• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    A core-shell composition for purifying contaminated water and/or biological-medical systems such as tissues, cells or blood. The invention relates to a core-shell composition comprising a core of magnetic nanoparticles and a shell of a double-layered hydroxide compound, and the process for obtaining same. Also, the invention relates to the use of said composition to purify contaminated water, especially useful for the removal of harmful contaminants such as arsenic, to make water suitable for human consumption. In addition, the invention relates to the use of said composition to purify biological-medical systems such as tissues, cells or blood. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2621190A1
    申请号:ES201531323
    申请日:2015-09-18
    公开日:2017-07-03
    发明作者:Lluís BALCELLS ARGEMÍ；Konstantinos Symeonidis；Carlos MARTÍNEZ BOUBETA
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

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    A nucleo-cortex composition to purify contaminated water and / or biological-medical systems such as tissues, cells or blood.
    DESCRIPTION
    The invention relates to a core-shell composition comprising a core of magnetic nanoparticles and a crust of a double laminar hydroxide compound, and its method of obtaining. Also, the invention relates to the use of said composition to purify contaminated water, especially useful for the removal of harmful contaminants such as arsenic, to make the water suitable for human consumption. In addition, the invention relates to the use of said composition to purify biological-medical systems such as tissues, cells or blood.
    STATE OF THE TECHNIQUE
    The presence of arsenic is considered one of the most important contamination problems of drinking water since long-term consumption correlates with the risk of cardiovascular diseases, diabetes, as well as skin, lung, bladder and as a consequence with the increase in mortality. The maximum total arsenic contaminant level was recently set at 10 qg / l in the EU and the US.
    Numerous procedures have been proposed for the efficient removal of heavy metals from water, including chemical precipitation, ion exchange, membrane filtration and electrochemical technologies, and so on. However, adsorption is the most convenient and popular procedure due to its simplicity, high efficiency and low energy requirements. However, common adsorbents often only have low adsorption capacities, slow adsorption rates and limited intervals of conditions under which they can be applied.
    Recently, it has been discovered that nano-sized particles such as iron, iron oxide or magnesium oxide can be used to remove contaminants such as arsenic from water, that is, contaminants will be captured and stabilized in the
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    surface of the nanopartlcuias by means of forces, which include but are not necessarily limited to, van der Waals and electrostatic attraction, thereby removing them from the water. In practice, however, the adoption of nanoparticles in water technology is faced with a number of limitations related to technical, economic and safety issues, by becoming competitive. Above all, the dimensions of the small particles constitute an inconvenience considering the susceptibility of the compositional and structural changes during storage, their degradation or dissolution during the application and elimination and the difficulty in their complete separation and recovery after contact with water. .
    DESCRIPTION OF THE INVENTION
    The present invention discloses a nucleo-cortex composition (also called nucleo-cortex nanohlbrid in this document) comprising a core of magnetic nanoparticles and a very thin crust of a double laminar hydroxide compound (HDL), in which said very thin crust of HDL completely covers said magnetic core.
    This composition (in this document HDL in Fe nanoparticles) can be used to purify contaminated water. The composition is a useful magnetic adsorbent for the removal of harmful contaminants from drinking water, underground water resources, industrial and mining wastewater, secondary waste from the regeneration of other adsorbents. Noxious contaminants are, for example, As (V) and As (III) that appear as negatively or neutrally charged oxy-ions (for example HAsO42 ", H2AsO3") in water. Likewise, the composition of the invention can be used for the purification of biological / medical systems such as tissues, cells or blood.
    During the water treatment, the HDL cortex, which completely covers the nucleus of magnetic nanoparticles, comes directly in contact with the contaminated water providing the maximum adsorption efficiency possible per mass of HDL. The magnetic core is considered completely inert for the adsorption process and is not exposed to any contact with water. This configuration also guarantees a surface area
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    specific specimen for the nano-hybrid as defined by the specific surface of the substrate (the magnetic nanoparticle core) and the porosity of the formed HDL layer itself (HDL cortex).
    The main advantages of the present invention are the following:
    - The core-cortex composition shows a chemical stability for a wide pH range, from 5 to 12.
    - A high efficiency of arsenic removal has been obtained in a variety of water systems such as drinking water, underground water resources, industrial and mining wastewater and secondary waste from the regeneration of other adsorbents.
    - The process of obtaining the core-cortex composition in a multi-phase continuous flow reactor that uses low-cost and environmentally friendly reagents.
    - The composition of the nucleus-cortex (magnetic adsorbent) with the contaminants in the adsorbent can be separated and recovered using an external magnetic field.
    A first aspect of the present invention relates to a core-cortex composition (in this document "composition of the invention") characterized in that it comprises:
    • a nucleus of at least one magnetic nanoparticle;
    • a crust of a double laminar hydroxide compound (HDL) of formula I
    (OH) 3 (CO,) „
    [I]
    wherein M is selected from Mg or Ca; in which x ranges between 0 and 0.3; in which n ranges from 0 to 10; Y
    wherein said cortex completely covers said core and wherein said cortex is between 0.1 nm and 10 nm thick.
    In a preferred embodiment, the magnetic nanoparticle is selected from the list
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    consisting of Fe and its iron alloys, Fe3O4, Y-Fe2O3, CoFe, CoFe2O4, NiFe2O4, MnFe2O4, MgFe2O4 and a combination thereof.
    In another preferred embodiment, the magnetic iron nanoparticle has a size ranging from 3 nm to 100 nm.
    A second aspect of the present invention relates to a process for obtaining the composition of the invention (in this document "process of the invention") characterized in that it comprises at least the following steps:
    a) deposit a double laminar hydroxide of the formula I
    (OH) 3 (CO,) „
    [I]
    wherein M is selected from Mg or Ca; in which x ranges between 0 and 0.3; and in which n ranges from 0 to 10;
    in magnetic nanoparticles; Y
    b) treat the coated particles obtained in step a) at a temperature range of between 20 ° C and 95 ° C for a period of time between 6 h and 36 h.
    In a preferred embodiment, the magnetic nanoparticles of step a) are prepared by precipitation of salts at a pH greater than 10.
    Examples of salts are as follows:
    Bivalent iron salts selected from the list consisting of FeSO4, FeCl2, (NH4) 2Fe (SO4) 2.
    Trivalent iron salts are selected from the list consisting of Fe2 (SO4) 3, FeCl3,
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    Faith (NO3) 3.
    Preferably, the other bivalent metal salts are selected from the list consisting of C0SO4, CoCl2, Co (NO3) 2, NiCl2, NiSO4, Ni (NO3) 2, MgSO4, MgCl2, Mg (NO3) 2, MnSO4, MnClz
    Mn (NO3) 2.
    Preferably, the magnetic nanoparticles of step a) are prepared by precipitating salts at pH ranging from 10 to 13.
    Preferably the pH of step a) is controlled by the addition of one or more of the reagents NaOH, NaHCO3, Na2CO3, KOH, KHCO3, and K2CO3.
    The capacity of reduction or oxidation of the solution obtained in step a) is measured. Preferably the redox potential of the dispersion of magnetic nanoparticles ranges between -1.2 V and -0.5 V during the preparation of magnetic particles.
    In order to control the redox potential in step a), a reducing environment is used, which is selected from hydrazine, NaBH4, NaHSO3, Na2S2O3, Na2S2O4, Na2S2O5, Na2S and a combination thereof, so that the preparation of Magnetic nanoparticles are carried out under this reducing environment.
    Thus, in another preferred embodiment of the process of the present invention step a) is carried out by precipitation of magnesium or calcium salts in the presence of a carbonate reagent of a concentration between 0.01 M and 2 M and under the following conditions:
    • at a pH greater than 8; Y
    • at a temperature range between 50 ° C and 95 ° C.
    Preferably, the magnesium salts are selected from the list consisting of MgSO4, MgCl2 and Mg (NO3) 2.
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    Preferably, the carbonate reagent is selected from the list consisting of Na2CO3, NaHCO3, K2CO3 and KHCO3.
    Preferably, step a) is carried out at a pH ranging from 8 to 13.
    Preferably, the redox potential of step a) ranges from -0.9 V to -0.3 V.
    The formation of the composition of the invention is carried out under less alkaline, strongly oxidative conditions and heating by means of the only precipitation, for example, of Mg2 + and its incorporation / diffusion to the oxidized surface of nanoparticles, for example of Fe3 +. The growth of the HDL crust with these parameters results in a material with a positive surface charge density and anion exchange capacity, properties that increase, for example, the efficiency in arsenic adsorption and retain it at significant levels over a wide pH range. In particular, the development of HDL under such mild alkaline conditions allows at the same time: i) the incorporation of CO32 ions "into the structure that increases the ion exchange capacity; and ii) the conservation of the positive surface charge required for the approach of negatively charged arsenic oxyions.
    A further embodiment of the present invention provides a process of the invention, which is carried out in a continuous flow reactor, in which each stage is carried out in a separate reactor. The nucleo-cortex composition is prepared in different stages under a well regulated condition of pH, redox potentials and temperature capable of being optimized separately in each phase. For example, magnetic nanoparticles are prepared in a first reactor, stage a) in a second reactor and stage b) in a third reactor, each operating under different conditions.
    An important advantage of the synthesis of the nucleo-cortex composition of the invention is the low cost process as defined by the serial and continuous flow operation of the described phases. Compared to the currently available batch processes, the preparation of the composition of the invention combines the possibility of fully controllable and stable reaction conditions in each phase and the production at
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    industrial scale
    A third aspect of the invention relates to the use of the composition of the invention to purify biological-medical systems such as tissues, cells or blood.
    A fourth aspect of the invention relates to the use of the composition of the invention to purify contaminated water.
    Preferably, the composition of the invention is a magnetic adsorbent of a dispersion / separation device for the removal of harmful contaminants from drinking water, underground water resources, industrial and mining wastewater and secondary waste from the regeneration of other adsorbents.
    In the present invention, harmful contaminants are heavy metals such as arsenic, hexavalent chromium, mercury, nickel, lead, antimony, vanadium, cadmium and uranium.
    In a preferred embodiment, the composition of the invention is a magnetic adsorbent for the removal of arsenic from drinking water, underground water resources, industrial and mining wastewater, secondary waste from the regeneration of other adsorbents for a wide range. of working pH, from 5 to 12.
    The last aspect of the invention relates to a process for purifying contaminated water characterized in that it comprises the following steps:
    a) putting the contaminated water in contact with the composition of the invention; Y
    b) separate the insoluble matter from water by applying a magnetic field of 0.03 Teslas and 3 Teslas.
    The magnetism of the magnetic nanoparticles of the nucleus is another important parameter towards the separation of the adsorbent after its application. The stabilization of the magnetic nanoparticles of the nucleus implies a magnetization value above 200
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    emu per gram of core magnetic material that is proportional to the separation produced by an external applied magnetic field. The potential for magnetic separation is increased in the case of these nanoparticles of the core-cortex as a result of the high percentage of the magnetic core compared to the thin layer of HDL. The adsorbent has a relatively high magnetism. The absorbent with absorbed contaminants can be separated and recovered using an external magnetic field procedure, and recovery is easy. Therefore, the absorbent, the process and the application have good industrial application values.
    Another important issue is that the isolated core-cortex magnetic nanoparticles provide the advantage of aggregation induced separation after initial chain formation when the field is applied. This effect introduces the possibility of complete separation under significantly lower intensities of the applied field.
    Unless defined otherwise, all the technical and scientific terms used in this document have the same meaning as commonly understood by someone with basic knowledge of the subject to which the invention belongs. Procedures and materials similar or equivalent to those described herein may be used in the practice of the present invention. Throughout the description and the claims the word "understand" and its variations are not intended to exclude other technical characteristics, additives, components, or stages. Additional objects, advantages and features of the invention will become apparent to those skilled in the art upon examination of the description or can be learned by the practice of the invention. The following examples and drawings are provided by way of illustration and are not intended to be limiting of the present invention.
    BRIEF DESCRIPTION OF THE DRAWINGS
    FIG. 1 Scheme of the growth mechanism of the functional nucleus-cortex composition.
    FIG. 2. Scheme of the procedure for obtaining the core-cortex composition
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    functional.
    FIG. 3. Adsorption isotherms for As (V) and As (III) at pH 10 for HDL in Fe nanoparticles with a diameter of approximately 40 nm and various compositions.
    FIG. 4. Adsorption capacity in 10 pg / l of residual As (V) for various adsorption pH for HDL in optimal Fe nanoparticles compared to common arsenic adsorbents consisting of Fe Hydroxides, magnetite and zero Valencia adsorbents.
    EXAMPLES
    Preparation of the core-cortex composition of the invention
    A nano-hybrid / functional nucleus-cortex composition with an internal magnetic core coated by a Mg (1-X) Fex (OH) 2 (CO3) n, in which 0 <x <0.3, 0 <n has been prepared <10, [see Figure 1]. Its production has been achieved in a three-phase continuous flow reactor after a precipitation route shown in Figure 2. In a first phase of an agitation reactor, magnetic nanoparticles consisting of Fe and iron alloys, Fe3O4, Y-Fe2O3 , CoFe2O4, NiFe2O4, MnFe2O4, or MgFe2O4 are first prepared by precipitating appropriate bivalent or trivalent iron salts (FeSO4, FeCl2, (NH4) 2Fe (SO4) 2, Fe2 (SO4) 3, FeCl3, Fe (NO3) 3 ) or other bivalent metal salts (M2 +: CoSO4, CoCl2, Co (NO3) 2, NiCl2, NiSO4, Ni (NO3) 2, MgSO4, MgCl2, Mg (NO3) 2, MnSO4, MnClz
    Mn (NO3) 2) under strongly alkaline (pH> 10), at a temperature of 20 ° C and under a reducing environment with a redox potential of between -1.2 V and -0.5 V for less than 20 minutes ( one). The dispersion of particles leaving the outflow stream feeds a second agitation reactor where the precipitation of magnesium salts occurs under an alkaline environment (pH> 8), controlled carbonate concentration (0.01-2 M), temperature ( 70 ° C) and redox potential between -0.9 V and -0.3 V for one hour resulting in the coating of the nanoparticles by a magnesium carbonate hydroxide (2). In a third reactor, the suspension produced is matured for several hours (6 h - 36 h) under an elevated temperature (90 ° C) to allow diffusion of the interface between the magnetic phase and the crust to stabilize the Mg- HDL Faith (3). The product is thoroughly washed (4) and dried or else
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    stored in the form of an aqueous dispersion (5).
    Example 1: Fe nanoparticles coated with HDL with x = 0.1
    In the first phase, Fe nanoparticles are prepared in a 0.1 m3 agitation reactor by precipitation of 0.1 M FeSO4, under strongly alkaline conditions (pH = 10), under a reducing environment with a redox potential adjusted to -1.2 V by the continuous addition of hydrazine solution and at a temperature of 20 ° C (1). The retention time in the first reactor is 15 minutes. The dispersion of particles leaving the outflow stream feeds the second agitation reactor (0.4 m3) where the precipitation of 0.02 M MgSO4 occurs under an alkaline environment (pH = 10), controlled carbonate concentration (0, 05 M) by the addition of Na2CO3, temperature (70 ° C) and redox potential of -0.9 V resulting in the coating of the nanoparticles by a magnesium carbonate hydroxide (2). The retention time in the second reactor is 1 hour. In a tank of the third reactor (6 m3), the suspension produced is matured for 20 h under an elevated temperature (90 ° C) and slow agitation to allow the diffusion of the interface between the magnetic phase and the crust to stabilize the HDL of Mg-Fe (3). The product is thoroughly washed (4) and thickened and stored in the form of an aqueous dispersion (5). This procedure results in the formation of Fe nanoparticles coated with HDL with a core diameter of 40 nm, a crust thickness of 5 nm and a crust composition Mg0.9Fe0.1 (OH) 2 (CO3) 2.
    Example 2: Fe nanoparticles coated with HDL with x = 0.3
    In the first phase, Fe nanoparticles are prepared in a 0.1 m3 agitation reactor by precipitation of 0.1 M FeSO4, under strongly alkaline conditions (pH = 10), under a reducing environment with a redox potential adjusted to -1.2 V by the continuous addition of hydrazine solution and at a temperature of 20 ° C (1). The retention time in the first reactor is 15 minutes. The dispersion of particles leaving the outflow stream feeds the second agitation reactor (0.4 m3) where the precipitation of 0.08 M MgSO4 occurs under an alkaline environment (pH = 10), controlled carbonate concentration (0, 05 M) by adding Na2CO3, temperature (70 ° C) and redox potential of -0.9 V giving
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    as a result the coating of the nanoparticles by a magnesium carbonate hydroxide (2). The retention time in the second reactor is 1 hour. In a tank of the third reactor (12 m3), the suspension produced is matured for 30 h under an elevated temperature (90 ° C) and slow agitation to allow diffusion of the interface between the magnetic phase and the crust to stabilize the HDL of Mg-Fe (3). The product is thoroughly washed (4) and thickened and stored in the form of an aqueous dispersion (5). This procedure results in the formation of Fe nanoparticles coated with HDL with a core diameter of 40 nm, a crust thickness of 7 nm and a crust composition Mg0jFe0.3 (OH) 2 (CO3) 4.
    Example 3: FeL3 nanoparticles coated with HDL
    In the first phase, Fe3O4 nanoparticles are prepared in a 0.1 m3 stirring reactor by the coprecipitation of 0.1 M FeSO4 and 0.2 M Fe2 (SO4), under strongly alkaline conditions (pH = 12), under a reducing environment with a self-adjusted redox potential at -0.9 V and at a temperature of 20 ° C (1). The retention time in the first reactor is 15 minutes. The dispersion of particles leaving the outflow stream feeds the second agitation reactor (0.4 m3) where the precipitation of 0.02 M MgSO4 occurs under an alkaline environment (pH = 10), controlled carbonate concentration (0, 05 M) by the addition of Na2CO3, temperature (70 ° C) and redox potential of -0.9 V resulting in the coating of the nanoparticles by a magnesium carbonate hydroxide (2). The retention time in the second reactor is 1 hour. In a tank of the third reactor (8 m3), the suspension produced is matured for 20 h under an elevated temperature (90 ° C) and slow agitation to allow the diffusion of the interface between the magnetic phase and the crust to stabilize the HDL of Mg-Fe (3). The product is thoroughly washed (4) and thickened and stored in the form of an aqueous dispersion (5). This procedure results in the formation of Fe3O4 nanoparticles coated with HDL with a core diameter of 30 nm, a crust thickness of 4 nm and a crust composition Mg0.83Fe0.17 (OH) 2 (CO3) 2.
    Example 4: HDL-coated MnFe2O4 nanoparticles
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    In the first phase, MnFe2O4 nanoparticles are prepared in a 0.1 m3 agitation reactor by coprecipitation of 0.1 M FeSO4 and 0.2 M MnSO4, under strongly alkaline conditions (pH = 12), under a reducing environment with a self-adjusted redox potential at -0.9 V and at a temperature of 20 ° C (1). The retention time in the first reactor is 20 minutes. The dispersion of particles leaving the outflow stream feeds the second agitation reactor (0.3 m3) where the precipitation of 0.02 M MgSO4 occurs under an alkaline environment (pH = 10), controlled carbonate concentration (0, 05 M) by the addition of Na2CO3, temperature (70 ° C) and redox potential of -0.9 V resulting in the coating of the nanoparticles by a magnesium carbonate hydroxide (2). The retention time in the second reactor is 1 hour. In a tank of the third reactor (6 m3), the suspension produced is matured for 20 h under an elevated temperature (90 ° C) and slow agitation to allow the diffusion of the interface between the magnetic phase and the crust to stabilize the HDL of Mg-Fe (3). The product is thoroughly washed (4) and thickened and stored in the form of an aqueous dispersion (5). This procedure results in the formation of HDL coated MnFe2O4 nanoparticles with a core diameter of 20 nm, a crust thickness of 3 nm and a crust composition Mg0.9Fe0.1 (OH) 2 (CO3) 3.
    Evaluation of the core-cortex composition prepared for the removal of As (V) and As (III) from water
    The HDL actuation in Fe nanoparticles obtained to adsorb As (V) and As (III) was evaluated by batch adsorption experiments after dispersing a quantity of nanoparticles in 0.2 m3 of water with an initial arsenic concentration of 5 mg / l. Figure 3 shows the adsorption isotherms for As (V) and As (III) in water of pH 10 for HDL in Fe nanoparticles with a diameter of approximately 40 nm and various HDL compositions with x = 0, 0.1, 0 , 2 and 0.3. The results indicate that the nanoparticles coated by HDL with x = 0.2 are the most efficient being able to remove As (V) and As (III) in almost 100% and reach a residual concentration below the limit of the regulations of drinking water (10 pg / l).
    Comparison of adsorption capacity between the nucleus-cortex composition of the
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    invention and commercial adsorbents
    Figure 4 shows the adsorption capacity in 10 pg / l of residual As (V) for various adsorption pH for HDL in Fe Fe nanoparticles (40 nm, x = 0.2) compared to common arsenic adsorbents consisting of hydroxides of Fe, magnetite and adsorbents of Valencia zero. The HDL in Fe nanoparticles indicates a significant and almost constant adsorption capacity regardless of the pH of the water. Iron hydroxides widely available in the market show greater efficiency in acidic and neutral pH values but become completely inactive under alkaline conditions. Compared to iron and iron oxides, HDL coated nanoparticles indicate better performance at any pH value and are the only effective adsorbent at high pH values.
    Comparison between the nucleus-cortex composition of the invention and a composition of spherical magnetite nanoparticles of an average diameter of 50 nm dispersed within a hydrotalcite of Fe described in "arsenic removal from aqueous solution with Fe- Hydrotalcite supported magnetite nanoparticle" T Turk et al. Journal of Industrial and Engineering Chemistry 20 (2014) 732-738.
    The nucleo-cortex nanoparticles of the invention also show significantly greater efficiency compared to a composition of spherical magnetite nanoparticles of an average diameter of 50 nm dispersed within a Fe hydrotalcite described by T. Turk et al. Journal of Industrial and Engineering Chemistry 20 (2014) 732738. The adsorption capacity given for 10 pg / l of residual arsenic is only 0.04 pg of As / mg. In addition, the pH dependence on efficiency is strong given that it is maximized at pH 9. This difference occurs as a result of the acidity and redox of the preparation as! as the lower specific surface area of the nanoparticles supported by HDL described.
    Application of the nucleus-cortex composition in a continuous flow drinking water treatment system
    A concentrated dispersion of 40 nm Fe nanoparticles coated with HDL with x = 0.2 (0.5 g / l) is continuously added at a rate of 0.1 m3 / h in a 1 m3 agitation tank and enters in contact with contaminated water (50 pg of As / i, pH = 7) that is continuously pumped at a rate of 0.5 m3 / h. The treated water containing the particles charged 5 with As, flows out of the tank and passes through a magnetic separator or a nanofiltration system to completely remove the solid.
    Magnetic separation of the nucleus-cortex composition after being used for purification of contaminated water
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    The magnetic separation system is sequenced in the outflow of the water treatment unit used to treat water contaminated by the nanoparticles of the core-cortex composition. In one case, the magnetic separator consists of a horizontal or vertical tube 1 m long with a diameter of 10 cm. The tube is placed in the magnetic field 15 of between 0.03 and 3 Teslas generated by parallel rectangular permanent magnets consisting of NdFeB. Alternatively, the magnetic field can be generated by an electroiman. The tube may contain a filler material (cables, wool, fiberglass) so that the gradient of the applied magnetic field is increased and aids in the separation of the nanoparticles. The nanoparticles are separated in a proportion 20 of 100% and the treated water without the contaminant leaves the separator.
    权利要求:
    Claims (14)
    [1]
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    1. A core-cortex composition characterized in that it comprises:
    • a core of at least one magnetic nanoparticle;
    • a crust of a double laminar hydroxide compound of formula I
    (OH) 3 (CO,) „
    [I]
    wherein M is selected from Mg or Ca; in which x ranges between 0 and 0.3; in which n ranges from 0 to 10; Y
    wherein said cortex completely covers said core and wherein said cortex is between 0.1 nm and 10 nm thick.
    [2]
    2. The core-cortex composition according to the preceding claim, wherein the magnetic nanoparticle is selected from the list consisting of Fe, Fe3O4, and Fe2O3, CoFe, CoFe2O4, NiFe2O4, MnFe2O4, MgFe2O4 and a combination of the same.
    [3]
    3. The nucleo-cortex composition according to any of claims 1 or 2, wherein the magnetic nanoparticle has a size ranging from 3 nm to 100 nm.
    [4]
    4. A process for obtaining the core-cortex composition according to any one of claims 1 to 3 characterized in that it comprises at least the following steps:
    a) deposit a double laminar hydroxide of the formula I
    O), (CO,) „
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    wherein M is selected from Mg or Ca; in which x ranges between 0 and 0.3; and in which n ranges from 0 to 10;
    in magnetic nanoparticles; Y
    b) treat the coated particles obtained in step a) at a temperature range of between 20 ° C and 95 ° C for a period of time between 6 h and 36 h.
    [5]
    5. The process according to the preceding claim, wherein the magnetic nanoparticles of step a) are prepared by precipitating salts at a pH greater than 10, preferably at a pH ranging from 10 to 13.
    [6]
    6. The process according to the preceding claim, wherein the salts are
    selected from the list consisting of FeSO4, FeCl2, (NH4) 2Fe (SO4) 2, Fe2 (SO4) 3, FeCl3, Fe (NO3) 3, CoSO4, CoCb, Co (NO3) 2, NiCfe, NiSO4, Ni ( NO3) 2, MgCb, Mg (NO3) 2, MnSO4 and
    MnClz Mn (NO3) 2.
    [7]
    7. The process according to any of claims 5 or 6, wherein the redox potential of the dispersion of magnetic nanoparticles ranges between -1.2 V and -0.5 V during the preparation of magnetic particles.
    [8]
    8. The process according to any of claims 5 to 7, wherein the preparation of magnetic nanoparticles is carried out under a reducing environment selected from hydrazine, NaBH4, NaHSO3, Na2S2O3, Na2S2O4, Na2S2O5, Na2S and a combination of the same.
    [9]
    9. The process according to any of claims 4 to 8, wherein step a) is carried out by precipitation of magnesium or calcium salts, preferably selected from the list consisting of MgSO4, MgCl2 and Mg ( NO3) 2, in
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    presence of a carbonate reagent, of a concentration of between 0.01 M and 2 M, preferably the carbonate reagent is selected from the list consisting of Na2CO3, NaHCO3, K2CO3 and KHCO3, and under the following conditions:
    • at a pH greater than 8; preferably at a pH ranging from 8 to 13, and
    • at a temperature range between 50 ° C and 95 ° C.
    [10]
    10. The process according to revindication 9, in which the redox potential of stage a) ranges from -0.9 V to -0.3V.
    [11]
    11. The process according to any of claims 4 to 10, which is carried out in a continuous flow reactor, wherein each stage is carried out in a separate reactor.
    [12]
    12. Use of the composition according to any of claims 1 to 3 to purify biological-medical systems such as tissues, cells or blood.
    [13]
    13. Use of the composition according to any of claims 1 to 3, to purify contaminated water.
    [14]
    14. A process to purify contaminated water characterized in that it comprises the following stages:
    a) bringing the contaminated water into contact with the composition according to claims 1 to 3; Y
    b) separate the insoluble matter from water by applying a magnetic field of 0.03 Teslas and 3 Teslas.
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    ES2621190B1|2018-04-09|
    WO2017046252A1|2017-03-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2010010052A1|2008-07-22|2010-01-28|Akzo Nobel N.V.|Coated particles|
    EP2706040A1|2012-09-07|2014-03-12|Baden-Württemberg Stiftung gGmbH|Particle for recovering an anion from an aqueous solution|
    ES2365082B1|2010-03-08|2012-08-08|Consejo Superior De Investigaciones Científicas |PROCEDURE FOR OBTAINING MATERIALS WITH SUPERPARAMAGNETIC BEHAVIOR|CN108689472B|2017-04-11|2021-11-19|香港大学|Coated nano zero-valent iron material and preparation method and application thereof|
    WO2022014377A1|2020-07-17|2022-01-20|パナソニックＩｐマネジメント株式会社|Catalyst, catalyst for water electrolysis cell, water electrolysis cell, water electrolysis device, and method for producing catalyst|
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