PROCESS FOR THE PREPARATION OF CONTINUOUS PHYLLOMINERAL SYNTHETIC PARTICLES

专利摘要:
The invention relates to a process for the preparation of phyllomineral synthetic particles formed of constituent chemical elements in stoichiometric proportions comprising at least one chemical element selected from the group consisting of silicon and germanium, and at least one chemical element selected from the group consisting of divalent metals and trivalent metals, by continuous solvothermal treatment at a pressure greater than 1 MPa and at a temperature of between 100 ° C. and 600 ° C., by continuously circulating the reaction medium in a solvothermal treatment zone of a continuous reactor (15) with a residence time of the reaction medium in said solvothermal treatment zone adapted to obtain continuously, at the output of said solvothermal treatment zone, a suspension comprising said phyllomineral synthetic particles.
公开号:FR3019813A1
申请号:FR1453334
申请日:2014-04-14
公开日:2015-10-16
发明作者:Cyril Aymonier；Cedric Slostowski；Angela Dumas；Pierre Micoud；Roux Christophe Le；Francois Martin
申请人:Centre National de la Recherche Scientifique CNRS；Universite Paul Sabatier Toulouse III；
IPC主号:

专利说明:

[0001] FIELD OF THE INVENTION The invention relates to a process for the preparation of synthetic phyllomineral particles such as phyllosilicates.
[0002] Many minerals such as borates or silicates are used in various industrial fields. The phyllosilicate mineral particles, such as talc, are for example used in the form of fine particles in many industrial sectors, such as: thermoplastics, elastomers, paper, paint, varnishes, textiles, metallurgy, pharmacy, cosmetics, phytosanitary products or fertilizers in which phyllosilicates such as talc are used, by incorporation into a composition, as an inert filler (for their chemical stability or for the dilution of active compounds of higher cost ) or functional loads (for example to enhance the mechanical properties of some materials).
[0003] Throughout the text, the term "phyllominéral particle" means any mineral particle having a crystalline structure comprising at least one tetrahedral layer and at least one octahedral layer. It can for example be phyllosilicates. Natural talc, which is a hydroxylated magnesium silicate of formula Si4Mg3010 (OH) 2, belongs to the family of phyllosilicates. Phyllosilicates are constituted by a regular stack of elementary sheets of crystalline structure, the number of which varies from a few units to several thousand units. Among the phyllosilicates (lamellar silicates), the group comprising in particular talc, mica and montmorillonite is characterized in that each elemental sheet is constituted by the association of two layers of tetrahedrons located on either side of a layer of octahedra. This group corresponds to phyllosilicates 2: 1, including smectites. In view of their structure, phyllosilicates 2: 1 are also referred to as T.O.T. (Tétraèdreoctaèdre-tetrahedron).
[0004] The octahedral layer of phyllosilicates 2: 1 is formed of two planes of ions O 2 'and OH' (in the molar proportion O 2 '/ OH' of 2/1). On either side of this middle layer come two-dimensional networks of tetrahedra, one of whose vertices is occupied by an oxygen of the octahedral layer, while the other three are by substantially coplanar oxygens.
[0005] For most of their applications, phyllosilicates, and in particular talc, are sought which have a high purity, fine particles (micrometric or even sub-micron in at least one direction), and good structural and crystalline properties. WO2013 / 004979 discloses a process for the preparation of a composition comprising synthetic mineral particles such as talc by a co-precipitation reaction of a precursor hydrogel in the presence of a carboxylate salt followed by a hydrothermal treatment of said precursor hydrogel. a temperature of 300 ° C and an autogenous pressure of the order of 8MPa. A method according to WO2013 / 004979 makes it possible to obtain synthetic mineral particles having satisfactory structural properties, especially close to those of natural talcs. This process also makes it possible to reduce the preparation time of the synthetic mineral particles (from 3 to 10 days) and constitutes the fastest known process for obtaining phyllosilicate particles. A duration of several days and / or an anhydrous heat treatment (annealing) at 550 ° C. for 5 hours is necessary to increase the crystallinity of the synthesized particles so as to approach the structural characteristics of a natural talc. However, it is necessary to improve the compatibility of a method for synthesizing such synthetic inorganic particles with high industrial requirements, in terms of efficiency, cost-effectiveness and structural qualities of the synthetic mineral particles obtained. In this context, the invention aims to provide a method for preparing phyllomineral synthetic particles in larger amounts and / or in shorter times than other methods of the state of the art. The invention also aims at providing a process for the preparation of phyllomineral synthetic particles whose duration is considerably reduced compared with the preparation time required in a process for preparing such particles described in the state of the art. The invention therefore aims to provide such a method whose implementation is simple and fast, and is compatible with the constraints of an industrial scale operation. The aim of the invention is to propose a process for the preparation of phyllomineral synthetic particles of high purity and having a thin particle size and a low dispersion, as well as a crystalline structure very close to that of natural phyllominerals, in particular natural phyllosilicates, and particular of natural talc. The invention also aims at providing a preparation method for precisely adjusting the characteristics of phyllomineral synthetic particles, in particular synthetic phyllosilicate particles obtained.
[0006] The invention also aims at providing a process for preparing compositions comprising phyllomineral synthetic particles having structural properties very close to those of natural phyllosilicates and in particular talc. The invention also aims in particular to provide a method for preparing compositions comprising synthetic phyllosilicate mineral particles that can be used in place of natural talc compositions in various applications. The invention therefore also aims at providing compositions obtained by a process according to the invention. To this end, the invention relates to a method for preparing phyllomineral synthetic particles, formed of chemical elements, said constituent chemical elements, in predetermined proportions, called stoichiometric proportions, said constituent chemical elements comprising at least one chemical element chosen from the a group formed of silicon and germanium, and at least one chemical element selected from the group consisting of divalent metals and trivalent metals, by a treatment, called a solvothermal treatment, of a reaction medium comprising a liquid medium and containing said stoichiometric proportions said constituent chemical elements of said phyllomineral synthetic particles, wherein: said solvothermal treatment is carried out continuously at a pressure greater than 1 MPa and at a temperature of between 100 ° C. and 600 ° C., the reaction medium is circulated continuously in a zone, called zone e of solvothermal treatment, a continuous reactor with a residence time of the reaction medium in said solvothermal treatment zone adapted to obtain continuously, at the output of said solvothermal treatment zone, a suspension comprising said phyllomineral synthetic particles. Indeed, the inventors have surprisingly found that a process according to the invention makes it possible to obtain phyllomineral synthetic particles exhibiting remarkable structural and crystalline properties, and in particular structural properties that can be very close to those of natural phyllosilicates, and especially of a natural talc, continuously and in a surprisingly short duration, from a few seconds to a few minutes, while durations of several hours (typically of the order of 6 hours in W02013 / 004979), or even several days, a priori incompatible with a continuous implementation, were heretofore considered necessary to obtain a sufficient transformation of a reaction medium comprising a liquid medium containing said stoichiometric proportions of said constituent chemical elements of said phyllomineral synthetic particles. It is therefore the first synthesis of such phyllomineral synthetic particles - in particular phyllosilicates - continuously, that is to say lamellar particles comprising at least one tetrahedral layer associated with at least one octahedral layer. This result is all the more surprising since it is a priori necessary to dilute the reaction medium more than in the case of discontinuous processes of the state of the art, this dilution making it possible to facilitate continuous feeding. and the continuous circulation of the reaction medium in the reactor. A process according to the invention also makes it possible to prepare phyllosilicate particles whose properties and characteristics can be finely adjusted, in particular as a function of the duration of the solvothermal treatment (residence time), and with a solvothermal treatment at reduced temperatures, considered until now as insufficient. Throughout the text, the term "continuous reactor", any reactor for working with continuous flows and allowing a mixture of chemical species present in the reaction medium. Any known continuous reactor can be used in a process according to the invention. Thus, advantageously and according to the invention, said continuous reactor is a continuous reactor of constant volume. In a particularly advantageous variant of a process according to the invention, a continuous reactor chosen from the group consisting of piston reactors (or piston-type flow reactors) is used. Such a piston reactor is adapted so that all the chemical species of the reaction medium containing said stoichiometric proportions of said constituent chemical elements of said phyllomineral synthetic particles introduced simultaneously into the solvothermal treatment zone have the same residence time in the solvothermal treatment zone. It may for example be tubular reactors in which the flow of the reaction medium is carried out in a laminar, turbulent or intermediate regime. In addition, it is possible to use any continuous cocurrent or countercurrent reactor with respect to the introduction and bringing into contact of the various compositions and / or liquid media contacted in a process according to the invention. invention. The solvothermal treatment zone of the reactor has at least one inlet adapted to allow the continuous introduction of at least one starting composition into said solvothermal treatment zone of the reactor, and at least one outlet through which said suspension is continuously recovered. comprising said phyllomineral synthetic particles. The reaction medium comprising a liquid medium and said stoichiometric proportions of said constituent chemical elements of said phyllomineral synthetic particles present in the solvothermal treatment zone of the reactor is formed from at least one starting composition and is subjected to said solvothermal treatment, it is that is to say heating under pressure, so as to evolve spontaneously and continuously under the effect of this sole solvothermal treatment, until a suspension of phyllomineral synthetic particles delivered continuously at the outlet of the solvothermal treatment zone of the reactor. Thus, advantageously and according to the invention, the solvothermal treatment zone of the reactor comprises at least one conduit, called a reaction conduit, in which the reaction medium continuously circulates between at least one inlet adapted to allow the continuous introduction of at least one starting composition and at least one outlet through which the suspension comprising said phyllomineral synthetic particles is continuously recovered. Said reaction conduit may for example be in the form of a tube or a pipe whose diameter and shape are adapted to allow the circulation of the reaction medium between at least one inlet and at least one outlet of the treatment zone solvothermal. Advantageously and according to the invention, said solvothermal treatment is carried out by circulating said reaction medium in said reaction conduit, extending between at least one introduction inlet of at least one starting composition and at least one recovery outlet of said suspension of phyllomineral synthetic particles. The residence time of the reaction medium in the said solvothermal treatment zone of the reactor is therefore adjusted as a function of the internal volume of this reaction conduit between the inlet and the outlet, the flow rate and the density of the reaction medium circulating in this reaction conduit. .
[0007] Advantageously and according to the invention, the pressure of the solvothermal treatment is controlled by controlling the pressure prevailing inside said reaction duct, for example by means of a pressure regulator. In particular, the pressure is controlled so that the pressure prevailing inside said reaction duct is greater than the saturation vapor pressure of the liquid medium. Advantageously and according to the invention, the temperature of the solvothermal treatment is controlled by controlling the temperature of the reaction conduit. The temperature can be controlled by any appropriate means, for example by arranging said reaction conduit inside an enclosure in which the temperature is controlled. Other embodiments are possible, for example by providing said reaction conduit with a double jacket and controlling the temperature of the jacket. The temperature of the reaction medium in the reactor is adapted to allow said phyllomineral synthetic particles to be obtained, depending in particular on the pressure and the residence time during which the solvothermal treatment is carried out. In particular, advantageously and according to the invention, said solvothermal treatment is carried out at a temperature of between 200 ° C. and 600 ° C., in particular between 250 ° C. and 450 ° C., and in particular between 350 ° C. and 400 ° C. . For example, advantageously and according to the invention, the reaction conduit extends inside an enclosure, and the temperature inside the enclosure is controlled at a value between 100 ° C. and 600 ° C. , especially between 200 ° C and 500 ° C, and more particularly between 350 ° C and 400 ° C. Advantageously and according to the invention, the temperature and the pressure of the solvothermal treatment are controlled by controlling the temperature of the reaction conduit and, respectively, the pressure prevailing inside said reaction conduit. Advantageously and according to the invention, the characteristics and the amount of liquid medium in the reaction medium are adapted to allow a continuous introduction of at least one starting composition into the solvothermal treatment zone of the reactor -particularly in the reaction conduit. and continuously circulating the reaction medium in the solvothermal treatment zone of the reactor -particularly in the reaction conduit-to an outlet thereof. In particular, advantageously and according to the invention, the reaction medium has a suitable viscosity (by a suitable choice of the liquid medium and / or adjustment of the quantity of liquid medium) so as to allow it to flow continuously at the inlet of the liquid medium. the solvothermal treatment zone of the reactor, in particular at the inlet of the reaction conduit, and the continuous circulation of the resulting reaction medium in the reactor, in particular in the reaction conduit. In addition, the viscosity of the reaction medium is also chosen so as to obtain a suspension of phyllominéral synthetic particles at the outlet of the reactor that may flow from this outlet, at least in view of the supply pressure. The reaction medium may be formed from one or more starting composition (s). Advantageously and according to the invention, each starting composition comprises a liquid medium and at least a part of said stoichiometric proportions of said constituent chemical elements of said phyllomineral synthetic particles. Each starting composition is chosen such that all of said starting compositions comprise said stoichiometric proportions of said constituent chemical elements of said phyllomineral synthetic particles. If the reaction medium is formed from a single starting composition, it must then comprise all the constituent chemical elements in stoichiometric proportions of said constituent chemical elements of said phyllomineral synthetic particles, that is to say the stoichiometric proportions of at least one chemical element selected from the group consisting of silicon and germanium, and at least one chemical element selected from the group of divalent and trivalent metals.
[0008] In a particularly advantageous variant of a process according to the invention, the reaction medium is prepared continuously from at least a first starting composition comprising at least one mineral compound chosen from silicates and / or germanates, their solutions solids and mixtures thereof, and at least a second starting composition comprising at least one metal salt of at least one metal M (in particular a divalent or trivalent metal), said first and second compositions being brought into continuous contact with each other. upstream of at least one input of said solvothermal treatment zone. It is thus possible to prepare two starting compositions, one comprising at least one compound, said mineral compound, chosen from silicates and / or germanates, their solid solutions and their mixtures and the other comprising at least one metal salt of at least one metal M, or more than two starting compositions, each starting composition comprising at least one mineral compound chosen from silicates and / or germanates, their solid solutions and mixtures thereof and / or at least one metal salt of at least one At least one metal M. In fact, the inventors have surprisingly found that it is possible to prepare the reaction medium continuously, from several different starting compositions each containing at least a part of the constituent chemical elements necessary. to the synthesis of phyllomineral particles whereas such a continuous implementation requires a priori significant dilutions. This dilution before and in the solvothermal treatment zone is generally presumed to interfere with obtaining such phyllomineral particles. Indeed, in the starting reaction medium, the constituent chemical elements which, separately from each other, could not allow the formation of phyllomineral particles and would tend to form particles of a different structural and / or chemical nature, in fact allow such that they are brought into contact in a process according to the invention, obtaining phyllominéral synthetic particles, even in diluted medium. Advantageously and according to the invention, in each starting composition, the concentration (relative to the volume of the liquid medium) of said constituent chemical elements of said phyllomineral synthetic particles introduced at the inlet of the solvothermal treatment zone of the reactor may in particular be between 10 -3 mol / L and several mol / L, for example 10-2 mol / L or 1 mol / L. Advantageously and according to the invention, the reaction medium and each starting composition are at least partially hydrated (the solvothermal treatment of this reaction medium is then called hydrothermal treatment). Advantageously and according to the invention, said liquid medium is chosen from water, alcohols and mixtures thereof. In an advantageous variant of a process according to the invention, said alcohols are chosen from linear or branched alcohols comprising less than 10 carbon atoms, in particular comprising less than 7 carbon atoms, in particular from methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, propylene glycol and ethylene glycol. The liquid medium of the starting composition and the liquid medium of the reaction medium may for example be prepared solely with water or with a mixture of water and at least one alcohol. The solvothermal treatment of the reaction medium 5 is carried out in the solvothermal treatment zone of the reactor at a pressure that is suitable for obtaining said phyllomineral synthetic particles, particularly as a function of the temperature and the residence time during which the solvothermal treatment is carried out. Advantageously and according to the invention, said solvothermal treatment is carried out at a pressure of between 2 MPa and 50 MPa, in particular between 8 MPa and 40 MPa, and in particular between 22 MPa and 30 MPa. Here again, advantageously and according to the invention, this pressure of the solvothermal treatment is controlled by adjusting the pressure inside the reaction conduit in which the reaction medium circulates. Advantageously and according to the invention, the pressure of the solvothermal treatment is controlled by a pressure regulator. Advantageously and according to the invention, the reaction conduit is prolonged after leaving the reactor (that is to say from a zone in which the reaction conduit is maintained at a temperature corresponding to the temperature of the solvothermal reaction). a portion provided with a device for regulating the pressure (such as for example a micrometer or needle valve or an automatic pressure regulator) to a value, called nominal pressure, at which the solvothermal treatment must be carried out. The reaction medium is introduced into the reaction conduit with a predetermined flow rate as a function of the residence time, for example using at least one flow pump (volumetric pump). This device makes it possible to control the pressure within the assembly 25 of the continuous synthesis device and in particular within the reactor. It also makes it possible to ensure a transition between the pressure in the reactor and the ambient pressure at the outlet of the continuous synthesis device, when the phyllomineral synthetic particles are recovered in suspension or after possible filtration. Advantageously and according to the invention, the duration of the solvothermal treatment is continuously adjusted by controlling the residence time of the reaction medium in the said solvothermal treatment zone, in which it is subjected to the temperature and the pressure of the solvothermal treatment. The residence time of the reaction medium in the solvothermal treatment zone of the reactor is adapted to allow the continuous production of said phyllomineral synthetic particles, depending in particular on the temperature at which the solvothermal treatment is carried out. Advantageously and according to the invention, the reaction medium is circulated continuously in the solvothermal treatment zone of the reactor so that it has a residence time in the solvothermal treatment zone of less than 10 minutes, in particular less than 5 minutes. minutes, and more particularly less than 1 minute. In the embodiments in which the said solvothermal treatment zone is a reaction conduit, the residence time of the reaction medium is determined from the volume of the reaction conduit (between the inlet and the outlet of this reaction conduit) in which the reaction medium, the flow rate imposed in the reaction conduit and the density of the reaction medium (the latter being dependent on the temperature and the pressure of the solvothermal treatment). The relationship between the volume flow rate (Q) and the residence time (ts), the reactor volume (V,), the density (μl) of the reaction medium at the reactor inlet, and the density (mp) ) of the reaction medium in the reactor is as follows: Advantageously and according to the invention, said reaction medium is introduced into the reactor -particularly into said reaction conduit-with a flow rate chosen to obtain the appropriate residence time. Advantageously and according to the invention, said solvothermal treatment is carried out under supercritical or subcritical conditions, and in particular homogeneous subcritical conditions. In a particularly advantageous variant of a process according to the invention, the temperature and the pressure at which the solvothermal treatment is carried out are chosen so that the reaction medium, and in particular the liquid medium which it comprises, is supercritical conditions. Advantageously and according to the invention, said solvothermal treatment is thus carried out under conditions of temperature and pressure such that the reaction medium, in particular its liquid medium, is in supercritical conditions. In the presence of an essentially or solely aqueous reaction medium, the critical point of the water (according to the phase diagram of the water) being located at 22.1 MPa and at 374 ° C., for example a hydrothermal treatment is carried out in the reactor at a temperature greater than 375 ° C and a pressure greater than 22.3MPa, so as to be in supercritical conditions. To perform a hydrothermal treatment under subcritical conditions, it is placed at a temperature between 100 ° C and 373 ° C and at a pressure above the saturated vapor pressure of the liquid medium at the chosen temperature (above of the liquid-gas equilibrium curve of the phase diagram of the water), in particular at a pressure greater than 0.1 MPa. The invention applies to the preparation of all phyllomineral particles obtainable by solvothermal treatment (heating and pressure) of a precursor gel comprising said stoichiometric proportions of said constituent chemical elements of said phyllomineral synthetic particles, the transformation of this precursor gel producing said phyllomineral particles at the end of the solvothermal treatment. The invention relates more particularly and advantageously to a process for preparing phyllosilicate particles belonging to the group consisting of lamellar silicates, lamellar germanates, lamellar germanosilicates and mixtures thereof. Advantageously and according to the invention, a precursor silico / germano-metallic hydrogel precursor is then used, and said solvothermal treatment is carried out in the form of a continuous hydrothermal treatment of this silico / germano-metallic hydrogel. precursor. Advantageously and according to the invention, said precursor gel is prepared by a co-precipitation reaction between at least one mineral compound, chosen from silicates, germanates, their solid solutions and mixtures thereof, and at least one metal salt of from minus a metal M (in particular a divalent or trivalent metal).
[0009] Advantageously and according to the invention, any compound comprising at least one silicon and / or germanium atom adapted to react in said co-precipitation reaction of said precursor gel is used as the inorganic compound. In particular, advantageously and according to the invention, said mineral compound is chosen from the group consisting of sodium silicates and silicas (silicon dioxides). In particular, advantageously and according to the invention, sodium metasilicate is used as the mineral compound. In a particularly advantageous variant of a process according to the invention, at least one dicarboxylate salt of formula M (R 1-000) 2 is used as metal salt of at least one metal M in which: R 1 is chosen from hydrogen (-H) and alkyl groups containing less than 5 carbon atoms and, - M denotes at least one divalent metal having the formula Mgy (/) Coy (2) Zny (3) Cuy (4) Mny (5) Fey (6) Niy (7) Cry (8); each y (i) representing a real number of the interval [0; 1], and such that Iy (i) = 1. Advantageously and according to the invention, said co-precipitation reaction is carried out in the presence of at least one carboxylate salt of formula R2-COOM 'in which: M' denotes a metal chosen from the group consisting of Na and K, and - R2 is chosen from H and the alkyl groups comprising less than 5 carbon atoms. It is surprisingly found that this carboxylate salt is not degraded by the solvothermal treatment, and on the contrary participates in the efficiency and speed of the latter. The groups R1 and R2 may be the same or different. Advantageously and according to the invention, the groups R 1 and R 2 are chosen from the group consisting of CH 3 -, CH 3 -CH 2 - and CH 3 -CH 2 -CH 2 -. In particular, advantageously and according to the invention, the groups R 1 and R 2 are identical. Advantageously and according to the invention, a precursor gel is used, as precursor gel, comprising: - 4 silicon and / or germanium atoms according to the following chemical formula: 4 (SixGei_x), x being a real number of the interval [0; 1], - 3 atoms of at least one metal M, M denoting at least one divalent metal having the formula Mgy (/) Coy (2) Zny (3) Cuy (4) Mny (5) Fey (6) Niy ( 7) Cry (8) wherein each y (i) represents a real number of the interval [0; 1], and such that 8 1 y (i) = 1, i = 1 - (10-E) oxygen atoms ((10-E) O), E being a real number of the interval [0; 10r, - (2 + E) hydroxyl groups ((2 + E) (OH)), where E is a real number of the interval [0; 10 [.
[0010] It is therefore possible to use as chemical formula for such a precursor hydrogel the following chemical formula (I): ## STR2 ## . Water molecules can be further bound to the particles of this precursor hydrogel. They are water molecules adsorbed or physisorbed to the precursor hydrogel particles and not water molecules of constitution usually present in the interfoliar spaces of certain phyllosilicate particles. Another chemical formula for defining said precursor hydrogel is the following formula: (SixGei-x) 4M3011, nH2O, or also Si4M3O11, nH2O with respect to a silico-metallic precursor hydrogel. Such a silico / germano-metallic precursor hydrogel can be obtained by a co-precipitation reaction between at least one mineral compound, chosen from silicates, germanates, their solid solutions and their mixtures, and at least one metal salt of from less a divalent metal M.
[0011] Advantageously and according to the invention, said solvothermal treatment is carried out, in particular a hydrothermal treatment, so as to obtain continuously (after leaving the reactor) a suspension comprising particles of 2: 1 phyllosilicates type. In particular, advantageously and according to the invention, said hydrothermal treatment is carried out so as to obtain continuously a suspension comprising phyllosilicate particles having the following chemical formula (II): (Si, Gei_x) 41 43010 (01-1) 2 (II) wherein: - Si denotes silicon, - Ge denotes germanium, - M denotes at least one divalent metal having the formula Mgy (/) Coy (2) Zny (3) Cuy (4) Mny (5) Fey (6) Niy (7) Cry (8); each y (i) representing a real number of the interval [0; 1], and such that ly (i) = 1, i = 1 - x is a real number of the interval [0; 1]. In other variants of a process according to the invention, it is possible to use precursor gels comprising chemical elements in different proportions corresponding to the synthesis of other types of phyllominerals, for example phyllosilicates whose structure is of the TO type ( tetrahedron-octahedron) or TOTO type (tetrahedron-octahedron-tetrahedroctahedron), by analogy with 2: 1 phyllosilicates of the TOT type A precursor gel making it possible to prepare phyllomineral synthetic particles of the TO type comprises, for example: 2 atoms of silicon and / or germanium according to the following chemical formula: 2 (SixGei_x), x being a real number of the interval [0; 1], - 3 atoms of at least one metal M, M denoting at least one divalent metal having the formula Mgy (/) Coy (2) Zny (3) Cuy (4) Mny (5) Fey (6) Niy ( 7) Cry (8) wherein each y (i) represents a real number of the interval [0; 1], and such that 8 1 y (i) = 1, i = 1 - (5-E) oxygen atoms ((5-E) O), E being a real number of the interval [0; 5r, - (4 + E) hydroxyl groups ((4 + E) (OH)), E being a real number of the interval [0; 5 [.
[0012] In these precursor gels, the metal M may also designate a trivalent metal such as aluminum (Al) partially or totally substituted for said divalent metal. A precursor gel making it possible to prepare phyllomeric synthetic particles of T.O. or T.O.T. type. then will comprise 2 atoms of said trivalent metal (instead of 3 atoms of said divalent metal in order to respect the electrical neutrality). Advantageously, in certain embodiments, and according to the invention, the precursor gel is continuously prepared immediately upstream of its introduction into the solvothermal treatment zone. Thus, a process according to the invention makes it possible to carry out, in a single step, continuously, on the one hand, the preparation of the precursor gel, and, on the other hand, the solvothermal treatment of the reaction medium making it possible to continuously obtain a suspension of synthetic particles. phyllominérales. More particularly, advantageously and according to the invention, the reaction medium, and in particular the precursor gel, is prepared continuously, in particular by a co-precipitation reaction, starting from at least a first starting composition comprising at least a compound, said mineral compound, chosen from silicates and / or germanates, their solid solutions and their mixtures, and at least a second starting composition comprising at least one metal salt of at least one metal M chosen in the divalent metal and trivalent metal group, said first and second compositions being contacted continuously upstream of at least one inlet of said solvothermal treatment zone. To do this, advantageously and according to the invention, at least a first starting composition of each mineral compound is introduced continuously into at least a first portion of the conduit; and continuously introducing at least a second starting composition of each metal salt into at least a second conduit portion, each of the first conduit portion and the second conduit portion being connected to each other upstream of the solvothermal treatment zone to allow the continuous contacting of these two compositions, so as to form said precursor gel continuously upstream of an inlet of said reaction conduit. Thus, the reactor comprises, upstream of the inlet of the reaction conduit, a first portion of conduit in which a first starting composition comprising each mineral compound is introduced continuously, and a second portion of conduit in which is introduced in Continuously a second starting composition comprising each metal salt. Advantageously and according to the invention, the first starting composition is at least partially hydrated. Advantageously and according to the invention, the second starting composition is at least partially hydrated. Advantageously and according to the invention, the first starting composition 15 is capable of flowing. Advantageously and according to the invention, the second starting composition is capable of flowing. Advantageously and according to the invention, said first starting composition and said second starting composition are liquid compositions fed continuously under liquid pressure, the liquid phase of each of these compositions being adapted so that their mixture forms said liquid medium of reaction medium. Preferably, advantageously and according to the invention, the first starting composition and the second starting composition are both solutions formed in said liquid medium. Advantageously and according to the invention, the first portion of the conduit and the second portion of the conduit meet upstream of the inlet of the solvothermal treatment zone -particularly upstream of the inlet of the reaction conduit. in a third conduit portion connecting each of the first and second conduit portions and the inlet of the solvothermal treatment zone, the precursor gel forming (by co-precipitation) continuously in said third conduit portion. Advantageously and according to the invention, the reactor thus has a third portion of conduit extending downstream of the first conduit portion and the second conduit portion, said third conduit portion extending to an inlet of the conduit portion. reaction duct. In other words, said third portion of duct forms an intermediate portion between on the one hand, said first duct portion, the second duct portion and, on the other hand, the reaction duct (in which the solvothermal treatment is carried out. reaction medium for obtaining phyllominéral particles, and in particular phyllosilicatées particles). In this third portion of conduit, each mineral compound and each metal salt are contacted to form the precursor gel by continuous co-precipitation.
[0013] Advantageously and according to the invention, the flow rate of the precursor gel composition within the third portion of the duct and the length of the third portion of the duct are adapted to allow the continuous formation of the precursor gel upstream-especially immediately upstream of the inlet to the reactor-in particular the reaction line, that is to say before the solvothermal treatment. Preheating to a temperature above room temperature may optionally be provided in this third portion of conduit, before the entry of the reaction conduit. Advantageously and according to the invention, the suspension comprising phyllomineral particles, and in particular phyllosilicate particles, is cooled downstream of its exit from the solvothermal treatment zone. Each duct (or portion of duct) of the continuous synthesis device used for the implementation of a process according to the invention has dimensions adapted to allow continuous circulation of the various compositions (starting composition (s), reaction medium and obtained suspension comprising the phyllomineral synthetic particles). Each duct and duct portion may in particular have dimensions centifluidic (internal diameter greater than 1 cm) or millifluidic (internal diameter greater than 1 mm) or microfluidic (internal diameter less than 1 mm and especially less than 750ium). Advantageously and according to the invention, a reaction conduit 30 having an internal diameter greater than 1 millimeter is used. In addition, the continuous reactor may have additional inputs located before the solvothermal treatment zone, at the level of the solvothermal treatment zone or after leaving the solvothermal treatment zone and before the exit of the suspension obtained. Such inputs may allow the introduction of a gas or a dense medium, for example a liquid (water or alcohol for example to control the proportion of liquid medium or to control the pH at any stage of the process) and / or a solid. It may for example also be grafting compositions using at least one water-soluble oxysilane having the formula (III): A-Si-O-R 4 (III) c) R 5 wherein A denotes a group selected from methyl and hydrocarbon groups comprising at least one heteroatom; and R3, R4 and R5, are the same or different, and selected from hydrogen and linear alkyl groups comprising 1 to 3 carbon atom (s). Said oxysilane may, for example, be introduced before the solvothermal treatment zone and be a soluble trialkoxysilane in an aqueous medium and of the following formula: ## STR3 ## In which: R 3, R 4 and R 5, are identical or different, and chosen from linear alkyl groups comprising 1 to 3 carbon atoms, R 7 is chosen from the group consisting of: linear alkyl groups comprising 1 to 18 carbon atoms, - n is an integer between 1 and 5, and - X 'is an anion whose thermal stability is compatible with the temperature and the residence time of the solvothermal treatment , and for example an anion in which X is chosen from chlorine, iodine and bromine, and may also be compositions for functionalization of the phyllomineral synthetic particles, for example with magnetite particles, precipitation activators, catalysts of the precipitation or transformation reaction at least one suspension starting composition comprising phyllomineral synthetic particles or silver particles.
[0014] Advantageously and according to the invention, a suspension comprising particles of phyllosilicates 2: 1 type is obtained. More particularly, advantageously and according to the invention, there is obtained a suspension comprising phyllosilicate particles according to formula (II). In particular, the phyllosilicate particles obtained by a process according to the invention have, in X-ray diffraction, the following characteristic diffraction lines: a plane (001) situated at a distance of between 9.40 Å and 12.50 Å; - a plane (003) located at a distance between 3.10A and 3.30A; - a plane (060) located at a distance between 1.51A and 1.53A.
[0015] More particularly, the phyllosilicate particles obtained by a process according to the invention have, in X-ray diffraction, the following characteristic diffraction lines: a plane (001) located at a distance of between 9.40 Å and 12.50 Å; a plane (002) situated at a distance between 4.60 Å and 5.0011; - a plane (003) located at a distance between 3.10A and 3.30A; - a plane (060) located at a distance between 1.51A and 1.53A.
[0016] Such phyllosilicate particles are obtained in particular when using a precursor gel according to the above-mentioned formula (I). The suspension comprising phyllosilicate particles obtained by a process according to the invention can be dried by any powder drying technique. Advantageously and according to the invention, subsequent to said solvothermal treatment, said synthetic particles obtained by freeze-drying are dried. The drying can also be carried out by means of an oven, for example at a temperature between 60 ° C. and 130 ° C., for 1 hour to 48 hours, under microwave irradiation, or else by atomization.
[0017] The invention also relates to a method and a composition that can be obtained by a process according to the invention characterized in combination by all or some of the characteristics mentioned above or below. Other objects, features and advantages of the invention appear on reading the following description of one of its preferred embodiments given by way of non-limiting example, and which refers to the appended figures in which: FIG. 1 is a schematic view of a phyllomineral synthetic particle preparation device used in a process according to the invention; FIGS. 2, 5, 7, 8, 9 represent X-ray diffractograms (RX); Phyllomineral particles obtained by the examples given below with a process according to the invention, - Figures 3, 4, 6 represent Fourier transform infrared absorption spectra of phyllomineral synthetic particles obtained by the examples given below. following with a method according to the invention, - Figures 10 and 11 are photographs of scanning electron microscopy field effect of synthetic particles phyllom obtained in an example given below with a method according to the invention. A / - GENERAL PROTOCOL FOR THE PREPARATION OF PHYLLOMINERAL SYNTHETIC PARTICLES ACCORDING TO THE INVENTION 1 / - Device for preparing phyllomineral synthetic particles In a process according to the invention, a reactor 15 is used for the preparation of phyllomineral synthetic particles continuously (such as illustrated in FIG. 1) comprising: a first portion 11 of conduit in which a first aqueous solution comprising at least one mineral compound chosen from silicates, germanates, their solid solutions and their mixtures is introduced; a second portion; 12 of conduit in which is introduced a second aqueous solution 21 comprising at least one metal salt of at least one metal M, - a third portion 13 of conduit disposed after the first portion 11 of conduit and the second portion 12 of conduit and extending to an inlet 9 of a reaction chamber 16, the first portion 11 of conduit and the second portion 12 of conduit joining at a point 17 from which the third conduit portion 13 begins; - a reaction conduit 14 extending from the inlet 9 into the reaction chamber 16, and after the third portion 13 of conduit. A peristaltic pump 18 continuously feeds the first conduit portion 11 with the first aqueous solution contained in a reservoir 30 with stirring. A second peristaltic pump 19 continuously feeds the second portion 12 of conduit with the second aqueous solution 21 contained in a tank 31 with stirring. For the purpose of controlling the temperature within the reaction conduit 14, the reaction chamber 16 is a furnace comprising a heating sleeve comprising ceramic material resistors. The reaction conduit 14 is in the general shape of a coil wound in multiple turns inside the heating sleeve, until it leaves the latter through an outlet 8 constituting the outlet of the reaction chamber 16. A co-precipitation reaction of a phyllomineral particle precursor gel takes place in the third portion 13 of conduit, upstream of the inlet 9, that is to say before the solvothermal treatment. The temperature of the precursor gel composition within the third conduit portion 13 is close to room temperature. The length of the third portion 13 of conduit may be surprisingly short, of the order of a few centimeters, and is for example between 10cm and 20cm. In the examples, this length is of the order of 15 cm. In addition, it is possible to introduce other solutions such as solutions for functionalization or grafting of the particles or to add a solvent at different levels of the device, for example to entries 4, 5 located before the solvothermal treatment zone, at an inlet 6 located at the level of the solvothermal treatment zone or at an inlet 7 located after the exit of the solvothermal treatment zone and before the exit of the suspension obtained. A pressure regulator 2 is disposed downstream of the reaction chamber 16 in connection with a fifth portion 10 of conduit extending from the outlet 8 of the reaction conduit 14 and the reaction chamber 16 to a container 25. in which a suspension comprising the phyllomineral synthetic particles obtained is recovered. The closure of a valve 32 interposed on the fifth portion 10 of conduit makes it possible to circulate the suspension obtained at the outlet 8 of the reaction conduit 14 in a circuit 33 which makes it possible to pass this suspension through a porous sinter 34 adapted to retain the particles and allow their recovery. The porous sinter 34 is immersed in an ice bucket 35 for cooling the suspension leaving the reactor. In this case, valves 36 and 37 disposed on the branch circuit 33 are open. The porous sinter 34 is chosen so as to retain the phyllomineral particles synthesized by separating them from the liquid medium which carries them. The sintered material is for example made of 316L stainless steel with a pore size of 50. When the porous sinter is clogged with phyllomineral particles, it is sufficient to open the valve 32 and to close the valves 36 and 37, to directly recover the suspension in the container 25, this suspension being cooled by passing through the ice container. 35, then washed and centrifuged several times to recover the phyllomineral particles which can then be dried, for example in an oven. In another variant (not shown), it is of course also possible to provide several frits in parallel, which allows to direct the suspension obtained at the outlet of the reaction conduit 14 to another sinter as soon as the previous is clogged by the particles phyllominérales. 2 / - Preparation of a silico / germano-metallic precursor gel The silico / germano-metallic gel may be prepared by a co-precipitation reaction involving, as reagent, at least one inorganic compound comprising silicon and / or germanium, at least one dicarboxylate salt of formula M (Ri-000) 2 (M denoting at least one divalent or trivalent metal and R 1 being selected from H and alkyl groups comprising less than 5 carbon atoms) in the presence of at least minus a carboxylate salt of the formula R 2 COOM 'in which M' denotes a metal selected from the group consisting of Na and K, and R2 is selected from H and the alkyl groups having less than five carbon atoms. This co-precipitation reaction makes it possible to obtain a hydrated silico / germano-metallic hydrogel having the talc stoichiometry (4 Si / Ge for 3 M, M having the formula Mgy (/) Coy (2) Zny (3) Cuy ( 4) Mny (5) Fey (6) Niy (7) Cry (8); 8 each y (i) representing a real number of the interval [0; 1], and such that Iy (i) = 1. The silico / germano-metallic gel is prepared by a co-precipitation reaction carried out starting from: 1. an aqueous solution of penta-hydrated sodium metasilicate or an aqueous solution of sodium metagermanate, or a mixture of these two solutions in the molar proportions x / (1-x), 2. a solution of salt (s) dicarboxylate, prepared with one or more salt (s) dicarboxylate of formula M (Ri-000) 2 diluted (s) ) in a carboxylic acid, such as acetic acid, and 3. a solution of carboxylate salt (s), prepared with one or more carboxylate salt (s) of formula R2-COOM 'diluted in water distilled.
[0018] The preparation of this silico / germano-metallic hydrogel is carried out according to the following protocol: 1. the solutions of metasilicate and / or sodium metagenate and carboxylate salt (s) of formula R 2 -COOM 'are mixed 2. there is added rapidly the solution of salt (s) dicarboxylate of formula M (Ri-000) 2; the coprecipitation hydrogel is formed instantly. In addition, it is possible to subject the preparation medium of said hydrogel to ultrasound. At the end of this precipitation, a silico / germano-metallic hydrogel is obtained comprising: - 4 (SixGei-x), - 3 atoms of at least one metal M, M denoting at least one divalent metal having the formula Mgy ( /) Coy (2) Zny (3) Cuy (4) Mny (5) Fey (6) Niy (7) Cry (8) in which each y (i) represents a real number of the interval [0; 1], and such that 8 Iy (i) = 1, i = 1 - (10-E) oxygen atoms ((10-E) O), E being a real number of the interval [0; 10r, - (2 + E) hydroxyl groups ((2 + E) (OH)), where E is a real number of the interval [0; 10r, 20 in an aqueous solution of salt (s) carboxylate said hydrogel being highly hydrated (water molecules being bonded to the hydrogel particles without being water constitution) and having a consistency more or less gelatinous. The hydrogel can also be recovered after centrifugation (for example between 3000 and 15000 rpm for 5 to 60 minutes) and removal of the supernatant (carboxylate salt solution), optionally washing with demineralized water (by two successive washes and centrifugations) and then drying, for example in an oven (60 ° C., 2 days), by lyophilization, by spray drying or by drying under irradiation of microwaves. The silico / germano-metallic particles of formula (I) below: 4 (Si, Gei,) 3 M ((10-E) O) ((2 + E) (OH)) can thus be stored in the form of a powder (in the presence or absence of the carboxylate salt (s) depending on whether water washing has been carried out or not) for possible subsequent hydrothermal treatment. The precursor gel may be prepared continuously as provided in the phyllomineral particle preparation device described above, or on the contrary beforehand, that is to say outside the device for preparing phyllomineral particles described above, and then fed continuously as needed directly into the third conduit portion 13 or directly to the inlet 9 of the reaction conduit 14. In each case, it is important to control the dilution of the precursor gel introduced into each portion of the conduit and into the reaction conduit 14 so as to allow continuous circulation of the reaction medium 15 in the reaction conduit 14, and in all conduits for feeding said precursor gel composition to the inlet 9 of the reaction chamber 16. The precursor hydrogel concentration in said precursor gel composition introduced at the inlet of the reaction chamber 16 is advantageously between 10 -3 mol / L and several mol / L, for example of the order of 0.01 mol / L. It should be noted that this concentration is much lower than the concentrations used in the processes for the preparation of phyllomineral synthetic particles such as phyllosilicates of the state of the art. 3 / - Hydrothermal treatment of said silico / germanometallic hydrogel The precursor hydrogel of formula (I) above, dried or not, as previously obtained, is subjected to a hydrothermal treatment in the reaction conduit 14 when it enters the chamber 16 of reaction. Hydrothermal treatment is a solvothermal treatment which can in particular be carried out under supercritical or subcritical, and in particular subcritical, homogeneous conditions. Thus, it is possible to choose the temperature and the pressure at which this solvothermal treatment is carried out so that the precursor gel composition introduced at the inlet of the reactor, and in particular the solvent (s) it comprises is under supercritical conditions or under homogeneous subcritical conditions, i.e., above the liquid-gas equilibrium curve of the solvent, and so that the solvent is present in the liquid state and not in the form of a liquid-gas mixture or gas alone. At the end of this hydrothermal treatment, a suspension is obtained comprising phyllosilicate mineral particles in an aqueous solution of carboxylate salt (s). At the end of this hydrothermal treatment, the suspension obtained is recovered by filtration, for example by means of a ceramic sinter, or else by centrifugation (between 3000 and 15000 revolutions per minute, for 5 to 60 minutes) and then elimination of the supernatant. The supernatant solution contains one or more salt (s) of formula R1-COOM 'and / or R2-COOM' and can be stored in order to recover this (these) carboxylate salt (s) and to recycle them.
[0019] The composition comprising recovered mineral particles may optionally be washed with water, in particular with distilled or osmosis water, for example by carrying out one or two washing / centrifugation cycles. The composition comprising mineral particles recovered after the last centrifugation can then be dried: in an oven at a temperature of between 60.degree. C. and 130.degree. C., for 1 to 24 hours, or else by lyophilization, for example in a CHRIST ALPHA® 1-2 LD Plus lyophilizer, for 48 hours to 72 hours, by microwave irradiation, by spraying, or by any other powder drying technique. Finally, a divided solid composition is obtained whose color is a function of the nature of the (s) dicarboxylate salt (s) of formula M (Ri-000) 2 used for the preparation of the silico / germano-metallic gel (and also, if appropriate, respective proportions of this (s) salt (s) dicarboxylate).
[0020] The inventors have thus been able to note that not only an extremely short time (less than one minute) of hydrothermal treatment under supercritical conditions is sufficient to allow a conversion of the initial gel into a crystallized and thermally stable material, but also that the Synthetic mineral particles obtained have improved crystallinity. The phyllosilicate mineral particles contained in a talcose composition obtained by a process according to the invention have remarkable properties in terms of purity, crystallinity and thermal stability, and for an extremely short hydrothermal treatment duration (with respect to the duration hydrothermal treatment previously required in a known talcose compound preparation process), and without the need for subsequent anhydrous (annealing) heat treatment. B / - ANALYSIS AND STRUCTURAL CHARACTERIZATION The analysis results of a talcose composition obtained by following the previously discussed protocol are hereinafter reported. These results confirm that the invention actually leads to the formation of synthetic phyllosilicate mineral particles having structural characteristics (including lamellarity and crystallinity) very similar to those of natural talc. They also show that, in particular by the choice of the temperature and the duration of implementation, the invention makes it possible to synthesize, in an extremely simple manner, synthetic, stable and pure synthetic silico / germano-metallic mineral particles having a size and defined and predictable crystalline characteristics. The analyzes were carried out in particular by X-ray diffraction, infrared and observations by electron microscopy. The collected data are presented in the accompanying figures and in the examples, and are hereinafter commented. 1 / X-Ray Diffraction Analyzes X-ray diffraction (RX), a natural talc such as talc from the ARNOLD mine (State of New York, USA), is known to present the rays. following characteristics of diffraction (from the publication of Ross M., Smith WL and Ashton WH, 1968, "Triclinic Talc and Associated Amphiboles from Governor Mining District, New York, American Mineralogist," volume 53, pages 751-769): for the plane (001), a line located at a distance of 9.34 Å; for the plane (002), a line located at a distance of 4.68 Å; for the plane (020), a line located at a distance of 4.56 Å; for the plane (003), a line situated at a distance of 3.115 Å; for the plane (060), a line located at a distance of 1.52 Å. FIGS. 2, 5, 7, 8, 9 show RX diffractograms of the particles obtained in the examples below, on each of which is represented the relative intensity of the signal (number of strokes per second) as a function of the angle 20. The X-ray diffractograms shown were recorded on a CPS 120 device marketed by INEL (Artenay, France). This is a curved detector diffractometer for real time detection over an angular range of 120 °. The acceleration voltage used is 40kV and the intensity of 25mA. The Bragg relation giving the structural equidistance is: d11 = 0.89449 / sin0 (with the use of a cobalt anticathode). This X-ray diffraction analysis confirms that there is a great structural similarity between the phyllosilicate mineral particles of the talcose compositions prepared according to the invention and the natural talc particles. In particular, the diffraction lines corresponding respectively to the (003) and (060) planes have positions which coincide perfectly with those of the reference diffraction lines for natural talc. 2 / - Near infrared analyzes In infrared, it is known that natural talc has, in the near infrared, a 7185cm-1 vibration band representative of the vibration of the Mg 3 -OH bond. The acquisition of the spectra shown in FIGS. 3, 4 and 6 was carried out with a NICOLET 6700-FTIR spectrometer over a range of 9000 cm -1 at 4000 cm -1. 3 / - Microscopic Observations and Evaluation of the Particle Size Given the great fineness of the powders that can constitute the talcose compositions in accordance with the invention, the size and the particle size distribution of the phyllosilicate mineral particles which compose them were appreciated by observation scanning electron microscopy and field effect and transmission electron microscopy. The examples which follow illustrate the preparation process according to the invention and the structural characteristics of the compositions comprising synthetic mineral particles, and in particular talcose compositions comprising phyllosilicate mineral particles, thus obtained. EXAMPLE 1 A solution of magnesium acetate is prepared on the one hand by adding 1.60817 g of magnesium acetate tetrahydrate (Mg (CH 3 COO) 2, 4H 2 O) in 5 mL of acetic acid CH 3 COOH at 1 mol / L and 245 mL of magnesium acetate. 'distilled water. On the other hand, a sodium metasilicate solution is prepared by adding 2,12136 g of sodium metasilicate pentahydrate (Na 2 OSiO 2, 5H 2 O) in 250 mL of distilled water. The peristaltic pumps 18, 19 make it possible to bring the two solutions separately by means of steel ducts having an outer diameter of 1/8 inch (3.175 mm) and an internal diameter of 1.57 mm, and at a flow rate of 2 ml / min each, a total flow of 4 ml / min at point 17 where the mixing of the two solutions occurs continuously, a few centimeters before the inlet 9 of the conduit 14 reaction. The temperature in the chamber 16 is 400 ° C., and the pressure in the reaction conduit 14 is maintained (thanks to the pressure regulator 2) greater than 22.1 MPa (between 25 MPa and 27 MPa), so that the medium The reaction which circulates inside the reaction conduit 14 in the enclosure 16 is under conditions above the critical point of water (374 ° C., 221 bar). The precursor gel, resulting from the mixing and co-precipitation of the two solutions involved in the third portion 13 of conduit upstream of the inlet 9 of the reaction conduit 14, thus undergoes a hydrothermal treatment in the enclosure 16 of reaction, which makes it possible to transform this precursor gel into a synthetic talc suspension. The residence time in the reaction conduit 14 between the inlet 9 and the outlet 8 is 23 seconds. After cooling the suspension from the outlet 8 of the reactor 15 is a colloidal suspension of synthetic talc particles in a saline aqueous medium (sodium acetate). It has the appearance of a white milky composition that settles in several tens of minutes. This suspension is subjected to a centrifugation cycle (10 min at 8000 rpm). After centrifugation, on the one hand a talcose composition is recovered, and on the other hand a supernatant solution comprising in particular sodium acetate, the latter then being recoverable and possibly recycled. The recovered talcose composition is then subjected to two successive cycles of washing with demineralized water and centrifugation (10 min at 8000 rpm). The talcose composition recovered after centrifugation is finally dried in an oven at 60 ° C for 12 hours. The X-ray diffractogram of the talc particles obtained according to the invention is represented by the curve 40 in FIG. 2. The X-ray diffractogram of this talcose composition exhibits diffraction lines corresponding to the diffraction lines of the talc, and in particular the lines of diffraction features: - a plane (001) located at a distance of 10.05A; a plane (002) located at a distance of 4.96 Å; a plane (020) located at a distance of 4.59 Å; A plane (003) located at a distance of 3.19 Å; a plane (060) located at a distance of 1.53 Å. Curve 40 is similar to that obtained by the method of WO2013 / 004979 at 300 ° C but with a hydrothermal treatment of 3 hours. Curve 44 in FIG. 2 is a comparative diffractogram of talc particles obtained by the method of WO2013 / 004979 at 300 ° C. with a 6-hour hydrothermal treatment, which are considered a reference.
[0021] Moreover, it can be seen that by repeating this example several times, almost identical diffractograms are obtained, demonstrating the excellent reproducibility of the process according to the invention. FIG. 3 represents the infrared absorption spectra of the particles obtained according to the invention in this example 1 (curve 37), by comparing them with the infrared absorption spectrum of the talc particles obtained by the method of WO2013 / 004979 to 300 ° C with a hydrothermal treatment of 1 hour (curve 38) and the infrared absorption spectrum of talc particles obtained by the method of WO2013 / 004979 at 300 ° C with a hydrothermal treatment of 2 hours (curve 39). FIG. 4 represents the infrared absorption spectra of the particles obtained according to the invention in this example 1 according to the invention in 23s (curve 45), and of talc particles obtained by the method of WO2013 / 004979 at 300 ° C. with a hydrothermal treatment of 3h (curve 46); talc particles obtained by the method of WO2013 / 004979 at 300 ° C with a 2-hour hydrothermal treatment (curve 47); talc particles obtained by the method of WO2013 / 004979 at 300 ° C with a hydrothermal treatment of 1 hour (curve 48). FIGS. 10 and 11 are photographs taken with a Field Effect Scanning Electron Microscope (SEM-FEG) illustrating phyllosilicate particles obtained in this example. Sub-micron talc particles (visible in the photos of FIGS. 10 and 11 in a form in which the particles are agglomerated together) having a larger dimension of the order of 200 Å to 3000 Å, a thickness of less than 100 Å are obtained. 25 corresponding to some stacked leaflets. EXAMPLE 2 A solution of magnesium acetate is prepared on the one hand by adding 3.216 g of magnesium acetate tetrahydrate (Mg (CH 3 COO) 2, 4H 2 O) in 10 ml of acetic acid CH 3 COOH at 1 mol / l and 490 ml of water. distilled. On the other hand, a sodium metasilicate solution is prepared by adding 4.24284 g of sodium metasilicate pentahydrate (Na 2 SO 2 O 5 .5H 2 O) in 500 ml of distilled water. In this example, the two solutions 20, 21 are fed by the pumps 18, 19 with a flow rate of 4 mL / min each, ie a total flow rate of 8 mL / min of reaction medium in the reaction line 14. The residence time in the reactor (in the reaction conduit 14 between the inlet 9 and the outlet 8) is 11 seconds. The other reaction conditions are identical to those of Example 1. The X-ray diffractogram of the talc particles obtained is represented by the curve 41 in FIG. 2. The X-ray diffractogram of this talcose composition has diffraction lines corresponding to the lines of diffraction of talc, and in particular the following characteristic diffraction lines - a plane (001) at a distance of 10.47 Å; a plane (020) located at a distance of 4.57 Å; A plane (003) located at a distance of 3.19 Å; a plane (060) located at a distance of 1.53 Å. Curve 41 is similar to that obtained by the method of WO2013 / 004979 at 300 ° C but with a hydrothermal treatment of 1 hour. EXAMPLE 3 A solution of magnesium acetate is prepared by adding 3.2165 g of magnesium acetate tetrahydrate (Mg (CH 3 COO) 2, 4H 2 O) in 10 ml of acetic acid CH 3 COOH at 1 mol / l and 490 ml of carbon dioxide. 'distilled water. On the other hand, a sodium metasilicate solution is prepared by adding 4.24325 g of sodium metasilicate pentahydrate (Na 2 OSiO 2, 5H 2 O) in 500 mL of distilled water. The reaction conditions are identical to those of Example 1. The ceramic sinter 34 is used at the outlet to separate the talc particles by filtering the suspension. The particles are manually recovered from the sinter (without washing or centrifugation) and then dried in an oven. On the other hand, the salted solution can be recovered at the sintered outlet and then dried to recover the salt. When the sinter 34 is filled with talc particles, the remainder of the synthesized product can be recovered in the container 25, without passing through the sintered material. This part of the product is centrifuged, then washed / centrifuged twice. The talcose composition then recovered is then dried in an oven. The X-ray diffractograms of the talc particles obtained in this example 3 are represented by the curves 42 and 43 in FIG. 2. The curve 42 is obtained with the particles recovered by the sintered material. Curve 43 is obtained by the particles recovered by washing and centrifugation without the sinter.
[0022] The X-ray diffractogram of the talcose composition represented by the curve 42 has diffraction lines corresponding to the talc diffraction lines, and in particular the following characteristic diffraction lines: a plane (001) situated at a distance of 10.08 Å; a plane (002) located at a distance of 4.90 Å; a plane (020) located at a distance of 4.53 Å; a plane (003) located at a distance of 3.20A; a plane (060) located at a distance of 1.52 Å. The X-ray diffractogram of the talcose composition represented by the curve 43 has diffraction lines corresponding to the diffraction lines of the talc, and in particular the following characteristic diffraction lines: a plane (001) located at a distance of 10.54. ; a plane (002) located at a distance of 4.91 Å; A plane (020) located at a distance of 4.56 Å; a plane (003) located at a distance of 3.19 Å; a plane (060) located at a distance of 1.52 Å. The curves 42 and 43 are similar to that obtained by the method of WO2013 / 004979 at 300 ° C. but with a hydrothermal treatment of 2 hours. FIG. 5 compares the RX diffractograms of the particles obtained in Example 1 according to the invention in 23s (curve 53), and of talc particles obtained by the method of WO2013 / 004979 at 300 ° C. with a hydrothermal treatment of 3h. (curve 54); particles obtained on the sinter in Example 3 according to the invention in 23s (curve 55) and talc particles obtained by the method of WO2013 / 004979 at 300 ° C with a hydrothermal treatment of 2 hours (curve 56); particles obtained in Example 2 according to the invention in lls (curve 57) and talc particles obtained by the method of WO2013 / 004979 at 300 ° C with a hydrothermal treatment of 1 hour (curve 58). FIG. 6 compares infrared absorption spectra of particles obtained according to the invention in example 1 (curve 62), in example 2 (curve 63), and in example 3 (curve 64 for those obtained from the sintered curve 65 for those obtained out of the sinter). EXAMPLE 4 A solution of magnesium acetate is prepared by adding 3.2165 g of magnesium acetate tetrahydrate (Mg (CH 3 COO) 2, 4H 2 O) in 10 ml of acetic acid CH 3 COOH at 1 mol / l and 490 ml. distilled water. On the other hand, a sodium metasilicate solution is prepared by adding 4.24325 g of sodium metasilicate pentahydrate (Na 2 OSiO 2, 5H 2 O) in 500 mL of distilled water. Three successive tests are carried out under identical reaction conditions to those of Example 1, by varying the temperature of the hydrothermal treatment and the flow rates according to the following table: Test 1 2 3 temperature (° C) 350 375 400 flow rate of each salt (mL / min) 7.5 6 2 total flow rate (mL / min) 15 12 4 Curve 72 73 74 The RX diffractograms of the phyllosilicate particles obtained are represented by curves 72, 73 and 74, respectively in FIG. 7. Curve 72 corresponds to the temperature of 350 ° C, curve 73 corresponds to the temperature of 375 ° C, and curve 74 corresponds to the temperature of 400 ° C (similar to that of Example 1). The curves 72 and 73 are almost identical. As can be seen, a process according to the invention also makes it possible to obtain phyllosilicate particles having the structure of a talc under homogeneous subcritical conditions. In addition, under supercritical conditions, the structural characteristics of the particles are even better and as can be seen through the curve 74, the crystallinity of the particles obtained under these conditions is exceptional and similar to that of a natural talc. The X-ray diffractogram of the talcose composition represented by the curve 72 has diffraction lines corresponding to the talc diffraction lines, and in particular the following characteristic diffraction lines: a plane (001) situated at a distance of 12.09 Å; a plane (020) located at a distance of 4.57 Å; a plane (003) located at a distance of 3.25 Å; a plane (060) located at a distance of 1.53 Å. The X-ray diffractogram of the talcose composition represented by the curve 73 has diffraction lines corresponding to the diffraction lines of the talc, and in particular the following characteristic diffraction lines: a plane (001) located at a distance of 11.9 °. ; a plane (020) located at a distance of 4.55 Å; A plane (003) located at a distance of 3.25 Å; a plane (060) located at a distance of 1.53 Å. The X-ray diffractogram of the talcose composition represented by the curve 74 has diffraction lines corresponding to the talc diffraction lines, and in particular the following characteristic diffraction lines: a plane (001) situated at a distance of 10.21 Å ; - a plane (002) located at a distance of 4.98A; a plane (020) located at a distance of 4.61A; a plane (003) located at a distance of 3.22 Å; A plane (060) located at a distance of 1.53 Å. FIG. 8 compares the X-ray diffractograms of the particles obtained in test 2 (at 375 ° C.) according to the invention (curve 80), and of talc particles obtained according to the protocol described by WO2013 / 004979 at 230 ° C. with a hydrothermal treatment of 6 hours (curve 81), and talc particles obtained by the method of WO2013 / 004979 at 300 ° C with a hydrothermal treatment of 1 hour (curve 82). FIG. 9 compares the RX diffractograms of the particles obtained in test 3 (at 400 ° C.) according to the invention (curve 90), and of talc particles obtained by the method of WO2013 / 004979 at 300 ° C. with a treatment. hydrothermal 3 hours (curve 91).
[0023] It is found that the average size of the elementary particles obtained in the examples above is generally less than 3000 Å. The size of the particles can of course vary depending in particular on the residence time and the temperature in the hydrothermal treatment zone, an increase in the residence time allowing, for example, an increase in the size of the particles essentially in the plane (a, b). ) of the crystal lattice of the particles (i.e., the width and length of the particles). The above examples also show that it is easy to precisely adjust the structural characteristics of the phyllosilicate particles obtained by modifying the residence time, i.e., the duration of the solvothermal treatment, and / or the temperature of the solvothermal treatment. The invention can be the subject of many variants. In particular, it is possible to provide several main conduits arranged in parallel in the same reactor; it is possible to prepare the precursor gel (or particles corresponding to this precursor gel) in advance to be able to use it as needed to perform the solvothermal treatment; the device making it possible to continuously apply the temperature and the pressure of the solvothermal treatment to the reaction medium initially constituted by the precursor gel may be the subject of various embodiments ...

权利要求:
Claims (4)
[0001]
CLAIMS 1 / - Process for the preparation of phyllomineral synthetic particles formed of chemical elements, said constituent chemical elements, in predetermined proportions, called stoichiometric proportions, said constituent chemical elements comprising at least one chemical element chosen from the group consisting of silicon and germanium and at least one chemical element selected from the group consisting of divalent metals and trivalent metals, by a so-called solvothermal treatment of a reaction medium comprising a liquid medium and containing said stoichiometric proportions of said constituent chemical elements of said synthetic particles phyllominérales, in which: said solvothermal treatment is carried out continuously at a pressure greater than 1 MPa and at a temperature between 100 ° C. and 600 ° C., the reaction medium is circulated continuously in a zone, called the solvo treatment zone; thermal, of a continuous reactor (15) with a residence time of the reaction medium in said solvothermal treatment zone adapted to obtain continuously, at the output of said solvothermal treatment zone, a suspension comprising said phyllomineral synthetic particles.
[0002]
2 / - Method according to claim 1, characterized in that one uses a reactor (15) continuous at constant volume.
[0003]
3 / - Method according to any one of claims 1 or 2, characterized in that the solvothermal treatment zone of the reactor (15) comprises at least one conduit, said reaction conduit (14), wherein continuously circulates the reaction medium between at least one inlet (9) adapted to allow the continuous introduction of at least one starting composition and at least one outlet (8) by which the suspension comprising said phyllomineral synthetic particles is continuously recovered.
[0004]
4 / - Method according to claim 3, characterized in that the temperature is controlled by controlling the temperature of the reaction conduit (14). 5. The process as claimed in claim 1, wherein said solvothermal treatment is carried out at a pressure of between 2 MPa and 50 MPa. 6 / - Process according to any one of claims 1 to 5, characterized in that adjusts the duration of the continuous solvothermal treatment by controlling the residence time of the reaction medium in the solvothermal treatment zone, in which it is subject at the temperature and pressure of the solvothermal treatment. 7 / - Process according to any one of claims 1 to 6, characterized in that the reaction medium is circulated continuously in the reactor (15) so that it has a residence time in the zone solvothermal treatment less than 10 minutes. 8 / - Process according to any one of claims 1 to 7, characterized in that said reaction medium is introduced into the solvothermal treatment zone with a flow rate chosen to obtain the appropriate residence time. 9 / - Process according to any one of claims 1 to 8, characterized in that said solvothermal treatment is carried out under conditions of temperature and pressure such that said reaction medium is in supercritical conditions. 10 / - Process according to any one of claims 1 to 9, characterized in that the reaction medium is prepared continuously from at least a first starting composition comprising at least one compound, said mineral compound, chosen among the silicates and / or germanates, their solid solutions and their mixtures, and of at least a second starting composition comprising at least one metal salt of at least one metal M selected from the group consisting of divalent metals and metals trivalents, said first and second compositions being contacted continuously upstream of at least one inlet of said solvothermal treatment zone. 11 / - Method according to claim 10, characterized in that said first starting composition is continuously fed into at least a first portion (11) of conduit and said second starting composition in at least a second portion (12) each of the first portion (11) of conduit and the second portion (12) of conduit being connected to each other enamont of the solvothermal treatment zone to allow the continuous contact of these two compositions. 12 / - Method according to claim 11, characterized in that the first portion (11) of duct and the second portion (12) of duct meet upstream of at least one inlet of the solvothermal treatment zone, in a third portion (13) of conduit connecting each of the first and second conduit portions and the inlet of the solvothermal treatment zone. 13 / - Process according to any one of claims 1 to 12, for the preparation of phyllosilicate synthetic particles belonging to the group consisting of lamellar silicates, lamellar germanates, lamellar germanosilicates and mixtures thereof, characterized in that as a precursor gel, a precursor silico / germano-metallic hydrogel, and in that said solvothermal treatment is carried out in the form of a continuous hydrothermal treatment of this silico / germano-metallic precursor hydrogel. 14 / - Method according to claim 13, characterized in that, as precursor gel, a silico / germano-metallic precursor hydrogel comprising: - 4 silicon atoms and / or germanium according to the following chemical formula : 4 (SixGei_x), where x is a real number of the interval [0; 1], - 3 atoms of at least one metal M, M denoting at least one divalent metal having the formula Mgy (/) Coy (2) Zny (3) Cuy (4) Mny (5) Fey (6) Niy ( 7) Cry (8) wherein each y (i) represents a real number of the interval [0; 1], and such that 8 1 y (i) = 1, - (10-E) oxygen atoms ((10-E) O), E being a real number of the interval [0; 10r, - (2 + E) hydroxyl groups ((2 + E) (OH)), where E is a real number of the interval [0; 10r, and in that said hydrothermal treatment is carried out so as to obtain continuously a suspension comprising phyllosilicate particles having the following chemical formula (II): (SixGei-X) 4M301o (OH) 2 (II) in which - Si designates silicon, - Ge denotes germanium, - M denotes at least one divalent metal having the formula Mgy (/) Coy (2) Zny (3) Cuy (4) Mny (5) Fey (6) Niy (7) Cry ( 8); each y (i) representing a real number of the interval [0; 1], and such that Iy (i) = 1, 1 = 1 - x is a real number of the interval [0; 1]. 10

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同族专利:

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优先权:

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申请号 | 申请日 | 专利标题

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FR1453334A|FR3019813B1|2014-04-14|2014-04-14|CONTINUOUS PROCESS FOR THE PREPARATION OF SYNTHETIC PHYLLOMINERAL PARTICLES|FR1453334A| FR3019813B1|2014-04-14|2014-04-14|CONTINUOUS PROCESS FOR THE PREPARATION OF SYNTHETIC PHYLLOMINERAL PARTICLES|

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EP15725732.0A| EP3131852A1|2014-04-14|2015-04-13|Process for the continuous preparation of phyllomineral synthetic particles|

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JP2016562504A| JP6502384B2|2014-04-14|2015-04-13|Continuous preparation process of synthetic layered mineral particles|

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US15/304,124| US10221072B2|2014-04-14|2015-04-13|Process for the continuous preparation of phyllomineral synthetic particles|

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PCT/FR2015/050984| WO2015159006A1|2014-04-14|2015-04-13|Process for the continuous preparation of phyllomineral synthetic particles|

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KR1020167031605A| KR20170008226A|2014-04-14|2015-04-13|Process for the continuous preparation of phyllomineral synthetic particles|