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EP3233722A1 - Procédé de préparation de matériaux de type oxyde, de matériaux de type hydroxyde double lamellaire, de matériaux de type hydroxyde et de matériaux à base de carbonate - Google Patents

Procédé de préparation de matériaux de type oxyde, de matériaux de type hydroxyde double lamellaire, de matériaux de type hydroxyde et de matériaux à base de carbonate

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Publication number
EP3233722A1
EP3233722A1 EP15817202.3A EP15817202A EP3233722A1 EP 3233722 A1 EP3233722 A1 EP 3233722A1 EP 15817202 A EP15817202 A EP 15817202A EP 3233722 A1 EP3233722 A1 EP 3233722A1
Authority
EP
European Patent Office
Prior art keywords
materials
metal
alcohol
carbonate
preparation
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.)
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Application number
EP15817202.3A
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German (de)
English (en)
Inventor
Stephan A. Schunk
Carlos LIZANDARA
Cornelia FUTTER
Timo EMMERT
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BASF SE
Original Assignee
BASF SE
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Filing date
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Application filed by BASF SE filed Critical BASF SE
Publication of EP3233722A1 publication Critical patent/EP3233722A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
    • C01B13/326—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process of elements or compounds in the liquid state

Definitions

  • the present invention relates to the synthesis of oxide materials, layered double hydroxide materials (LDH materials), hydroxide materials and carbonate-based materials with high surface area and controlled size.
  • the invention also relates the formation of mixed metal hydroxides and hydroxycarbonates with high surface areas, which can serve as precursor materials to de- liver oxidic materials after thermal treatment.
  • LDH materials are an im- portant subclass of metal hydroxides used in the above mentioned fields. LDHs structures are preferably described with the following formula:
  • M(ll) and M(lll) are divalent and trivalent cations, respectively,
  • A denotes the interlayer anion
  • n denotes the charge of the interlayer anion
  • x and y denote the respective fraction constants.
  • LDHs The structural flexibility of the LDHs, which allows them to incorporate a variety of different metals in the brucite layers and suitable anions in the interlayer has increased the interest in these materials.
  • POMs polyoxometalates
  • further routes reporting the introduction of different interlayer boron-containing anions or metalates of vanadium, niobium, tantalum, molybdenum or tungsten have been described, for example by A. Bhattacharyya et al. in EP 0 536 879 A1 published in 1993 (named AMCO Corporation as assignee).
  • Mg-AI-LDH compounds can range from a few m 2 /g up to over 300 m 2 /g, depending on the preparation method and the constituents of the LDH.
  • the chemical composition of the LDHs does not have a pronounced effect on the obtained specific surface areas (published in Microporous and Mesoporous Materials 67 (2004) p. 1-17).
  • LDHs are usually obtained via the reconstruction method (Journal of Scientific & industrial Research Vol. 68, April 2009, pp. 267-272), which starts with the calcination of metal salts under inert gas atmosphere. Then, the solid is added to a solution containing decarbonated water with a guest molecule, wherein the pH (7-8) is adjusted by NaOH. The precipitate is aged at room temperature, filtered, washed with decarbonated water thoroughly and dried under vacuum.
  • the co-precipitation method may be mentioned, in which process metal salts are brought in contact with aqueous solutions containing bases like sodium hydroxide, sodium carbonate or bicarbonate or mixtures thereof (published in Journal of Scientific & industrial Research Vol. 68, April 2009, pp. 267-272).
  • This method has been widely described in the literature and typically deals with a mixed solution of two different metal salts in water, which is added drop wise over time to an aqueous solution containing guest species, while stirring under inert atmosphere.
  • the pH-value of the solution is adjusted (to pH 7-8) with NaOH to induce co-precipitation.
  • the precipitate is aged, filtered, washed with water thoroughly and dried under vacuum.
  • sol-gel approach Another interesting route for the synthesis of Mg-AI-LDHs with high surface areas is the so- called sol-gel approach.
  • the synthesis procedure is as follows: the desired alcohol is refluxed, and thereafter the trivalent metal M'(OR)3 is added and dissolved into the alcohol; the mixture is stirred for 1 h. Afterwards, a 3 N HN0 3 solution is added dropwise, under vigorous stirring for 1 h, leading to the formation of a transparent solution. The transparent solution is subsequently cooled to room temperature and acetic acid is added under vigorous stirring for 1 h. In the following step, the system is cooled to 0 °C and the divalent metal M(OR)2 is slowly added.
  • the solution is stirred at room temperature for 24 h and then deionized water is slowly added, allowing the hydrolysis to complete itself.
  • the gel is poured into a glass vessel and is aged for 24 h at room temperature.
  • the products are dried overnight at 80 °C (J. Phys. Chem. C, 2007, 1 11 (2), pp 642-651 ) and BET sorption measurements with nitrogen shows that materials with a surface area in the range between 290 and 332 m 2 /g had been obtained.
  • M(0) is reacted with high boiling alcohols under formation of hydrogen to yield M (I I) or/and M(lll) alkoxides and then the metal alkoxides admixture is hydro- lyzed by adding aqueous solutions in order to yield LDHs, mixed hydroxy-carbonates or hydroxides.
  • the surface areas of the LDH materials with small inorganic anions is in the range of 180-190 m 2 /g for LDHs.
  • one of the objectives to be solved by the present invention is to provide a method for preparing a high surface area high purity oxide materials, LDH materials, metal and/or mixed metal hydroxides, metal and mixed metal hydroxycarbonates, which materials have controlled size and shape, which materials can, for example, serve as metal oxide based support materials with improved properties for use as catalysts or other applications.
  • Another objective is to develop a synthesis which is energy efficient and environmentally friendly.
  • a fur- ther objective is to develop a synthesis which leads to the preparation of oxide materials, LDH materials, metal and/or mixed metal hydroxides, metal and mixed metal hydroxycarbonates which show high purity.
  • the synthesis process should be flexible in such a way that it allows for the preparation of a wide range of different oxide materials, LDH materials, metal and/or mixed metal hydroxides, metal and mixed metal hydroxycarbonates.
  • the above mentioned objectives and other objectives are solved by providing a process for the preparation of oxide materials, hydroxides and/or carbonate-based materials, which comprises the hydrolysis and condensation of at least one metal alkoxide in the presence of mono-, di- and/or trivalent alcohol(s) and/or glycol ethers from the group of C6 - C40 alcohol, more prefera- bly C6 - C20 alcohol, even more preferably C6 - C12 alcohol, most preferably C6 alcohol, wherein the at least one metal alkoxide comprises at least one metal cation, preferably a multivalent metal cation, wherein the process is characterized in that: a) a water free solution comprising high-boiling alcohol and at least one metal alkoxide is prepared,
  • step b) the water free solution prepared by step a) is brought into contact with an aqueous liquid and the resulting solution is mixed for a time period, which is > 1 min, preferably, > 10 min, more preferably > 100 min, whereby the water free solution and/or the aqueous liquid comprises as co-solvent methanol and/or ethanol, preferably methanol and whereby the liquid components form a system which is monophasic,
  • step b) the solution of step b) is subjected to i) washing treatment and drying process, ii) washing treatment and re-dispersion or iii) drying process.
  • mixing step b) is performed at a temperature in the range from 0 - 100 °C, more preferably 10 - 80 °C, even more preferably 25 - 80 °C.
  • high-boiling alcohol means mono-, di- and/or trivalent alcohol(s) and/or glycol ethers from the group of C6 - C40 alcohol, more preferably C6 - C20 alcohol, even more preferably C6 - C12 alcohol, most preferably C6 alcohol.
  • the present invention relates to a process for the preparation of LDH materials and/or carbonate-based materials which comprises the hydrolysis and condensation of at least two metal alkoxides in the presence of mono-, di- and/or trivalent alcohol(s) and/or glycol ethers from the group of C6 - C40 alcohol, more preferably C6 - C20 alcohol, even more preferably C6 - C12 alcohol, most preferably C6 alcohol, and the metals of the metal alkoxide comprises a divalent metal cation, trivalent metal cation and/or metal cations of higher valency (i.e. more than trivalent) and whereby the step a) is characterized in that a water free solution comprising high- boiling alcohol and metal alkoxides, which alkoxides comprise at least two different metal species, is prepared.
  • Step c) includes one of the following steps: i) washing treatment and drying process, ii) washing treatment and re-dispersion or iii) drying process.
  • the term "monophasic" is used to describe a homogeneous liquid mixture containing water, high- boiling alcohol and co-solvent which is fully miscible, i.e. no phase separation can be observed.
  • biphasic is used to describe a liquid mixture containing water, high-boiling alcohol and co-solvent which is not miscible and forms two phases.
  • monophasic does not include mixtures which are obtained after the hydrolysis of the alkoxides, i.e. the monophasic mixtures may change into systems which have a second phase due to the change in the overall composition of the mixture and due to the presence solids.
  • water-free solution relates to a solution (before water is added) that comprises not more than 1000 ppm of water, preferably not more than 500 ppm of water, most preferably not more than 100 ppm.
  • the term refers to the molar amount of alcohol which is used for the dissolution of the metal alkoxide.
  • Fig. 1 a shows the XRD pattern which had been obtained for sample S1 by measuring the diffraction data of the powdered sample over the range from 15 to 55 2 ⁇ [°].
  • the stoichiometric composition of sample S1 is Mg 6 Al2(OH)i8 whereby the details of the synthesis of the sample are illustrated in table 1.
  • Fig. 1 b) shows a SEM of sample S1 with a resolution of 75 000 : 1. Larger agglomerations and heavily inter grown material which consists of smaller sub-particles. The sub-particles have a size of less than 50 nm and smaller. Small sub-particles appear to show an isotropic distribution and the structure between the sub-particles appears to be porous.
  • Fig. 1 c shows a SEM of sample S3 with a resolution of 75 000 : 1. Larger agglomerations of thin plate like particles which are inter-grown in a random orientation. The diameter of the plate like particles in the range from 50 - 100 nm and the thickness in the range from 4 to 8 nm. Porous regions between the aggregates.
  • Fig. 1 d shows a TEM of sample S7 with a resolution of 200 000 : 1.
  • Fig. 2 a) shows the XRD pattern which had been obtained for sample 4 by measuring the diffraction data of the powdered sample over the range from 15 to 55 2 ⁇ [°].
  • the stoichiometric composition of sample S1 is Mg 6 Al2(OH) i8 whereby the details of the synthesis of the sample are illustrated in table 1.
  • Fig. 2 b shows a SEM of sample S4 with a resolution of 75 000 : 1.
  • Fig. 3 a shows the XRD pattern which had been obtained for sample S8 by measuring the dif- fraction data of the powdered sample over the range from 15 to 55 2 ⁇ [°].
  • the stoichio metric composition of sample S1 is Mg 6 Al2(OH)i8 whereby the details of the synthesis of the sample are illustrated in table 1.
  • Fig. 3 b shows a SEM of sample 8 with a resolution of 200 000 : 1.
  • Fig.4 shows the XRD's obtained for samples S13, S14, S15 and S16 whereby the graphs are provided in a stacked arrangement. The details of the synthesis of the materials are described in table 1.
  • Fig.5 Thickness of LDHs vs. signal intensity ratio (left axes). LDHs thickness vs. specific surface area of the LDH materials (right axes); in the white box: materials synthesized using co-solvents; in the black box: materials synthesized without the use of co-solvents.
  • Fig. 6 XRD of samples S23 and S24 from table 1 (b: boehmite structure)
  • Fig. 7 shows the ternary phase diagram for a system which is based on water, hexanol and methanol.
  • the black squares indicate that a monophasic system was obtained (i.e. good mixing properties), whereas the unfilled (white) squares indicate the composi- tions, for which a biphasic mixture (i.e. non-mixing) was obtained.
  • Fig. 8 shows the ternary phase diagram for a system which is based on water, hexanol and ethanol.
  • the black squares indicate that a monophasic system was obtained whereas the unfilled (or white) squares indicate that a biphasic mixture was obtained.
  • the process of the invention leads to the formation of a precipitate.
  • re-dispersion may be ac- complishede by de-agglomeration and stabilization of nano-particles, which forming a stable colloidal solution.
  • the solid phase consisting of nano-particles is dispersed in a liquid phase.
  • the procedure which is used for the formation of the stable suspensions and/or colloidal solutions may include operations like dispersing the precipitated products.
  • a re-dispersion of material which had been subjected to a drying process may be carried out.
  • the formation of the dispersions or the re-dispersion may be supported or promoted by the addition of liquid agents or mixtures of liquid agents.
  • Additives such as soluble polymers, salts or surfactants may be added in order to improve the stability of such colloidal solutions. All the above mentioned objectives and many other objectives are achieved by performing the hydrolysis of the alkoxide precursors in the presence of low-boiling alcohols (namely ethanol and/or methanol) which act as co-solvents to allow for solubility of the aqueous compound in the high-boiling alcohol reaction media.
  • organome- tallic precursors and alkoxides helps to induce or promote the formation of oxide materials, LDHs mixed metal-carbonates, hydroxycarbonates and hydroxide materials in such way that an improved control of the properties of the materials is achieved.
  • These properties preferably are surface area, particle size and / or morphology of the resulting materials.
  • materials with increased surface area and well-defined size and shape can be obtained by the process of the present invention.
  • the invention provides a method to tune LDH preparation on the molecular scale and to control the final structure, size and shape and properties of the LDH materials which are prepared according to the process of the invention. Furthermore, this approach for the synthesis of the materials allows to recycle used solvents, with the advantage over process known form the art of having a control over crystallization parameters, by means of controlling the mixing properties that allow the growth of well-defined materials with high surface areas without the need to exchange the anion at fixed x (M(l 1)1 -x M(lll)x (OH) 2 (An-)x/n . yH 2 0) (general formula for LDH materials).
  • the benefits of growing oxides, LDHs, mixed metal-carbonates, hydroxycarbonates and hydroxide materials in a monophasic system is that this allows for better control of the nucleation and growth processes of the particles resulting in better control over the size and shape of the final materials.
  • the hydrolysis and condensation of metal alkoxide precursors in a solution or system of hexanol/methanol/water has been found as to be particularly favorable for the preparation of the oxide materials, LDH materials, mixed metal-car- bonates, hydroxycarbonates and hydroxide materials with sizes below 500 nm, isotropic and nanoplate-like morphology, surface areas >300 m 2 /g and synthetically achievable variety of different compositions.
  • Two different approaches can be used for the preparation of the precursor solutions which contain the organometallic compounds for the synthesis of the oxide materials, LDH materials, mixed metal-carbonates, hydroxycarbonates and hydroxide materials.
  • the metal alkoxide comprises two or more multivalent ions
  • the trivalent metal ion comprises at least one species from the group of Al, Ga, In, Fe, Co, Mn, Cr, La, Pr, Ce, Nd, Sm, Gd, Dy, Ho, Er, Yb, Lu, Sc and/or Y
  • the divalent metal ion comprises at least one spe- cies from the group of Mg, Ca, Sr, Ba, Be, Zn, Cd, Cu, Ni, Co, Mn, Zr and/or Fe and/or metal-ion with a valency higher than trivalent, which comprises at least one species of the group of Zr, Ti, Hf, Cr, Mn, Fe.
  • the system may also comprise alkoxides of monovalent metal-ions of the group Li, Na or K.
  • the synthesis of the alkoxide precursors can be achieved by formation of the alkoxide precursor mixtures and hydrogen, by mixing the metal component(s) as powders, flakes or granulates of the metals with high boiling alcohols (C6-C40) and allowing for reaction at elevated temperatures.
  • the synthesis of the heterometallic alkoxide is implemented via alcohol interchange-reaction by mixing metal alkoxides which contains C1 to C5 group as alkoxide group and with high-boiling alcohols (C6-C40) and/or glycol ethers and allowing for reaction at elevated temperatures and distill off the C1 to C5 alcohols.
  • C6-C40 high-boiling alcohols
  • the synthesis of the of the oxide materials, LDH materials, mixed metal-carbonates, hydroxycarbonates and hydroxide materials the synthesis is based on the use of metal alkoxides (which is termed herein as the "second approach").
  • all synthetic operations are performed under inert atmosphere avoiding the presence of water and oxygen in order to ensure intact precursor materials and to allow for the purity of the oxide, LDH, mixed metal-carbonates, hydroxycarbonates and hydroxide materials precursors.
  • the formation of nanostructured oxide materials, LDH materials, mixed metal-car- bonates, hydroxycarbonates and hydroxide materials can be achieved by hydrolyzing the precursor present in a high-boiling alcohol, in the presence of a hydrolysis solution containing co- solvents.
  • the concentration of reactants and the crystallization temperature are preferably ad- justed in a suitable range before water/co-solvent admixture is added to the solution which is forming the oxide materials, LDH mixed metal-carbonates, hydroxycarbonates and hydroxide materials formation.
  • the organometallic precursor solutions of oxides, LDH mixed metal-carbonates, hydroxycarbonates and hydroxide materials and the H 2 0/co-solvent solution are separately adjusted to be at the respectively required temperature ("tempered"), which is preferably between 0 - 100°C, more preferred 15 - 90 °C, most preferred 25 - 80°C whereby the tempered solutions are stirred for a defined time period prior to mixing, preferably the this time period is > 1 min, more preferably > 10 min, most preferred >1 h.
  • the solutions are kept under inter gas atmosphere.
  • the precursor solutions are mixed under vigorous stirring for a defined time period which is preferably > 1 min, more preferably > 10min, most preferred >100 min. additional stirring is al- lowed in order to ensure the complete hydrolysis of the organometallic LDHs mixed metal-carbonates, hydroxycarbonates and hydroxide materials precursors.
  • washing step After aging the precipitate, the precipitate is filtered off from the mixture and subjected to washing step. Washing of the precipitated can be performed with aqueous or non-aqueous solvents and may involve steps like re-dispersion of the precipitate in the solvent or washing of a filter cake on the filter. Typical washing procedures are known to those who are skilled in the art. Washing can be performed with non-polar, polar aprotic, polar protic solvents and/or mixtures thereof. Examples for washing solvents are acetone, methanol, ethanol or pro- panol and water.
  • the precipitate is dried either using vacuum drying, freeze drying or oven drying.
  • the washing step with water preferably accomplishes two functions.
  • first function in washing the precipitate, undesired compounds are removed from the final product.
  • second function the monophasic solvent system is shifted to a biphasic one, enabling the organic solvent recycling.
  • the process for the preparation of oxide materials, LDH materials and/or carbonate- based materials is characterized in that the metal alkoxide comprises a trivalent metal-ion and a divalent metal-ion, the trivalent metal-ion may be selected from the group of Al, Fe, Co, Mn, La, Ce, Ga and/or Cr, and the divalent metal ion may be selected from the group of Mg, Zr, Zn, Cu, Ni, Co, Mn, Ca and/or Fe.
  • Other metals of other valency may also be used in the preparation procedure. Preferably these other metals are also used in the form of alkoxides.
  • the preparation of the metal alkoxide of high-boiling alcohols is part of the process and that the metal alkoxide of high-boiling alcohols is formed by:
  • the process for the preparation of oxide materials, LDH materials, metal and mixed metal hydroxides, metal and mixed metal hydroxycarbonate materials is characterized in that the resulting solution comprises a molar ratio of water to co-solvent in the range from 0.85 : 0.05 to 0.05 : 0.85, preferably in the range from 0.65 :0.05 to 0.05 : 0.45, and more preferably in the range from 0.45 : 0.45 to 0.25 : 0.45.
  • the process for the preparation of oxide materials, LDH materials, metal and mixed metal hydroxides, metal and mixed metal hydroxycarbonates is characterized in that the liquid containing alcohol and water may comprises dissolvable carbonate salt, preferably ammonium carbonate.
  • the process for the preparation of LDH materials, metal and mixed metal hydroxides, metal and mixed metal hydroxycarbonates is characterized in that the molar ratio of high-boiling alcohol to metal is in the range from 1 : 1 to 40 :1 , preferably from 1.5 : 1 to 20 : 1 , and more preferably in the range from 2 : 1 to 18 : 1 , and whereby the high-boling alcohol preferably comprises mono-, di- and/or trivalent alcohol(s) and/or glycol ethers from the group of C6 - C40 alcohol, more preferably C6 - C20 alcohol, even more preferably C6 - C12 alcohol, most preferably C6 alcohol.
  • the process for the preparation of oxides, LDH materials, metal and mixed metal hydroxides, metal and mixed metal hydroxycarbonates is characterized in that the molar ratio of co-solvent to high-boiling alcohol is in the range from 0.25 : 1 to 10 : 1 , preferably in the range from 0.75 : 1 to 7.5 : 1 , more preferably in the range from 1 : 1 to 5 : 1.
  • the molar ratio of co-solvent to high-boiling alcohol is in the range from 0.25 : 1 to 10 : 1 , preferably in the range from 0.75 : 1 to 7.5 : 1 , more preferably in the range from 1 : 1 to 5 : 1.
  • the stoichiometric specification of the amount of the alcohol content shall not include the amount of alcohol which is bound to the metal within the alkoxide.
  • the metal alkoxides are present in the form of C1 to C5 alkoxides. Possibility to recover liquid components by recycling:
  • the process for the preparation of oxide materials, LDH materials, metal and mixed metal hydroxides, metal and mixed metal hydroxycarbonates is characterized in that the process involves a recycling step by which at least a part of the high-boiling alcohol and/or hydrocarbons is recovered.
  • a recycling step by which at least a part of the high-boiling alcohol and/or hydrocarbons is recovered.
  • the removal of the co-solvent can lead to phase separation between high-boiling alcohol and water which allows the recovery of the high-boiling alcohol.
  • the recovery of hydrocarbons relates to the use of hydrocarbons for washing of the precipitated materials.
  • the process for the preparation of oxide materials, LDH materials, metal and mixed metal hydroxides, metal and mixed metal hydroxycarbonates is characterized in that the drying step (c) comprises a process out of the group of filtration, belt filtration, vacuum filtration, spray drying, oven drying, freeze drying and the temperature of the drying is in the range from -50 to 150 °C, preferably in the range from -50 to 100 °C, and more preferably in the range from -15 to 80 °C.
  • the invention also relates to oxide materials, LDH materials, metal and mixed metal hydroxides, metal and mixed metal hydroxycarbonates which are prepared according to process which had been described within the description and the claims, whereby the materials are characterized as follows: in case that the process is used for the preparation of LDH materials, the LDH materials have a BET-surface area > 250 m 2 /g, preferably > 300 m 2 /g, more preferably > 350 m 2 /g and/or an average particle size in the range from 5 to 120 nm, preferably 10 to 100 nm, more preferably in the range from 20 to 80 nm and having an anisotropy ratio (Dx,y crystal di- rections / Dz crystal direction) between 3 and 25.
  • the LDH materials have a BET-surface area > 250 m 2 /g, preferably > 300 m 2 /g, more preferably > 350 m 2 /g and/or an average particle size in the range from 5 to 120 nm, preferably 10 to 100
  • the oxide hydroxide materials have a BET-surface area which is > 350 m 2 /g, preferably > 400 m 2 /g, more preferably > 450 m 2 /g, and/or whereby the average particle size is in the range from 1 to 50 nm, preferable from 5 to 40 nm.
  • the LDH materials, metal and mixed metal hydroxides, metal and mixed metal hydroxycarbonates materials comprise at least one divalent metal from the group of Mg, Ca, Sr, Ba, Be, Zn, Cd, Cu, Ni, Co, Mn, Zr and/or Fe and at least one trivalent metal from the group of Al, Ga, In, Fe, Co, Mn, Cr, La, Pr, Ce, Nd, Sm, Gd, Dy, Ho, Er, Yb, Lu, Sc and/or Y, preferably the divalent metal comprises Mg and the trivalent metal comprises Al.
  • Another aspect of the present invention relates to the use of oxide materials, LDH materials, metal and mixed metal hydroxides, metal and/or mixed metal hydroxycarbonates which are pre- pared by a process according to the claims and/or description, as carrier for catalysts or as compound for the preparation of catalysts.
  • Glycol ethers are capable to coordinate to the metal center via alcohol oxygen and the ether oxygen. This behavior of glycol ethers inhibites the M-O-M bridging tendency of the alkoxides and allow the solubilisation of the metal alkoxides.
  • the resulting alkoxides of coordianted metals are well soluble in organic solvents.
  • the use of such complexing alcohols like for example glycols or glycol ethers is explicitly included.
  • washing process shall mean an operation performed in order to remove undesired compounds like the remaining high-boiling alcohol in the final product (primary, secondary and/or tertiary C6-C40 alcohols) at the surface of the precipitated particles.
  • the high-boiling alcohol is firstly exchanged by one or more low-boiling solvent.
  • This low-boiling solvent has to accomplish two functions, be soluble in the high boiling alcohol and water. Afterwards, the low-boiling alcohol can be exchanged with water, before to proceed to the drying process.
  • the low-boiling solvents can be such as acetone, methanol, ethanol, n- propanol and/or iso-propanol.
  • drying process within the meaning present disclosure shall be any operation which is performed to remove the rest of the solvent and/or water present in the product of the precipitated particles, after the washing process has been finished.
  • the procedures include explicitly the use of elevated temperatures, reduced pressures, controlled atmosphere (which can be varied) or other means to control the final quality of the dried product.
  • co-solvent shall mean a solvent which allows miscibility between two solvents which are not miscible.
  • examples for co-solvents shall include organic solvents that are not miscible with water: here a co-solvent is used to increase the solubility of the poorly water-soluble organic compound.
  • the role of the co-solvent is to bring an initially biphasic system into a mo- nophasic one.
  • the advantage for the invention is that by use of a co-solvent the solvent system is homogeneous which allows better control of nucleation and particle growth, compared to sys- terns which are is heterogeneous, due to the solid/liquid interphase. In homogeneous solvent systems mass transport during particle growth is facilitated and allows an easier control.
  • co-solvent relates to methanol and/or ethanol, whereby methanol is preferred.
  • the anisotropy ratio is provided as measure to characterize the form of the nanoparticles by giving the deviation from the isotropic form.
  • the isotropic form of a particle is characterized by an anisotropy ratio of [xyz]. In the case of nanoplate like morphology, this is calculated by measuring the length of the crystal along the x,y crystal directions and divided the value by the length of the crystal along the z crystal direction. The length of the nanoparticle along the x,y crystal direction can be extracted from the TEM and/or SEM images.
  • the length of the nanoparticle along the z crystal direction can be extracted from the XRD data, extracting the crystallite size from the [00I] reflexes (in the case of LDH, the [003] and [006] reflexes) using the Debye-Scher- rer formula and/or extracting the length from the SEM and/or TEM images.
  • low -boiling alcohol shall mean any alcoholic compound hav- ing 1 to 5 carbons, generally described as C1 - C5 alcohol, including primary-, secondary-, tertiary-, unsaturated- and cyclic alcohols.
  • high-boiling alcohol refers to any alcohol compound which has 6 to 40 carbons, generally described as C6 - C40 alcohol, including primary-, secondary-, tertiary-, unsaturated- and cyclic alcohols, more preferably C6 - C20 alcohol, even more preferably C6 - C12 alcohol, most preferably C6 alcohol.
  • the process of the present invention may be used in a continuous reaction process, whereby the continuous operation is favorable vis-a-vis discontinuous operation in order to improve the process control with respect to mixing and diffusion.
  • Tailor made materials i.e. oxide materials, LDH materials and/or carbonate-based materials
  • the materials can be used for the production of tailored catalyst supports or catalysts
  • the materials can be employed as drug delivery systems or drug carriers, furthermore the materials have potential as additives or admixtures for drilling liquids which are used for oil and gas recovery (so-called tracking liquids).
  • Further applications are in the field of semiconducting materials, magnetic materials, insulators, fire retardant materials, and/or components for transistors, solar cells, nano-composites and/or hybrid materials.
  • Oven drying had been performed by using an oven from the company Binder (model FD-1 15). All samples were dried at 80 ° C for 24 h. Freeze-drying: For the freeze-drying equipment from the company Christ had been used (the model was an Alpha 1-4). The samples were frozen to - 30 ° C and at -10 0 C and dried at 256 mbar for 24 h.
  • Rotary evaporator As rotary evaporator was used an equipment from the company Heidolph (the model was Laborota 4001). The samples were dried at 80 0 C, 100 mbar and 120 min- 1 for 24 h. Methods as used for the characterization of the materials
  • Figure 7 and Figure 8 show ternary diagrams which give a summary of the liquid samples which were prepared to indicate the phase behavior of hexanol as high boiling alcohol in the presence of water.
  • Examples for liquids were prepared for different molar compositions of hexanol/metha- nol/water and hexanol/ethanol/water respectively. Miscible compositions are represented in black squares and non-miscible compositions are represented in white squares.
  • Table 1 shows a summary of the samples which had been prepared in the present of different solvents and synthesis conditions. All samples had been washed with a mixture of acetone and water with the exception of samples S17, S18, and S19 which had been washed with a mixture of methanol and water. All samples had been dried in a static oven with exception of samples S18 and S19. Sample S18 had been freeze dried and sample 19 had been dried by rotary drier. Sample S20 had been prepared with molar Fe content of 0.25 (instead of Al) and sample S21 had been prepare with a molar Zn 5 content of 0.25 instead of Al.

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Abstract

La présente invention concerne la synthèse de matériaux de type oxyde, de matériaux de type hydroxyde double lamellaire (matériaux LDH), de matériaux de type hydroxyde et de matériaux à base de carbonate ayant une aire spécifique élevée et une taille et forme nanoparticulaire contrôlées ainsi que la formation d'hydroxydes métalliques mixtes et d'hydroxycarbonates ayant des aires spécifiques élevées qui peuvent servir de matériaux précurseurs pour obtenir des matériaux de type oxyde après traitement thermique. Le procédé selon l'invention concerne la préparation de matériaux de type oxyde sur la base d'alcoxydes métalliques qui sont hydrolysés dans des conditions très contrôlées en présence d'un alcool à haut point d'ébullition et à bas point d'ébullition, l'alcool à bas point d'ébullition devant servir de co-solvant.
EP15817202.3A 2014-12-19 2015-12-16 Procédé de préparation de matériaux de type oxyde, de matériaux de type hydroxyde double lamellaire, de matériaux de type hydroxyde et de matériaux à base de carbonate Withdrawn EP3233722A1 (fr)

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EP3371161A1 (fr) 2015-11-04 2018-09-12 Basf Se Procédé pour la préparation d'acide furan-2,5-dicarboxylique
CN108473455A (zh) 2015-11-04 2018-08-31 巴斯夫欧洲公司 用于制备包含5-(羟基甲基)糠醛和特定的hmf酯的混合物的方法
WO2017221451A1 (fr) * 2016-06-24 2017-12-28 日本碍子株式会社 Couche fonctionnelle comprenant un hydroxyde double stratifié, et matériau composite
WO2018029189A1 (fr) 2016-08-08 2018-02-15 Basf Se Catalyseur pour l'oxydation de l'éthylène en oxyde d'éthylène
JP2019536774A (ja) 2016-11-30 2019-12-19 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Ｍｏｒ骨格構造の銅変性ゼオライトを用いて、モノエタノールアミンをエチレンジアミンに変換する方法
CN111686812B (zh) * 2019-03-13 2023-04-07 北京大学深圳研究生院 配体活化的过渡金属层状双羟基化合物、制备方法及用途
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CN111939912B (zh) * 2019-05-15 2023-05-23 国家纳米科学中心 一种钴基催化剂及其制备方法和用途
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