EP2802535A1 - Plant and method for nanoparticle generation - Google Patents

Plant and method for nanoparticle generation

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Publication number
EP2802535A1
EP2802535A1 EP11810694.7A EP11810694A EP2802535A1 EP 2802535 A1 EP2802535 A1 EP 2802535A1 EP 11810694 A EP11810694 A EP 11810694A EP 2802535 A1 EP2802535 A1 EP 2802535A1
Authority
EP
European Patent Office
Prior art keywords
nanoparticles
solution
production
metallic oxides
oxides according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11810694.7A
Other languages
German (de)
French (fr)
Inventor
Francesco Micali
Ivan LAFUENTI
Valentino BIANCO
Arturo De Risi
Marco MILANESE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TCT Srl
Original Assignee
TCT Srl
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by TCT Srl filed Critical TCT Srl
Publication of EP2802535A1 publication Critical patent/EP2802535A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C01G1/02—Oxides
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • 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
    • 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
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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

Definitions

  • the present invention relates to a machine for generating nanoparticles of various composition, morphology and dimensions.
  • thermo-vector fluids for a long time and with important results there have been used nanodimensioned materials in photocatalysis, photo-conversion, thermo-vector fluids, as molecular markers in biological field and in projecting organic/inorganic nanocomposed systems.
  • inorganic solids In the dimensional order of nanometers, inorganic solids have chemical-physical properties which depend only on the dimensions and the shape of the crystals .
  • the reduced dimensions lead to a variation of the electronic diagram from a band structure, typical of the macroscopic solids, to a system with discrete electronic levels at band edge.
  • the constituent can be, for example, inorganic crystals or super-molecular organic species. In both cases, their nanometric dimension gives the material extremely peculiar and unusual macroscopic properties with respect to the traditional materials ones.
  • stirring reactants made up of water, copper nitrate, acetic acid in a beaker or any other open vessel;
  • EP 1803497 describes a system and a method for generating nanoparticles in water solution (claim 1 ) , optimized for the uniform deposition of the same on a target surface (claims 6 to 8 ) .
  • Aim of the present invention is therefore to provide an apparatus and a method for the production of nanoparticles which overcomes the drawbacks of the methods known at the state of the art .
  • the present invention provides nanoparticles of various precursor materials, as better explained in the following description and in the claims, and of variable dimensions, even lower than 10 nm.
  • the object of the present invention solves the prefixed aims, since it is a plant for the production of nanoparticles, as better described in the following.
  • the reached temperature can vary and reach values greater than 100° by coordinating the working pressure and the temperature suitably so that phenomena of solution boiling are avoided during the reaction at high temperatures;
  • nanocrystals of iron oxide, iron, cerium or other metals in spherical or cylindrical shape and dimensions from few nanometers (5-10 nm) up to some hundreds nanometers.
  • the characterization of the nanoparticles morphology and dimensions occurs by controlling the process conditions, and in particular pressure, temperature and residence time of the solution in the various process steps.
  • the process is practically carried out in the plant for the production of nanoparticles according to the present invention, a scheme of which is shown in figure 7, and comprises a closed reactor (1), configured so that it is supplied by reactants contained in tanks (2, 3) o by means of a metering funnel (11).
  • the tanks (2, 3) and the metering funnel (11) can function at ambient temperature, since the solution in the reactor (1) is at ambient pressure .
  • the tank (2) can contain water
  • the tank (3) contains one of the precursor materials of nanoparticles to be produced, which can be acetic acid which takes part to the generation of spherical nanoparticles with high process yield.
  • the metering unit (11) is used to introduce the precursor reactants in the reactor (1) according to the kind of nanoparticles to be generated.
  • the precursor reactants in the reactor (1) there can be used copper nitrate or copper acetate to obtain nanoparticles of copper oxide CuO, cerium nitrate to obtain nanoparticles of cerium oxide CrC>2 or iron chloride and/or ferrous chloride to generate nanoparticles of iron oxide Fe 2 0 3 .
  • the reactor is further provided with means (12) for stirring the solution contained therein. It is clear that in the reactor (1), it is carried out the step 1 of the previously explained procedure. Out of the tank (1), a suitable thrust means (4) increases the solution pressure in the downstream portion of the plant, up to a controlled value. In the circuit branch downstream of the thrust means
  • reactants (6) preferably comprising sodium hydroxide and/or ammonium hydroxide.
  • These means for adding reactants can comprise another tank (61), possibly provided with means for stirring the content (611) , and thrust means (62) for increasing the pressure of other reactants up to the pressure in the circuit branch (7) in which the other reactant has to be injected.
  • the circuit downstream of the thrust means (4) is configured so that the solution can be re- circulated at controlled speed and pressure.
  • the path followed by the solution goes inside a heat exchanger (51), both before and after the solution is heated (5) and additivated with other reactants by means of elements (6, 611, 62) pre-arranged therefor.
  • a three-way valve (8) Downstream of the second passage in the exchanger (51) is positioned a three-way valve (8) which can be actuated to adjust the flow coming from the branch (81), directing it again upstream (82) of the pumping means (4) or downstream (83) for the final step of the process.
  • the valve (8) can be opened towards the downstream circuit (83) after the solution has circulated a sufficient time to make the desired reaction occur.
  • Downstream of the valve (8) are positioned means (9) for the separation of the water from the nanoparticles and for the washing, drying and storage of the nanoparticles (10) produced.
  • valve (8) allows to deviate the flow of the solution 1 after this one has reached the desired reaction temperature during the heating step through repeated cycles inside the coil provided with heating bands, and has remained at such temperature for a predetermined residence time. It is clear that in the circuit there are arranged means for pressure and temperature control, whose arrangement is immediate for one skilled in the art and therefore they are not shown in the figures.
  • the centrifugation occurs in the vortex (9) in a continuous way in order to separate the nanoparticles from the rest of the liquid solution going out from the synthesis process.
  • the separated nanoparticles are then charged in a tank (101) to be washed with ethanol. After stirring and washing the nanoparticles with ethanol in the tank (101) in the portion of the plant indicated as area 10, the next separation of the nanoparticles from ethanol is provided in the separator (102) .
  • the washed and separated nanoparticles are then charged in the dryer (104) by means of an automated process.
  • the water, contained in the solution where the just generated nanoparticles are dispersed, separated in the separation means (9) can be re-circulated upstream through the duct (91) .
  • the proposed plant is advantageous in that it avoids the use of reactors continuously stirred to make the reaction occur. In this way, since the reagent mass circulating is smaller with equal quantity of product, it is obtained a possibility of a more rapid and exact control of the process conditions .
  • the residence times can vary between few seconds to many hours according to the composition of the nanoparticles produced.
  • the generation of nano-particles of iron oxides and cerium oxides requires residence times at the upper limits of the indicated range.
  • the described plant can be applied for the generation in continuous mode of nanoparticles of metallic oxide in powder or dispersed in solution which can be used in any field of interest, for example the deposition of thin coating layers on surfaces, the dispersion of thermo-vector fluids to increase their thermo-dynamic capacity of heat absorbing and to improve their efficiency in the thermal exchange.
  • thermo-vector fluids can be used in thermo-dynamic solar plants.
  • Other applications relate to electronics, the realization of photoconductive materials, the sensitization, the generations of thermo-electrical materials and super-conductor materials, the implementation of propellants to improve their combustion.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compounds Of Iron (AREA)

Abstract

Method for the production of nanoparticles of metallic oxides comprising the steps of stirring the chemical reactants needed in liquid or solid phase; increasing pressure and temperature of the solution; adding a chemical reactant which favours the formation of nanoplarticles; centrifugation of the solid-liquid bi-phase solution containing the nanoparticles of dispersed metallic oxide; washing, drying and storage of the nanoparticles. Plant for the production of nanoparticles according to the described method.

Description

PLANT AND METHOD FOR NANOPARTICLE GENERATION
The present invention relates to a machine for generating nanoparticles of various composition, morphology and dimensions.
For a long time and with important results there have been used nanodimensioned materials in photocatalysis, photo-conversion, thermo-vector fluids, as molecular markers in biological field and in projecting organic/inorganic nanocomposed systems.
In the dimensional order of nanometers, inorganic solids have chemical-physical properties which depend only on the dimensions and the shape of the crystals .
In particular, while generally reducing the dimensions, an increase in the surface/volume ratio occurs and therefore the efficiency in the thermal exchange increases significantly as well; in the particular case of semiconductor solids, used in micro-electronics, the reduced dimensions (diameter of the particle with the hole-electron gap) lead to a variation of the electronic diagram from a band structure, typical of the macroscopic solids, to a system with discrete electronic levels at band edge. The constituent can be, for example, inorganic crystals or super-molecular organic species. In both cases, their nanometric dimension gives the material extremely peculiar and unusual macroscopic properties with respect to the traditional materials ones.
At the state of the art, there are known lab procedures for the production of nanoparticles. For example, at the state of the art it is known the procedure for the production of CuO particles which is provided with:
stirring reactants made up of water, copper nitrate, acetic acid in a beaker or any other open vessel;
- heating the mixture up to 100°C (water boiling point at ambient pressure) ,
- adding sodium hydroxide,
- stirring and precipitation of CuO nanoparticles. In the table below, there are reported the stoichiometries and the quantities of the reactants tested in lab for a generation of CuO nanocrystals according to the described procedure, yet known at the state of the art. From the data reported in figure 1, there can be observed how the different stoichimoetries tested lead to different results on the reaction yield. In figures 3 and 4 there are shown the distribution diagram of the nanoparticles diameters obtained by means of the adopted method and a TEM imagine of Nanorod of dimensions equal to seven nanometers, obtained as well by means of the method known at the state of the art, yet described.
The lab procedure described to obtain nanoparticles is limited by the small quantities which cannot be produced by a batch type continuous process and by the impossibility to realize the chemical process in high and variable pressure and temperature conditions, since the same process occurs at ambient pressure, and therefore, the maximum reaction temperature depends on the water boiling point and the ambient pressure.
Another example of what is known at the state of the art is the European patent application EP 1803497 which describes a system and a method for generating nanoparticles in water solution (claim 1 ) , optimized for the uniform deposition of the same on a target surface (claims 6 to 8 ) .
What is known at the state of the art is limited, since there are not known plants and procedures optimized for the production, according to a continuous process and in controlled conditions, of nanoparticles generated by various precursor materials, with different dimensions and different morphologies .
Aim of the present invention is therefore to provide an apparatus and a method for the production of nanoparticles which overcomes the drawbacks of the methods known at the state of the art .
According to another aim, the present invention provides nanoparticles of various precursor materials, as better explained in the following description and in the claims, and of variable dimensions, even lower than 10 nm.
The object of the present invention solves the prefixed aims, since it is a plant for the production of nanoparticles, as better described in the following.
Before describing the plant in detail, it is useful to describe the fundamental steps of the process which can be realized therein, whose main steps are the following:
1. stirring the chemical reactants needed in liquid or solid phase at ambient temperature, to obtain a water solution containing the reactants in the desired stoichiometry; 2. increasing the solution pressure;
3. increasing the solution temperature up to reach the desired process temperature in a controlled way. In this step the reached temperature can vary and reach values greater than 100° by coordinating the working pressure and the temperature suitably so that phenomena of solution boiling are avoided during the reaction at high temperatures;
4. adding sodium hydroxide, ammonium hydroxide or any other reagent which favours the formation of nanoparticles, according to the composition of the nanoplarticles to be produced;
5. reaction of the reactant introduced with the previously obtained solution;
6. precipitation of the nanoparticles, preferably by decantation;
7. centrifugation of the bi-phase solution containing the nanoparticles of dispersed metallic oxide;
8. washing, drying and storage of the sample of nanoparticles powder;
9. vaporization of the residual solution and recirculation of the water upstream of the process, for the preparation of step 1 solution. On the understanding that it is possible to use the above described method for the production of nanoparticles from different precursor materials, as a way of example figures 5 and 6 show diagrams of the procedures for the generation of nanoparticles of cerium oxide (Ce02) and iron oxide (Fe304) .
With suitable proportion of reagents and suitable process conditions it is possible to produce in continuous mode and in great quantities, for example, nanocrystals of iron oxide, iron, cerium or other metals, in spherical or cylindrical shape and dimensions from few nanometers (5-10 nm) up to some hundreds nanometers.
The characterization of the nanoparticles morphology and dimensions occurs by controlling the process conditions, and in particular pressure, temperature and residence time of the solution in the various process steps.
The process is practically carried out in the plant for the production of nanoparticles according to the present invention, a scheme of which is shown in figure 7, and comprises a closed reactor (1), configured so that it is supplied by reactants contained in tanks (2, 3) o by means of a metering funnel (11). The tanks (2, 3) and the metering funnel (11) can function at ambient temperature, since the solution in the reactor (1) is at ambient pressure .
As a way of example, the tank (2) can contain water, the tank (3) contains one of the precursor materials of nanoparticles to be produced, which can be acetic acid which takes part to the generation of spherical nanoparticles with high process yield.
The metering unit (11) is used to introduce the precursor reactants in the reactor (1) according to the kind of nanoparticles to be generated. As a way of example, there can be used copper nitrate or copper acetate to obtain nanoparticles of copper oxide CuO, cerium nitrate to obtain nanoparticles of cerium oxide CrC>2 or iron chloride and/or ferrous chloride to generate nanoparticles of iron oxide Fe203.
The reactor is further provided with means (12) for stirring the solution contained therein. It is clear that in the reactor (1), it is carried out the step 1 of the previously explained procedure. Out of the tank (1), a suitable thrust means (4) increases the solution pressure in the downstream portion of the plant, up to a controlled value. In the circuit branch downstream of the thrust means
(4) there are provided means for heating the fluid
(5) to the desired reaction temperature and means for adding further reactants (6) , preferably comprising sodium hydroxide and/or ammonium hydroxide. These means for adding reactants can comprise another tank (61), possibly provided with means for stirring the content (611) , and thrust means (62) for increasing the pressure of other reactants up to the pressure in the circuit branch (7) in which the other reactant has to be injected. The circuit downstream of the thrust means (4) is configured so that the solution can be re- circulated at controlled speed and pressure. The path followed by the solution goes inside a heat exchanger (51), both before and after the solution is heated (5) and additivated with other reactants by means of elements (6, 611, 62) pre-arranged therefor. Downstream of the second passage in the exchanger (51) is positioned a three-way valve (8) which can be actuated to adjust the flow coming from the branch (81), directing it again upstream (82) of the pumping means (4) or downstream (83) for the final step of the process. The valve (8) can be opened towards the downstream circuit (83) after the solution has circulated a sufficient time to make the desired reaction occur. Downstream of the valve (8) are positioned means (9) for the separation of the water from the nanoparticles and for the washing, drying and storage of the nanoparticles (10) produced.
As yet stated the valve (8) allows to deviate the flow of the solution 1 after this one has reached the desired reaction temperature during the heating step through repeated cycles inside the coil provided with heating bands, and has remained at such temperature for a predetermined residence time. It is clear that in the circuit there are arranged means for pressure and temperature control, whose arrangement is immediate for one skilled in the art and therefore they are not shown in the figures.
The centrifugation occurs in the vortex (9) in a continuous way in order to separate the nanoparticles from the rest of the liquid solution going out from the synthesis process. The separated nanoparticles are then charged in a tank (101) to be washed with ethanol. After stirring and washing the nanoparticles with ethanol in the tank (101) in the portion of the plant indicated as area 10, the next separation of the nanoparticles from ethanol is provided in the separator (102) . The washed and separated nanoparticles are then charged in the dryer (104) by means of an automated process.
The water, contained in the solution where the just generated nanoparticles are dispersed, separated in the separation means (9) can be re-circulated upstream through the duct (91) .
It is clear that in the described plant there are provided all the means for controlling the temperature and pressure known at the state of the art, and which one skilled in the art is able to use, once he/she knows the just described plant configuration, to make the same function in the best way.
With respect to what is known at the state of the art, the proposed plant is advantageous in that it avoids the use of reactors continuously stirred to make the reaction occur. In this way, since the reagent mass circulating is smaller with equal quantity of product, it is obtained a possibility of a more rapid and exact control of the process conditions .
By means of the process control thus obtained it is possible to influence the morphology and the dimensions of the nanoparticles produced.
The inventive plant is able to reproduce the synthesis process at temperatures between, as a way of example, T=20° Celsius and T=250°C. The pressure at which the solution is exposed during the reaction, in the circuit branch downstream of the thrust means (4) can vary between P=l bar and P=20 bar while maintaining the temperature of the liquid participating to the reaction at a value lower than the boiling point.
The residence times can vary between few seconds to many hours according to the composition of the nanoparticles produced. For example, the generation of nano-particles of iron oxides and cerium oxides requires residence times at the upper limits of the indicated range.
It is suitable to underline how the temperature at which the reaction occurs influences significantly the dimensions of the nanoparticles generated. The control of such temperature, allowed by the reaction development in a closed plant and controlled pressure conditions, also sensibly greater than the ambient pressure, allows to obtain nanoparticles of dimensions equal to few nm. For example, there have been obtained nanoparticles of copper oxide of dimensions approximately equal to 7 nm, whose production is not possible according to what known at the state of the art, and however not in continuous mode and with project yield.
As a way of example, in a pilot plant realized there have been obtained yields of 450 g/h of nanoparticles of copper oxide, but it is clear, given the kind of the process, that a different dimensioning of the plant allows the production of a very much greater quantity of nanoparticles, and finally, industrially relevant quantities to be produced .
The described plant can be applied for the generation in continuous mode of nanoparticles of metallic oxide in powder or dispersed in solution which can be used in any field of interest, for example the deposition of thin coating layers on surfaces, the dispersion of thermo-vector fluids to increase their thermo-dynamic capacity of heat absorbing and to improve their efficiency in the thermal exchange. As a way of example, such fluids can be used in thermo-dynamic solar plants. Other applications relate to electronics, the realization of photoconductive materials, the sensitization, the generations of thermo-electrical materials and super-conductor materials, the implementation of propellants to improve their combustion.

Claims

1. Method for the production of nanoparticles of metallic oxides, comprising the following steps: a. stirring the chemical reactants needed in liquid or solid phase, to obtain a water solution containing the reactants in the desired stoichiometry;
b. increasing the pressure of the solution obtained at 1;
c. increasing the solution temperature up to reach, in a controlled way, the desired process temperature;
d. adding a chemical reactant which favours the formation of nanoparticles, during the solution heating step;
e. reaction of the reactant introduced in step 4 with the previously obtained solution, for a determined reaction time;
f. precipitation of the nanoparticles, preferably by decantation;
g. centrifugation of the solid-liquid bi-phase solution containing the nanoparticles of dispersed metallic oxide;
h. washing, drying and storage of the nanoparticles .
2. Method for the production of nanoparticles of metallic oxides according to claim 1, further comprising the following step:
i. vaporization of the residual solution and recirculation of the water upstream of the process, for the preparation of step 1 solution.
3. Method for the production of nanoparticles of metallic oxides according to claim 1 or 2, characterized in that the washing of the nanoparticles in step h. is carried out by means of a solvent, and preferably by means of ethanol.
4. Method for the production of nanoparticles of metallic oxides according to any one of claims 1 to
3, characterized in that the reactant used in step d. is sodium hydroxide or ammonium hydroxide.
5. Method for the production of nanoparticles of metallic oxides according to claim 4, characterized in that said particles are particles of copper oxide or iron oxide or cerium oxide.
6. Method for the production of nanoparticles of metallic oxides according to any one of the preceding claims, characterized in that the pressure reached by the solution in step b. of the method is between 1 and 20 bar.
7. Method for the production of nanoparticles of metallic oxides according to any one of the preceding claims, characterized in that the temperature reached by the solution in step 3 of the method is between 20 and 250 °C.
8. Method for the production of nanoparticles of metallic oxides according to any one of the preceding claims, characterized in that the reaction time indicated in step e. is between few seconds and some hours according to the composition of the nanoparticles to be produced.
9. Plant for the continuous production of nanoparticles comprising:
means for stirring the water solution of reactants (1) needed for the formation of the nanoparticles;
- thrust means (4) for increasing the pressure of the solution taken by said stirring means (1); - means for heating (5) and adding other reactants (6) to the solution which is at a pressure higher than the ambient one;
means for re-circulating the solution (8) upstream of said thrust means (4);
means (9, 101, 102, 103, 104) for the precipitation, separation and washing of the nanoparticles .
EP11810694.7A 2011-10-27 2011-10-27 Plant and method for nanoparticle generation Withdrawn EP2802535A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IT2011/000361 WO2013061343A1 (en) 2011-10-27 2011-10-27 Plant and method for nanoparticle generation

Publications (1)

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EP2802535A1 true EP2802535A1 (en) 2014-11-19

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US10626021B2 (en) 2017-03-31 2020-04-21 Honda Motor Co., Ltd. Method of making metal and metal oxide nanoparticles
CN109433215A (en) * 2018-11-26 2019-03-08 新疆大学 One kind is based on heat treatment regulation CuOx-CeO2The method to interact between complex components

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