purity.
Claims (8)
1. the supercritical water process for thermosynthesizing of nano metal or metal oxide nano particles, is characterized in that, comprise the steps:
1) adopt pure water to dissolve soluble metallic salt, obtain soluble metal salt solution;
2) respectively the mixture of the soluble metal salt solution obtained and alkali lye or alkali lye, reducing agent and organic ligand is forced into supercritical pressure, and at normal temperatures both is carried out premixed, obtain the pre-reaction material for overcritical hydrothermal synthesis reaction; Wherein, the addition of the mixture of alkali lye or alkali lye, reducing agent and organic ligand should make pre-reaction material be neutral;
3) by step 2) pre-reaction material that obtains directly mixes with the supercritical water through preheating, be heated to supercriticality, and enter in supercritical water thermal synthesis reactor and carry out overcritical hydrothermal synthesis reaction, after question response completes, product is cooled, step-down and collection, obtain product sample;
4) the product sample of gained is carried out centrifugation, washing, dry, nano metal or metal oxide nano particles product can be obtained.
2. the supercritical water process for thermosynthesizing of nano metal according to claim 1 or metal oxide nano particles, is characterized in that: soluble metallic salt is sulfate, nitrate or chlorate.
3. the supercritical water process for thermosynthesizing of nano metal according to claim 1 or metal oxide nano particles, is characterized in that: when preparing soluble metal salt solution, carry out preheating to improve the solubility of soluble metallic salt to it.
4. the supercritical water process for thermosynthesizing of nano metal according to claim 1 or metal oxide nano particles, is characterized in that: reducing agent is hydrogen or formic acid, and it is for reducing to the metal ion of high-valence state.
5. the supercritical water process for thermosynthesizing of nano metal according to claim 1 or metal oxide nano particles, is characterized in that: the carboxyl containing polar functional group in the molecule of organic ligand or amido, and it has heat endurance in supercritical water simultaneously.
6. the supercritical water process for thermosynthesizing of nano metal according to claim 5 or metal oxide nano particles, is characterized in that: organic ligand is ethylenediamine tetra-acetic acid.
7. the supercritical water process for thermosynthesizing of nano metal according to claim 1 or metal oxide nano particles, is characterized in that: supercritical water thermal synthesis reactor is batch (-type) supercritical water thermal synthesis reactor or continuous supercritical water thermal synthesis reactor.
8. the supercritical water process for thermosynthesizing of nano metal according to claim 1 or metal oxide nano particles, is characterized in that: step 4) in, after pure water and absolute ethanol washing, at 60 DEG C, carry out vacuum drying again.
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| CN201410131897.1A CN103934468B (en) | 2014-04-02 | 2014-04-02 | The supercritical water process for thermosynthesizing of nano metal or metal oxide nano particles |
| PCT/CN2014/090721 WO2015149517A1 (en) | 2014-04-02 | 2014-11-10 | Supercritical hydrothermal synthesis method for metal or metal oxide nanoparticles |
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| CN201410131897.1A CN103934468B (en) | 2014-04-02 | 2014-04-02 | The supercritical water process for thermosynthesizing of nano metal or metal oxide nano particles |
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| CN103934468B true CN103934468B (en) | 2016-03-30 |
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Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103934468B (en) * | 2014-04-02 | 2016-03-30 | 西安交通大学 | The supercritical water process for thermosynthesizing of nano metal or metal oxide nano particles |
| CN104772470B (en) * | 2015-03-26 | 2017-03-01 | 太原理工大学 | The method that xenogenesis nucleus nano metal powder is prepared in closely/supercritical water thermal reduction |
| GB201700262D0 (en) * | 2017-01-06 | 2017-02-22 | Aegis Eng Ltd | Ehanced fabrics |
| CN109628164B (en) * | 2018-11-20 | 2021-01-08 | 太原理工大学 | Supercritical hydrothermal combustion method adopting nano fuel |
| CN109676144B (en) * | 2019-01-31 | 2020-07-28 | 西安交通大学 | Device and method for preparing nano metal powder based on supercritical hydrothermal synthesis technology |
| CN112091230A (en) * | 2019-06-18 | 2020-12-18 | 上海沪正实业有限公司 | Nano copper particles and preparation method thereof |
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| CN112276107B (en) * | 2019-07-25 | 2023-01-06 | 上海沪正实业有限公司 | Nano-copper particles and application thereof in preparation of nano-copper fabric after-finishing agent |
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| CN112337496B (en) * | 2020-11-11 | 2023-03-28 | 深圳大学 | Method for preparing ternary composite photocatalyst by combining supercritical water/supercritical organic matter |
| CN112317759B (en) * | 2020-11-11 | 2021-10-12 | 西南科技大学 | Preparation method of micro-nano silver powder |
| CN112499662A (en) * | 2020-11-13 | 2021-03-16 | 安徽清水湖新材料技术有限公司 | Copper oxide nano material and preparation method thereof |
| CN112475284B (en) * | 2020-11-24 | 2021-10-12 | 西南科技大学 | Surface modification method of micro-nano silver powder for conductive silver paste |
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| CN115536057B (en) * | 2022-10-11 | 2023-11-24 | 广西华锡集团股份有限公司 | Method for preparing nano metal oxide by using near supercritical fluid and production equipment |
| CN115676871B (en) * | 2022-11-04 | 2023-12-05 | 安徽铜冠产业技术研究院有限责任公司 | Preparation process of nanometer copper oxide powder |
| CN115784293A (en) * | 2022-11-18 | 2023-03-14 | 中国计量大学 | Method for preparing rare earth cerium sulfide by supercritical hydrothermal method |
| CN116275085B (en) * | 2023-05-11 | 2023-08-01 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Nano silver and graphene composite material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101612668A (en) * | 2009-07-13 | 2009-12-30 | 中国科学院生态环境研究中心 | The technology of synthesizing nano-silver by supercritical water treated scrap printed circuit board |
| CN103143720A (en) * | 2013-03-12 | 2013-06-12 | 沈阳化工大学 | Preparation method of superfine copper powder |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4399592B2 (en) * | 2004-03-10 | 2010-01-20 | 独立行政法人産業技術総合研究所 | Zirconium oxide crystal particles and production method thereof |
| JP5428016B2 (en) * | 2006-12-28 | 2014-02-26 | 国立大学法人東北大学 | Fine particle production method and fine particles produced by the method |
| JP5142021B2 (en) * | 2007-12-19 | 2013-02-13 | 株式会社リコー | Method and apparatus for producing independent dispersed metal fine particles and independent dispersed metal fine particle dispersion medium, and independently dispersed metal fine particles and independent dispersed metal fine particle dispersion medium |
| JP2010069474A (en) * | 2008-08-22 | 2010-04-02 | National Institute Of Advanced Industrial Science & Technology | Method and apparatus for synthesizing nanoparticle by circulation type supercritical hydrothermal synthesis |
| US8317894B2 (en) * | 2009-04-15 | 2012-11-27 | Korea Institute Of Science And Technology | Method of producing metal nanoparticles continuously and metal nanoparticles produced thereby |
| CN102618926B (en) * | 2011-01-31 | 2015-04-15 | 姜兴茂 | Method for preparing spherical nanomonocrystalline particle |
| CN103058277B (en) * | 2013-02-05 | 2014-10-15 | 山东国瓷功能材料股份有限公司 | Supercritical hydrothermal synthesis method of nanometer zirconium oxide powder |
| CN103949654B (en) * | 2014-04-02 | 2015-12-02 | 西安交通大学 | A kind of supercritical water thermal synthesis preparation system of nano particle |
| CN103934468B (en) * | 2014-04-02 | 2016-03-30 | 西安交通大学 | The supercritical water process for thermosynthesizing of nano metal or metal oxide nano particles |
| CN103935962B (en) * | 2014-04-02 | 2015-08-26 | 西安交通大学 | A kind of supercritical water thermal synthesis preparation system of nano-metal-oxide |
-
2014
- 2014-04-02 CN CN201410131897.1A patent/CN103934468B/en not_active Expired - Fee Related
- 2014-11-10 WO PCT/CN2014/090721 patent/WO2015149517A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101612668A (en) * | 2009-07-13 | 2009-12-30 | 中国科学院生态环境研究中心 | The technology of synthesizing nano-silver by supercritical water treated scrap printed circuit board |
| CN103143720A (en) * | 2013-03-12 | 2013-06-12 | 沈阳化工大学 | Preparation method of superfine copper powder |
Non-Patent Citations (3)
| Title |
|---|
| Hydrothermal synthesis of ZnO nanocrystals using microreactor;Kiwamu Sue等;《Materials Letters》;20040722;第58卷(第25期);第3229-3231页 * |
| Oxidation of Cu(II)-EDTA in supercriticalwater—Experimental results and modeling;Lu Zhou等;《Chemical Engineering Research and Design》;20130228;第91卷(第2期);第286-295页 * |
| 超临界水热合成制备纳米微粒材料;王晓娟等;《化学工业与工程技术》;20070430;第28卷(第2期);第18-20页 * |
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| WO2015149517A1 (en) | 2015-10-08 |
| CN103934468A (en) | 2014-07-23 |
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