• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a zeolite material in the form of aggregates of FAU zeolite nanocrystals, the process for preparing said material, and the zeolite agglomerates prepared from said material with a binder, as well as the uses of said material and agglomerated material. as adsorbents for gas phase or liquid phase separation operations, and more particularly in the processes for separating gaseous or liquid streams.
    公开号:FR3025789A1
    申请号:FR1458592
    申请日:2014-09-12
    公开日:2016-03-18
    发明作者:Serge Nicolas；Guillaume Ortiz；Ludivine Bouvier；Cecile Lutz
    申请人:Carbonisation et Charbons Actifs CECA SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the field of zeolites, particularly zeolites in the form of crystals of very small sizes, more particularly zeolites in the form of crystals of nanometric sizes. The present invention also relates to the process for the preparation of such zeolites in the form of crystals of nanometric sizes, as well as their use for preparing zeolite adsorbents by agglomeration with a binder. The use of zeolite crystals of very small dimensions, especially nanoscale, is of great interest when excellent transfer properties are sought. There are nowadays mainly three synthetic methods for obtaining small crystals, as taught in numerous publications (see, for example, T. Tago and T. Masuda, Zeolite Nanoctystals - Synthesis and Applications, Chapter 8, "Nanocrystals"). , Ed. INTECH, (2010), 326 pages, or Vuong-Gia Thanh, thesis dissertation "Synthesis and characterization of nanozeolites", December 2006, University of Laval, Quebec). These three methods of synthesis can be summarized as follows: 1) the synthesis in a very dilute medium and at low temperature, mostly below room temperature; these techniques have the disadvantage of being long and uneconomical on the industrial level; 2) synthesis in confined spaces such as carbon matrix pores, microemulsion droplets, polymer hydrogels, and the like; and 3) synthesis with growth inhibitors, optionally in the presence of an organic solvent, introduced into the reaction mixture after the ripening phase and aimed at limiting the growth of the crystals; these processes are uneconomical because of relatively long synthesis times; T. Tago et al. (ibid.) propose for example nonionic surfactants such as ethers derived from polyoxyethylene or ionic surfactants such as cetyltrimethylammonium bromide (CTAB), or sodium bis (2-ethylhexyl) sulfosuccinate (AOT) which cause rather long synthesis times, of the order of several days. Patent application JP2009155187 teaches for its part the synthesis of a faujasite type colloidal zeolite (FAU) of SiO 2 / Al 2 O 3 ratio of between 2 and 6, exhibiting a bipopulation of particles with a first average diameter of between 20 nm. And a second average diameter between 20 nm and 800 nm, the ratio of these average diameters varying from 1 to 5, and the lattice constant (UD) being between 24.60 Angstrom and 24, 90 Angstrom. The purpose sought in this application is to obtain very weakly agglomerated crystals. [0005] JP2008230886 discloses the synthesis of relatively uniform small-sized particles by inoculation with a clear nuclei solution, i.e. very small nuclei, obtained after a very long time of maturing, higher at 100 hours. This process therefore appears for this reason uneconomical and difficult to envisage on an industrial level. The synthesis, filtration and manipulation of this type of solids of nanometric dimensions, however, are difficult, due not only to the small dimensions of said solids, but also because of their low density. [0007] Attempts to make the handling of such nanometric-sized solids less difficult are illustrated, for example, in document US2012100066 which teaches a means for recovering zeolite nanocrystals by centrifugation followed by a contacting phase with a solution that allows the agglomeration of crystals between them. [0008] Some authors teach that such small zeolite objects can be aggregated in the form of secondary particles which are more easily manipulated and which will retain satisfactory transfer properties. For example, the patent application US20120227584 proposes aggregates of zeolite nanocrystals FAU of average diameter greater than or equal to 0.8 μm, the average diameter of the nanocrystals being less than or equal to 0.3 μm, and where at least 80% primary particles (nanocrystals) are aggregated. Here again, the synthesis, carried out in a diluted medium, is long, uneconomical and therefore difficult to envisage industrially. In addition, the zeolite objects must have a high crystallinity, or even maximum, in terms of volume Dubinin-Raduskevich and purity of the crystalline phase obtained by X-ray diffraction (or XRD). [0010] There remains therefore today a need for an economical, easily industrializable process for synthesizing aggregates of zeolite nanocrystals (s) exhibiting a high or even maximum crystallinity. The inventors have now discovered that it is possible to prepare such nanocrystals of zeolite (s), said nanocrystals being obtained in the form of aggregates and therefore easily handled, the preparation being simple, fast, economical and therefore easily adaptable at the industrial level. Thus, and according to a first object, the present invention relates to a zeolite material in the form of aggregates of FAU zeolite nanocrystals having at least the following characteristics: atomic ratio Si / Al between 1 and 1.4, inclusive, outer surface area of between 20 m2.g-1 and 80 M2.g-1, preferably between 30 M2.g-1 and 80 M2.g-1, number of nanocrystals between 50 nm and 500 nm, preferably between 50 nm and 400 nm, more preferably between 100 nm and 400 nm, more preferably between 100 nm and 300 nm, limits included, and 10 - average size in number of aggregates between 0.2 μm and 10 μm, preferably between 0.3 μm and 10 μm, more preferably between 0.5 μm and 8 μm. According to a preferred embodiment, the nanocrystals of zeolite (s) according to the present invention are nanocrystals of zeolite (s) type FAU, and in particular zeolite (s) selected (s) among X zeolites, MSX and LSX. By zeolite MSX (Medium Silica 15 X) is meant a zeolite of FAU type having an Si / Al atomic ratio of between about 1.05 and about 1.15, inclusive. By zeolite LSX (Low Silica X) is meant a zeolite of FAU type having an Si / Al atomic ratio equal to about 1. FAU X type zeolites are particularly preferred. [0014] The characteristics cited above give the zeolite material in the form of zeolite nanocrystals (s) aggregated according to the present invention, improved properties and quite surprising and interesting, compared to the zeolite materials known from the prior art. In particular, these aggregates of zeolitic nanocrystals have an intercrystalline mesoporosity quite interesting for further improving the transfer properties in applications where such properties are desired. The size of the aggregates of nanocrystals of zeolite (s) according to the present invention is expressed by their number average diameter by observation with scanning electron microscope (SEM), as indicated below. [0016] The size of the zeolite nanocrystals (s) forming the aggregates according to the present invention is also expressed by their number average diameter by scanning electron microscope (SEM) observation, as indicated below. The invention also has the advantage of making it possible to adjust and adjust both the size of the nanocrystals and the size of the aggregates, in particular as a function of the synthesis conditions explained below, and in particular according to the agent. nucleation and control agent. In the present invention, the outer surface is measured from the nitrogen adsorption isotherm by the t-plot method described later by applying the Harkins and Jura equation. The aggregates of nanocrystals of zeolite (s) according to the invention are solids comprising a microporous network connected to an intercrystalline mesopore network, and thus make it possible to reconcile the properties of accessibility to active sites of zeolites and those of crystallinity. and microporosity of said zeolites. Thus the zeolite nanocrystals (s) of the present invention have unexpected properties and open new perspectives as to their fields of industrial applications. In addition, the aggregates of zeolite nanocrystals (s) of the present invention may be subjected to one or more cationic exchanges (for example with alkali metal or alkaline earth metal salts), according to the invention. ion exchanges well known to those skilled in the art and commonly carried out on zeolitic materials. The aggregates of zeolite nanocrystals of the present invention are thus preferred or the exchangeable sites of the zeolites are occupied by ions selected from hydronium, lithium, sodium, potassium, calcium, barium, and the like, more preferably from lithium, sodium, potassium, calcium, and barium ions. According to a second aspect, the present invention relates to the process for preparing aggregates of zeolite nanocrystals (s) as just described. The method of the invention has the advantages of being easy to implement, easily transferable on an industrial scale, and this in particular because of the high yields of synthetic materials, the robustness of the process and its speed. More particularly, the process for synthesizing said aggregates of zeolite nanocrystals (s) according to the invention uses both a control agent and a seeding step with a nucleating agent, such as a gel, crystal, mineral particle, and others, as explained further in the description of the present invention. [0022] By "control agent" is meant a chemical compound that makes it possible to control the crystal growth of the zeolite crystals (s) while at the same time making it possible to obtain optimum crystallinity. The control agents which can be used in the process of the present invention are advantageously chosen from surfactants, structuring agents, crystal growth inhibitors, dispersing agents and other chemical compounds commonly used in the synthesis. of zeolitic materials. According to a preferred aspect, the control agents which can be used in the process of the present invention comprise at least one silicon atom, more preferably are chosen from organosilicon compounds, preferably still among the organo-silanes. In another preferred aspect, the control agents are compounds having at least one nitrogen atom, and more preferably at least one amine function, and more preferably at least one ammonium function. Among the most preferred control agents include organosilanes functionalized by at least one amine and / or ammonium function. More specifically, the process for preparing aggregates of zeolite nanocrystals (s) according to the invention comprises at least the following steps: a) preparation of a so-called growth gel, by mixing a source of silica with a source of alumina, at a temperature of between 0 ° C. and 60 ° C., b) adding to the growth gel of step a) a nucleating agent, at a temperature of between 0 ° C. and 60 ° C. ° C., c) adding to the reaction medium at least one control agent, d) crystallization reaction by increasing the temperature, e) filtration and washing of the zeolite crystals obtained, and f) drying and calcination. It should be understood that step c) of addition of control agent (s) may be performed at the same time as steps a) and / or b) or before and / or after the steps a) and / or b). In all cases, it is preferred that the control agent be present in the reaction medium before step d) of crystallization. However, it is preferred to add the control agent after step b). In addition, a latency time (rest time, with or without agitation) can be provided between steps a), b), c) and d). According to a preferred aspect, the growth gel comprises a homogeneous mixture of a source of silica (for example sodium silicate), a source of alumina (for example alumina trihydrate), a strong mineral base, such as for example, sodium hydroxide, potassium hydroxide, or calcium hydroxide to name only the main and most commonly used, and water. The method of the present invention is characterized by the use of the seeding technique (step b) with at least one nucleating agent well known to those skilled in the art, for example selected from a gel of nucleating, a crystal, for example a zeolite crystal, a mineral particle of any kind, for example a clay such as for example and without limitation kaolin, meta-kaolin, or other, and others, as well as their mixtures. According to a preferred aspect, the nucleating agent is a nucleation gel and more preferably, said nucleating gel comprises a homogeneous mixture of a source of silica (for example sodium silicate), a source of alumina (for example alumina trihydrate), a strong mineral base, such as, for example, sodium hydroxide, potassium hydroxide, or calcium hydroxide, to name only the main and most commonly used, and water. The homogeneity of the mixture can be obtained by any method well known to those skilled in the art, and for example and without limitation by means of a paddle stirrer, a mixer, or to using an Archimedean screw mixer as described in EP0818418. By way of non-limiting example, in a 3 liter reactor, with an Archimedean screw whose rotation is set at 300 rpm, a satisfactory homogeneity is obtained between a few minutes and a few tens of minutes. usually between 20 minutes and 30 minutes. The mixture is generally prepared at temperatures between 0 ° C and 60 ° C, preferably between 10 ° C and 40 ° C, and for practical and economic reasons, the mixture is more preferably room temperature, for example at 25 ° C. The homogenization period is then generally less than 2 hours. As indicated above, the process of the present invention is characterized in particular by the addition to the growth gel thus obtained of a nucleating agent, and preferably of a nucleation gel according to the defined concept, for example in US3947482. The added amount of nucleating agent can vary in large proportions, and the amount of nucleation gel added can generally be from 0.1% to 20%, preferably from 0.5% to 15% by weight, of more preferably between 1% and 10% by weight, inclusive, based on the weight of the growth gel. When the nucleating agent is a zeolite crystal, it is preferably a zeolite crystal of the same nature as the zeolite that it is desired to synthesize. The number average diameter of the seed crystal (zeolite crystal) can vary widely, and for example is typically between 0.1 .mu.m and 10 .mu.m, preferably between 0.1 .mu.m and 5 .mu.m. more preferably between 0.1 pm and 1 pm. According to a preferred embodiment, the seed crystal (zeolite crystal) is introduced in the form of an aqueous suspension. The amount of seed crystals introduced can also vary in large proportions and is typically between 0.1% and 10% by weight based on the total weight of growth gel. The method according to the present invention is also characterized by an addition step in the mixture [growth gel / nucleating agent] obtained in step b) of at least one control agent as defined above. . According to a preferred embodiment, the control agent is advantageously chosen from organosilanes and more preferably from N-phenylaminopropyltrimethoxysilane (PHAPTMS, better known under the trade name SIP), aminopropyltrimethoxysilane (APTMS), isobutyltriethoxysilane (IBTES), octadecyltrimethoxysilane (ODTMS), [3- (trimethoxysilyl) propyl] octadecyldimethylammonium chloride, [3- (trimethoxysilyl) propyl] hexadecyldimethylammonium chloride, [3- (trimethoxysilyl) propyl] chloride dodecyldimethylammonium chloride, [3- (trimethoxysilyl) propyl] octylammonium chloride, N- [3- (trimethoxysilyl) propyl] aniline, 342- (2-aminoethylamino) ethylamino] propyltrimethoxysilane, N43- (trimethoxysilyl) propylfN ' (4-vinylbenzyl) ethylenediamine, triethoxy-3- (2-imidazolin-1-yl) propylsilane, 143- (trimethoxysilyl) -propylurea, N- [3- (trimethoxysilyl) propyl] ethylenediamine, [ 3- (diethylamino) propyl] triméthox ylsilane, (3-glycidyloxypropyl) trimethoxysilane, 3- (trimethoxysilyl) propyl methacrylate, [2- (cyclohexenyl) ethyl] triethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, (3-aminopropyl) trimethoxysilane, mercaptopropyl) trimethoxysilane, (3-chloropropyl) trimethoxysilane, and the like, as well as mixtures of two or more of them in all proportions. Among the control agents listed above, N-phenylaminopropyltrimethoxysilane (SIP) and [3- (trimethoxysilylpropyl) -octadecyl) methylammonium chloride (TPOAC) are particularly preferred. [0037] Agents may also be used. higher molecular weight control and for example silylated polymers optionally carrying silanol function (s), such as, for example, poly (oxyethylene) ether-alkyl-trialkoxysilanes and polypropylene oxide-diamine-alkyl-trimethoxysilanes [0038] In addition to the aforementioned control agents, it is possible to add, simultaneously or sequentially, one or more oligomeric or polymeric additives, such as, for example, those selected from PPDA (Poly-Diallyldimethylammonium Polymer), PVB (PolyVinyl Butyral). ), polyethylene glycol) -block-poly (propylene glycol) -blockpoly (ethylene glycol), and for example those known commercially under the name Pluronic® P123 marketed s by BASF. The amount of control agent (s) used in the process of the present invention can vary in large proportions and in general this is such that the molar ratio of agent (s) control / A1203 is between 0.001 and 0.15, preferably between 0.001 and 0.12 inclusive. Among the organosilane type control agents listed above, those comprising at least one ammonium function form a subgroup of control agents that are particularly suitable for the process of the invention. Among the organosilanes which do not comprise an ammonium function, mention may be made, for example, of N- [3- (trimethoxysilyl) propyl] aniline, 3- [2- (2-aminoethylamino) -ethylamino] propyltrimethoxysilane, N- [3- (trimethoxysilyl) propyl] -N '- (4-vinylbenzyl) ethylenediamine, triethoxy-3- (2-imidazolin-1-yl) propylsilane, 1- [3- (trimethoxysilyl) propyl] urea, N- [3- (trimethoxysilyl) propyl] ethylenediamine, [3- (diethylamino) propyl] trimethoxysilane, (3-glycidyloxypropyl) trimethoxysilane, 3- (trimethoxysilyl) propyl methacrylate, [2- ( cyclohexenyl) ethyl] triethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, (3-aminopropyl) trimethoxysilane, (3-mercaptopropyl) trimethoxysilane, (3-chloropropyl) trimethoxysilane, N-phenylaminopropyltrimethoxysilane (SIP), aminopropyltrimethoxysilane (APTMS), isobutyltriethoxysilane (IBTES), octadecyltrimethoxysilane (ODTMS), silylated polymers, and the like, and than mixtures of two or more of them in all proportions. Among the control agents listed above, N-phenylaminopropyltrimethoxysilane (SIP) is particularly preferred. In the case of control agents which are organosilanes having no ammonium function and described above, it is preferred to use a control agent (s) / Al 2 O 3 mole ratio of between 0.01 and 0.01. 0.15, preferably between 0.01 and 0.12, inclusive. Among the control agents which are organosilanes comprising at least one ammonium function, it is preferred to use those chosen from [3- (trirethoxysilyl) propyl] octadecyldimethylammonium chloride, [3- (trimethoxysilyl) propyl] chloride. hexadecyldimethylammonium, [3- (trimethoxysilyl) propyl] -dodecyldimethylammonium chloride, [3- (trimethoxysilyl) propyl] octylammonium chloride, and the like, as well as mixtures of two or more of them in all proportions. Among the control agents listed above, [3- (trimethoxysilyl) propyl] octadecyldimethylammonium chloride, or TPOAC, is particularly preferred. In the case of organosilanes containing at least one ammonium function, as described above, it is furthermore preferable to use a starting control agent (s) / Al 2 O 3 mole ratio of between 0.001 and 0.015. , terminals included. The addition of the control agent (s) is carried out with stirring, for example as indicated previously in step a), and then the mixture is subjected to a maturation step, preferably with stirring, always at room temperature. the same temperature, for example at 25 ° C, with stirring, for a period ranging from a few minutes to several tens of minutes, typically for one hour. After this stage of maturation, the reaction mixture is engaged in step 10 d) of crystallization, still with stirring, but slower, typically between 20 rpm and 100 rpm, for example at 50 rpm, and increasing the temperature to a value generally between 60 ° C and 100 ° C, for example 75 ° C. The time required for crystallization is generally between a few hours and several tens of hours, advantageously between 8 hours and 48 hours. At the end of the crystallization step, the zeolite nanocrystals are extracted from the reaction medium by filtration, and then washed with one or more suitable solvent (s), aqueous and / or organic (s), but preferably aqueous and finally dried between 50 ° C and 150 ° C, according to the usual techniques known to those skilled in the art. The average size of the nanocrystals and aggregates may in particular be controlled by adjusting the amount and the nature of the nucleating agent (nucleation gel, or crystals, for example of zeolite, or others) and / or of the control agent. The aggregates of dried nanocrystals are then subjected to calcination, a step necessary to obtain a solid ready to be used in applications known to those skilled in the art and which implement zeolites. The calcination especially used to eliminate the control agent can be carried out according to any calcination method known to those skilled in the art. For example, and in a nonlimiting manner, the calcination of the zeolite nanocrystals comprising the control agent can be carried out under oxidizing and / or inert gas scavenging, with in particular gases such as oxygen, nitrogen, air dry and / or decarbonated air, an air depleted of oxygen, optionally dry and / or decarbonated, at a temperature or temperatures above 150 ° C., typically between 180 ° C. and 800 ° C., preferably between 200 ° C. and 650 ° C for a few hours, for example between 2 and 6 hours. The nature of the gases, the ramps of temperature rise and the successive stages of temperatures, their durations will be adapted according to the nature of the control agent. It would not be departing from the scope of the invention by carrying out one or more cationic exchanges (for example with alkali metal or alkaline earth metal salts), before or after the drying step. and / or calcination (step f)), according to conventional cation exchange techniques. As indicated above, the synthesis method of the invention is easy to implement and it is carried out in a relatively short time, and in particular in a reduced time by a factor of at least 4, relative to to synthetic processes known in the prior art which are very long, and / or which are carried out in a very diluted medium, which requires the handling of very large volumes of liquids. This simplicity and rapidity of synthesis do not, however, adversely affect the quality and the properties of the zeolite nanocrystals aggregates (s) thus obtained. Indeed, thanks to the method of the invention, it is possible to increase the selectivity of the synthesis to a zeolite nanocrystals aggregate structure (s). Indeed, with the methods of the prior art, the increase of the microporous volume of the zeolite and the maintenance of a high phase purity, with typically less than 5%, preferably less than 2% of pollutant phase (zeolite phase other than the FAU zeolite), are obtained only by means of very long crystallization times and at relatively low temperatures ( <80 ° C). These methods, however, never reach microporous volumes comparable to those of the invention. [0056] Thus, compared with the other processes for preparing aggregates of zeolite nanocrystals (s), the process of the invention is more productive and less expensive because it is carried out in a single step, of a duration relatively short (generally of the order of about a day) with a low amount of control agent, and therefore overall with a relatively low cost, or at least with a limited additional cost. The use of these aggregates of zeolite nanocrystals (s) is particularly advantageous in industrial processes such as adsorption, ion exchange, separation, and can also be envisaged in all technical fields in which zeolites are usually used, and in particular zeolite material in the form of aggregates of zeolite nanocrystals can be used as an adsorbent, in particular for gas phase or liquid phase separation operations, and more particularly in processes for separating gaseous or liquid streams, such as gas phase pressure swing adsorption processes, temperature or gas phase modulated adsorption processes, fixed bed adsorption processes without regeneration simulated moving bed separation methods, to name but a few non-limiting examples. It is furthermore particularly advantageous, especially for the applications mentioned above, to prepare solid zeolite materials from aggregates of zeolite nanocrystals according to the invention, by agglomeration with a binder. The agglomeration binder that can be used is well known to those skilled in the art and can be selected from clays, organic polymers, silicas, aluminas, and the like, as well as mixtures of two or more of between them. The binder that can be used in the context of the present invention may therefore be chosen from conventional binders known to those skilled in the art, zeolitizable or non-zeolizable, and preferably chosen from clays and clay mixtures, silicas and aluminas. colloidal silicas, alumina gels, and the like, and mixtures thereof. The clays are preferably chosen from: kaolins, kaolinites, nacrites, dickites, halloysites, attapulgites, sepiolites, montmorillonites, bentonites, illites and metakaolins, as well as mixtures of two or more of them in all proportions. The fibrous clays of the sepiolite or attapulgite type may also be used, the clay or the clays being generally capable of being formulated in the form of dry crushed powders and selected, or better still, of gel (ie delaminated clays) and dispersed, and optionally crushed, such as commercial clays Min-U-Gel®, Pansil®, Pangel®, Cimsil®, Attagel®, Actigel®, etc., having or not having undergone one or more chemical treatments . Such gels are for example described in EP170299 or US6743745. The binder content, expressed as anhydrous percentages, is less than or equal to 30%, preferably less than or equal to 20%, and advantageously less than or equal to 15%. [0062] Thus, according to another aspect, the invention relates to a zeolite agglomerate comprising at least one zeolite material in the form of aggregates of FAU zeolite nanocrystals (s) as defined above and at least one binder such as defined above, the binder content being less than or equal to 30%, preferably less than or equal to 20%, and advantageously less than or equal to 15%. It would not be departing from the scope of the invention by operating on the zeolite agglomerate one or more cationic exchanges, according to methods well known to those skilled in the art, and for example as described above, in particular using salt. (s) alkali or alkaline earth metals. The zeolite agglomerate defined above can be used in many applications and in particular those mentioned above for the zeolite material in the form of aggregates of nanocrystals of zeolite (s) of the invention, among others in industrial processes such as adsorption, ion exchange, separation, but also in all technical fields in which zeolites are usually used, and in particular the agglomerate comprising the aggregates of zeolite nanocrystals (s) can be used as an adsorbent, in particular for gas-phase or liquid-phase separations, and particularly in processes for separating gaseous or liquid streams, such as adsorption processes modulated by gas phase pressure, temperature or gas phase modulated adsorption processes, fixed bedless adsorption methods eration, separation processes in simulated moving bed, to name a few non-limiting examples. The present invention is now illustrated by the examples which follow and which are presented without any intention to limit the various embodiments of the invention. In the following examples, the physical properties of zeolite crystals are evaluated by methods known to those skilled in the art, the main of which are recalled below. Loss on ignition of zeolite crystals The loss on ignition is determined in an oxidizing atmosphere, by calcination of the sample in air at a temperature of 950 ° C. ± 25 ° C., as described in standard NF EN 196-2 (April 2006). The standard deviation of measurement is less than 0.1%. Dubinin-Raduskevitch Volume: The Dubinin-Raduskevitch volume is determined from the measurement of the nitrogen adsorption isotherm at its liquefaction temperature. Prior to adsorption, the zeolite adsorbent is degassed at between 300 ° C. and 450 ° C. for a period of between 9 hours and 16 hours, under vacuum (P). <6.7 x 10-4 Pa). The measurement of the adsorption isotherms is then carried out on an ASAP 2020 Micromeritics type apparatus, taking at least 35 measuring points at relative pressures of P / PO ratio of between 0.002 and 1. The microporous volume is determined according to FIG. Dubinin-Raduskevitch from the obtained isotherm, applying the ISO 15901-3 (2007) standard. The microporous volume evaluated according to the Dubinin-Raduskevitch equation is expressed in cm 3 of liquid adsorbate per gram of zeolite. The measurement uncertainty is ± 0.003 cm3.g-1. Size and morphology of crystals (SEM) The estimation of the number-average diameter of the nanocrystals and aggregates of zeolite nanocrystals (s) is carried out as indicated previously by observation under a scanning electron microscope. In order to estimate the size of the zeolite nanocrystals on the samples, a set of images is carried out at a magnification of at least 5000. The diameter of at least 200 crystals is then measured using a dedicated software, for example the Smile View software from the LoGraMi editor. The accuracy is of the order of 3%. The morphology of the nanocrystals and aggregates of nanocrystals of zeolite (s) 10 is qualified from SEM photos taken at magnification adapted to the size of the solids observed. Measurement of the External Surface (S ext in m2.q-1) by the so-called t-plot method: [0071] The t-plot calculation method exploits the data of the nitrogen adsorption isotherm Q ads = f (P / PO) and allows to calculate the microporous surface. The outer surface can be deduced therefrom by differentiating with the BET surface which measures the total porous area in m2.g1 (S BET = S microp. + S ext.). To calculate the microporous surface (S microp.) By the t-plot method, the curve Q ads (cm3.g-1) is plotted as a function of t = thickness of the layer depending on the partial pressure P / PO which would form on a non-porous reference solid (t log P / PO function: Harkins equation and applied Jura (ISO 15901-3: 2007)): [13.99 / (0.034-log (P / P0 )) 1/1, where in the range t between 0.35 nm and 0.5 nm, it is possible to draw a straight line which defines an adsorbed Y intercept which makes it possible to calculate the microporous surface; if the solid is not microporous the line goes through O.
    [0002] Elemental chemical analysis and analysis of Si / Al atomic ratio by X-ray fluorescence Elementary chemical analysis of the solids (nanocrystals, aggregates of nanocrystals, agglomerates) can be carried out according to various analytical techniques known to those skilled in the art. Among these techniques, mention may be made of the technique of chemical analysis by X-ray fluorescence as described in standard NF EN 30 ISO 12677: 2011 on a wavelength dispersive spectrometer (WDXRF), for example Tiger S8 of the Bruker company. X-ray fluorescence is a non-destructive spectral technique exploiting the photoluminescence of atoms in the X-ray domain, to establish the elemental composition of a sample. Excitation of the atoms generally by X-ray beam or by electron bombardment generates specific radiation after the ground state of the atom is returned. The X-ray fluorescence spectrum has the advantage of relying very little on the chemical combination of the element, which offers a precise determination, both quantitative and qualitative. A measurement uncertainty of less than 0.4% by weight is obtained conventionally after calibration for each oxide. These elementary chemical analyzes make it possible to verify the Si / Al atomic ratio of the zeolite, the measurement uncertainty of the Si / Alest atomic ratio of ± 5%. Qualitative and quantitative X-ray diffraction analysis This analysis makes it possible to identify the crystalline phases present in the Zo solid analyzed because each of the zeolite structures has a unique diffractogram defined by the positioning of the diffraction peaks and by their relative intensities. Aggregates of nanocrystals zeolite (s) are spread and smoothed on a sample holder by simple mechanical compression. The diffractogram acquisition conditions realized on the D5000 Brucker apparatus are the following: Cu-tube used at 40 kV-30 mA; - size of the slots (diverging, diffusion and analysis) = 0.6 mm; - filter: Ni; - rotating sample device: 15 rpm; - measuring range: 3 ° <20 <50 °; Step: 0.02 °; - counting time in steps: 2 seconds. The diffractogram obtained is interpreted using the EVA software with phase identification using the ICDD PDF-2 database, release 2011, which makes it possible to demonstrate a perfectly crystalline phase. The amount of zeolite fractions X is measured by XRD analysis. This analysis is carried out on a device of the Bruker brand, then the quantity of the zeolite fractions X is evaluated using the software TOPAS Bruker society. Example 1 (Comparative): Synthesis with nucleation gel and growth gel, without control agent a) Preparation of the growth gel in stirred reactor with Archimedean screw. In a stainless steel reactor of 3 liters equipped with a heating jacket, a temperature probe and a stirrer, a growth gel is prepared by mixing an aluminate solution containing 119 g of sodium hydroxide. sodium (NaOH), 128 g of alumina trihydrate (Al 2 O 3 .3H 2 O, containing 65.2% by weight of Al 2 O 3) and 195.5 g of water at 25 ° C., in 25 minutes, with a stirring speed of 300 rpm in a silicate solution containing 565.3 g of sodium silicate, 55.3 g of NaOH and 1997.5 g of water at 25 ° C. The stoichiometry of the growth gel is as follows: 3.48 Na 2 O / Al 2 O 3 / 3.07 SiO 2/180 H 2 O. Homogenization of the growth gel is carried out with stirring at 300 rpm for 25 minutes at 25 ° C. b) Addition of the nucleating gel [0082] 61.2 g of nucleation gel (ie 2% by weight) of composition 12 Na 2 O / Al 2 O 3 are added to the growth gel, at 25 ° C. with stirring at 300 rpm. SiO 2 was prepared in the same manner as the growth gel and aged for 1 hour at 40 ° C. After 5 minutes of homogenization at 300 rpm, the stirring speed is decreased to 100 rpm continued for 30 minutes. c) Crystallization The stirring speed is lowered to 50 rpm and the set point of the double jacket of the reactor is set at 80 ° C. so that the reaction medium rises to 75 ° C. in 80 minutes. . After standing for 22 hours at 75 ° C., the reaction medium is cooled by circulating cold water in the jacket to stop the crystallization. d) Filtration / Washing [0084] The solids are recovered on sintered material and then washed with deionized water to a neutral pH. e) Drying / Calcination [0085] In order to characterize the product, the drying is carried out in an oven at 90 ° C. for 8 hours, the loss on ignition of the dried product is 23% by weight. A zeolite X of Si / Al atomic ratio equal to 1.24 is obtained in the form of aggregates of very large size. Example 2 (comparative): Synthesis of zeolite X without addition of nucleation gel, and with addition of growth gel, and addition of control agent: SIP / Al 2 O 3 ratio = 0.02 a) Preparation of the growth gel in stirred reactor with Archimedean screw [0087] In a 3 liter stainless steel reactor equipped with a heating jacket, a temperature probe and an agitator, a growth gel is prepared by mixing an aluminate solution containing 119 g of sodium hydroxide (NaOH), 128 g of alumina trihydrate (Al 2 O 3 · 3H 2 O, containing 65.2% by weight of Al 2 O 3) and 195.5 g of water at 25 ° C. in 25 minutes with stirring speed of 300 rpm in a silicate solution containing 565.3 g of sodium silicate, 55.3 g of NaOH and 1997.5 g of water at 25 ° C. The stoichiometry of the growth gel is as follows: 3.48 Na 2 O / Al 2 O 3 / 3.07 SiO 2/180 H 2 O. The homogenization of the growth gel is carried out with stirring at 5 300 rpm for 25 minutes at 25.degree. b) Introduction into the reaction medium of the control agent [0089] 4.4 g of SIP are introduced into the reaction medium with a stirring speed of 300 rpm (SIP / Al 2 O 3 molar ratio = 0, 02). A maturation step is carried out at 25 ° C. for 1 hour at 300 rpm before starting the crystallization. C) Crystallization [0090] The stirring speed is lowered to 50 rpm and the set point of the jacket of the reactor is set at 80 ° C. so that the reaction medium rises to 75 ° C. in 80 ° C. minutes. After standing for 22 hours at 75 ° C., the reaction medium is cooled by circulating cold water in the jacket to stop the crystallization. D) Filtration / Washing [0091] The solids are recovered on sintered material and then washed with deionized water to neutral pH. e) Drying / Calcination [0092] In order to characterize the product, the drying is carried out in an oven at 90 ° C. for 8 hours, the loss on ignition of the dried product is 23% by weight. A zeolite X of Si / Al atomic ratio equal to 1.24 is obtained, in the form of large crystals, weakly aggregated. Example 3 (Invention) Synthesis of zeolite X with addition of nucleation gel and growth gel, and SIP / A1203 control agent = 0.04 a) Preparation of the growth gel in stirred reactor with Archimedean screw [0094 In a 3 liter stainless steel reactor equipped with a heating mantle, a temperature probe and a stirrer, a growth gel was prepared by mixing an aluminate solution containing 119 grams of sodium hydroxide. (NaOH), 128 g of alumina trihydrate (Al 2 O 3 .3H 2 O, containing 65.2% by weight of Al 2 O 3) and 195.5 g of water at 25 ° C. in 25 minutes with a stirring speed of 300 rpm -1 in a silicate solution containing 565.3 g of sodium silicate, 55.3 g of NaOH and 1997.5 g of water at 25 ° C. The stoichiometry of the growth gel is as follows: 3.48 Na 2 O / Al 2 O 3 / 3.07 SiO 2/180 H 2 O. The homogenization of the growth gel is carried out with stirring at 300 tr. min-1 for 25 minutes at 25 ° C. b) Addition of nucleation gel [0096] 61.2 g of nucleation gel (ie 2% by weight) of composition are added to the growth gel at 25 ° C. with stirring at 300 rpm. Na 2 O / Al 2 O 3/10 SiO 2/180 H 2 O prepared in the same manner as the growth gel, and matured for 1 hour at 40 ° C. After 5 minutes of homogenization at 300 rpm, the stirring speed is decreased to 100 rpm and continued for 30 minutes. c) Introduction into the reaction medium of the control agent [0097] 8.8 g of SIP are introduced into the reaction medium with a stirring speed of 300 rpm (SIP / Al 2 O 3 molar ratio = 0.04) . A maturation step is carried out at 25 ° C. for 1 hour at 300 rpm to start the crystallization. d) Crystallization [0098] The stirring speed is lowered to 50 rpm and the set point of the jacket of the reactor is set at 80.degree. C. so that the reaction medium rises to 75.degree. minutes. After standing for 22 hours at 75 ° C., the reaction medium is cooled by circulating cold water in the jacket to stop the crystallization. e) Filtration / Washing [0099] The solids are recovered on sintered material and then washed with deionized water to neutral pH. f) Drying / Calcination In order to characterize the product, the drying is carried out in an oven at 90 ° C. for 8 hours, the loss on ignition of the dried product is 23% by weight. [0101] Aggregates of zeolite X nanocrystals are obtained, aggregates whose atomic ratio Si / Al is equal to 1.24. Example 3a: (Invention) Synthesis of zeolite X with addition of nucleation gel and growth gel, and control agent: ratio SIP / A1203 = 0.12 [0102] The same procedure as Example 3 is carried out but adding 26.4 g SIP instead of 8.8 g to obtain a SIP / A1203 molar ratio equal to 0.12. Aggregates of nanocrystals of zeolite X are obtained, aggregates whose atomic ratio Si / Al is equal to 1.24. EXAMPLE 4 (according to the invention, Fig. 1) Synthesis of zeolite X with addition of nucleation gel and growth gel, and control agent: TPOAC / Al 2 O 3 ratio = 0.01 a) Preparation of In a 50 liter stainless steel reactor equipped with a heating mantle, a temperature probe and a stirrer, a growth gel is prepared by mixing with a stirring jar with an Archimedes' screw. an aluminate solution containing 1810 g of sodium hydroxide (NaOH), 1930 g of alumina trihydrate (Al 2 O 3 .3H 2 O, containing 65.2% by weight of Al 2 O 3) and 3000 g of water at 25 ° C. in 25 minutes with a stirring speed of 140 rpm in a silicate solution containing 8470 g of sodium silicate, 835 g of NaOH and 30100 g of water at 25 ° C. The stoichiometry of the growth gel is as follows: 3.48 Na 2 O / Al 2 O 3 / 3.07 SiO 2/180 H 2 O. The homogenization of the growth gel is carried out with stirring at 140 tr. min-1 for 25 minutes at 25 ° C. b) Addition of nucleation gel [0106] To the growth gel is added at 25 ° C., with stirring at 140 rpm, 923 g of nucleation gel (ie 2% by weight) of composition 12 Na 2 O / A1203 / 10 SiO2 / 180 H2O prepared in the same manner as the growth gel, and having matured for 1 hour at 40 ° C. After 5 minutes of homogenization at 140 rpm, the stirring speed is decreased to 50 rpm and continued for 30 minutes. C) Introduction into the reaction medium of the control agent [0107] 102 g of 60% TPOAC solution in methanol (MeOH) are introduced into the reaction medium with a stirring speed of 140 rpm. 1 (TPOAC / A1203 molar ratio = 0.01). A maturation step is carried out at 25 ° C. for 1 hour at 140 rpm to start the crystallization. D) Crystallization The stirring rate is reduced to 35 rpm and the set point of the jacket of the reactor is set at 80 ° C. so that the reaction medium rises to 75 ° C. in 80 minutes. After standing for 22 hours at 75 ° C., the reaction medium is cooled by circulating cold water in the jacket to stop the crystallization. E) Filtration / Washing The solids are recovered on sintered material and then washed with deionized water to neutral pH. f) Drying / Calcination In order to characterize the product, the drying is carried out in an oven at 90 ° C. for 8 hours, the loss on ignition of the dried product is 23% by weight. Aggregates of nanocrystals of zeolite X are obtained, aggregates whose atomic ratio Si / Al is equal to 1.24. EXAMPLE 5 (Comparative) Synthesis of zeolite X with addition of nucleation gel and growth gel with control agent: TPOAC / Al 2 O 3 ratio = 0.02 10112] The same procedure as in Example 4 is carried out but with the addition of 204 g of 60% TPOAC in methanol instead of 102 g in order to obtain a TPOAC / Al 2 O 3 molar ratio equal to 0.02. Aggregates of large zeolite X crystals are obtained, the Si / Al atomic ratio of which is equal to 1.24. Example 6 (Invention, Fig. 2) Synthesis of zeolite X with addition of microcrystals and growth gel, and with control agent: TPOAC / Al 2 O 3 ratio = 0.014 [0114] The same procedure is carried out as the example 4 where in step b) the nucleation gel is replaced by the introduction of 1% by weight of microcrystals (relative to the total weight of the growth gel) is 462 g anhydrous equivalent of zeolite X crystals (crystals of medium diameter diameter inoculation of about 0.8 μm, prepared as described in the synthesis example b) of the application WO2014 / 0907771), and wherein in step c) the amount of control introduced into the reaction medium is 142.8 g. Aggregates of zeolite X nanocrystals are obtained, aggregates whose atomic ratio Si / Al is equal to 1.24. The solids data obtained in Examples 1 to 6 above are summarized in Table 1 which follows. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a SEM image of the solid obtained in example 4. FIG. 2 is a SEM image of the solid obtained in example 6. TABLE 1 - Conditions of the syntheses Characteristics of aggregates of zeolite nanocrystals FAU Agent Example Type Molar ratio Surface Average size Average size of the aggregates 3 -1 - of seeding agent of external nanocrystals (Pm) VDB (cm .g) Diffract. Control Control / A1203 (m2, g-1) (nm) in Gel Without Example 1 2% Gel Nucleation 0 -> 10 0.335 X pure (comparative) SIP Example 2 No 0.02 25 900 few aggregates 0.326 X pure ( Comparative) Example 3 2) Gel Nucleation 0.04 53 400 1 0.343 X pure (invention) Example 3 bis 2% Gel Nucleation 0.12 52 400 1.5 0.344 X pure (invention) TPOAC Example 4 2% Gel Nucleation 0.01 65 300 2 0.351 X pure (invention) Example 5 2% Gel Nucleation 0.02 85 650 2.5 0.339 X pure (comparative) Example 6 1% Micro crystals 0.014 68 200 3.5 0.347 X pure (invention SIP = N-phenylaminopropyltrimethoxysilane TPOAC = [3- (trimethoxysilylpropyl) octadecyldimethylammonium chloride VDB (cm3.g-1) = Volume of Dubinin-Raduskevich expressed in cm3g-1, Diffract = Qualitative and quantitative analysis by diffraction of X-rays making it possible to identify the crystalline phases present in the solid analyzed pure X = zeolite FAU X with less than 2% of polluting phase.
    权利要求:
    Claims (12)
    [0001]
    REVENDICATIONS1. Zeolite material in the form of aggregates of zeolite nanocrystals (s) FAU having at least the following characteristics: atomic ratio Si / Al of between 1 and 1.4, limits included, external surface area of between 20 m2.g-1 and 80 m 2 g -1, preferably between 30 m 2 g -1 and 80 m 2 g -1, average number diameter of the nanocrystals between 50 nm and 500 nm, preferably between 50 nm and 400 nm, more preferably between 100 nm and 400 nm, more preferably between 100 nm and 300 nm, limits included, and - average size in number of aggregates between 0.2 pm and 10 pm, preferably between 0.3 pm and 10 pm more preferably between 0.5 μm and 8 μm.
    [0002]
    2. The zeolite material as claimed in claim 1, in which the nanocrystals of zeolite (s) are nanocrystals of zeolite (s) of FAU type chosen from zeolites X, MSX and LSX, preferably of the FAU X type.
    [0003]
    Zeolitic material according to Claim 1 or Claim 2, in which the exchangeable sites of the zeolites are occupied by ions chosen from among hydronium, lithium, sodium, potassium, calcium, barium and the like, more preferably from lithium ions. , sodium, potassium, calcium, and barium.
    [0004]
    A process for preparing zeolite nanocrystal aggregates as claimed in any one of claims 1 to 3, employing both a control agent and a seed step with a nucleating agent, such as gel, crystal, mineral particle, and others.
    [0005]
    5. Process according to claim 4, comprising at least the following steps: a) preparation of a so-called growth gel, by mixing a source of silica with a source of alumina, at a temperature of between 0 ° C. and 60 ° C, b) adding to the growth gel of step a) a nucleating agent, at a temperature between 0 ° C and 60 ° C, c) adding to the reaction medium at least one control agent, d) crystallization reaction by increasing the temperature, e) filtration and washing of the obtained zeolite crystals, and f) drying and calcination. 3025789 - 22 -
    [0006]
    6. Method according to one of claims 4 or 5, wherein the growth gel comprises a homogeneous mixture of a source of silica, a source of alumina, a strong mineral base, and water. 5
    [0007]
    7. Method according to one of claims 4 to 6, wherein the nucleating agent is selected from a nucleating gel, a crystal, a mineral particle, a clay, and mixtures thereof.
    [0008]
    8. Method according to one of claims 4 to 7, wherein the amount of control agent (s) used (s) is such that the molar ratio control agent (s) / A1203 starting is between 0.001 and 0.15, preferably between 0.001 and 0.12, limits included.
    [0009]
    9. Method according to one of claims 4 to 8, wherein the control agent is selected from organosilanes.
    [0010]
    10. Method according to one of claims 4 to 9, wherein the control agent is selected from N-phenylaminopropyltrimethoxysilane (SIP), aminopropyltrimethoxysilane (APTMS), isobutyltriethoxysilane (I BTES), octadecyltrimethoxysilane ( ODTMS), silylated polymers, [3- (trimethoxysilyl) propyl] octadecyldimethylammonium chloride (TPOAC), as well as mixtures of two or more of them in all proportions, and preferably among SIP and TPOAC.
    [0011]
    11. zeolite agglomerate comprising at least one zeolite material in the form of aggregates of nanocrystals of zeolite (s) FAU according to any one of claims 1 to 3 and at least one binder, the binder content being less than or equal to 30% preferably less than or equal to 20%, and advantageously less than or equal to 15%.
    [0012]
    12. Use of a material according to any one of claims 1 to 3 or an agglomerate according to claim 11, as an adsorbent, in particular for gas phase separation or liquid phase operations, and any particularly in the processes for separating gaseous or liquid streams, gas phase pressure swing adsorption processes, temperature or gas phase modulated adsorption processes, fixed bed adsorption processes without regeneration, separation methods into simulated moving beds.
    类似技术:
    公开号 | 公开日 | 专利标题
    FR3025789A1|2016-03-18|ZEOLITH NANOCRYSTAL AGGREGATES
    CA2909798C|2018-01-09|Zeolites with hierarchical porosity
    EP3030520B1|2021-06-09|Zeolite material made from mesoporous zeolite
    EP3041793A1|2016-07-13|Zeolites with hierarchical porosity
    CA2922167C|2018-08-28|Zeolitic adsorbents with large external surface area, process for preparing same and uses thereof
    EP3041792A1|2016-07-13|Zeolite material made from a mesoporous zeolite
    EP3218102B1|2020-12-23|Zeolite adsorbent made from a mesoporous zeolite
    FR3024667A1|2016-02-12|ZEOLITHIC ADSORBENTS WITH LOW BINDER AND HIGH EXTERNAL SURFACE, PREPARATION METHOD AND USES THEREOF
    EP3253484B1|2021-04-21|Use of zeolite adsorbents having a high external surface area
    EP3218100A1|2017-09-20|Zeolite adsorbents made from x zeolite with low binder content and low external surface area, method for preparation of same and uses thereof
    CA3044620C|2021-03-23|Zeolite adsorbent material, method of preparation and use for non-cryogenic separation of industrial gases
    同族专利:
    公开号 | 公开日
    US10300455B2|2019-05-28|
    FR3025789B1|2018-04-20|
    CN106999901A|2017-08-01|
    JP2017528405A|2017-09-28|
    CN106999901B|2020-06-16|
    KR20190095544A|2019-08-14|
    KR102099067B1|2020-04-08|
    EP3191401A1|2017-07-19|
    KR20170036030A|2017-03-31|
    US20170274350A1|2017-09-28|
    JP6577571B2|2019-09-18|
    KR102010676B1|2019-08-13|
    WO2016038307A1|2016-03-17|
    JP2019142765A|2019-08-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN103214003A|2013-04-09|2013-07-24|华南理工大学|Mesoporous Y-type zeolite molecular sieve and preparation method thereof|
    WO2015019013A2|2013-08-05|2015-02-12|Ceca S.A.|Zeolites with hierarchical porosity|
    WO2015028740A1|2013-09-02|2015-03-05|Ceca S.A.|Zeolites with hierarchical porosity|
    US3947482A|1974-03-20|1976-03-30|W. R. Grace & Co.|Method for producing open framework zeolites|
    EP0170299B1|1984-08-02|1990-01-17|Tolsa S.A., Industrial|A rheological grade sepiolite product and processes for its manufacture|
    FR2697241B1|1992-10-26|1994-12-16|Elf Aquitaine|Process for the synthesis of zeolites belonging to the structural family of faujasite.|
    FR2750973B1|1996-07-12|1998-10-30|Ceca Sa|USE OF A REACTOR AGITED BY AN ARCHIMEDIC SCREW TYPE SYSTEM FOR THE SYNTHESIS OF FAUJASITE LSX|
    FR2775617B1|1998-03-09|2000-04-07|Ceca Sa|DECARBONATION OF GASEOUS STREAMS USING ZEOLIC ADSORBENTS|
    US6743745B2|2002-01-22|2004-06-01|Zeochem|Process for production of molecular sieve adsorbent blends|
    FR2903978B1|2006-07-19|2010-09-24|Ceca Sa|AGGLOMERATED ZEOLITIC ADSORBENTS, PROCESS FOR THEIR PREPARATION AND USES THEREOF|
    JP5116326B2|2007-03-20|2013-01-09|日揮触媒化成株式会社|Synthesis method of micro faujasite type zeolite|
    JP5483814B2|2007-12-28|2014-05-07|日揮触媒化成株式会社|Colloidal faujasite type zeolite and its synthesis method|
    US9133037B2|2010-10-21|2015-09-15|Uop Llc|Processes for making nano zeolites and for recovery of nano zeolites from an aqueous suspension|
    US8852326B2|2011-03-07|2014-10-07|Exxonmobil Research And Engineering Company|Aggregates of small particles of synthetic faujasite zeolite|
    US8603433B2|2011-04-13|2013-12-10|Uop Llc|Aluminosilicate X-type zeolite compositions with low LTA-type zeolite|
    FR2999098B1|2012-12-12|2022-01-14|Ceca Sa|ZEOLITHIC ADSORBENTS, THEIR PREPARATION PROCESS AND THEIR USES|FR3009300A1|2013-08-05|2015-02-06|Ceca Sa|ZEOLITHES HIERARCHISED POROSITY|
    CN110508241A|2018-05-22|2019-11-29|中国石油化工股份有限公司|A kind of coalescence type adsorbent and preparation method thereof|
    EP3610945A1|2018-08-16|2020-02-19|Sibelco Nederland N.V.|A material and a method for the removal of pollutants from water|
    KR102220082B1|2019-07-23|2021-02-25|노경태|Aluminosilicates structure with novel structure and wool-like type morphology, manufacturing method thereof and HPLC column packed with the same as stationary phase|
    FR3103393A1|2019-11-27|2021-05-28|Arkema France|SEPARATION OF GAS FROM AIR|
    CN111732110B|2020-01-21|2022-02-25|中国石油大学|NaY zeolite and preparation method thereof|
    法律状态:
    2015-08-11| PLFP| Fee payment|Year of fee payment: 2 |
    2016-03-18| PLSC| Search report ready|Effective date: 20160318 |
    2016-08-16| PLFP| Fee payment|Year of fee payment: 3 |
    2017-08-10| PLFP| Fee payment|Year of fee payment: 4 |
    2017-10-27| TP| Transmission of property|Owner name: ARKEMA FRANCE, FR Effective date: 20170922 |
    2018-08-13| PLFP| Fee payment|Year of fee payment: 5 |
    2019-08-15| PLFP| Fee payment|Year of fee payment: 6 |
    2020-08-12| PLFP| Fee payment|Year of fee payment: 7 |
    2021-08-12| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1458592|2014-09-12|
    FR1458592A|FR3025789B1|2014-09-12|2014-09-12|ZEOLITH NANOCRYSTAL AGGREGATES|FR1458592A| FR3025789B1|2014-09-12|2014-09-12|ZEOLITH NANOCRYSTAL AGGREGATES|
    CN201580045441.6A| CN106999901B|2014-09-12|2015-09-10|Zeolite nanocrystal agglomerates|
    EP15771199.5A| EP3191401A1|2014-09-12|2015-09-10|Zeolite nanocrystal aggregates|
    KR1020197023083A| KR102099067B1|2014-09-12|2015-09-10|Zeolite nanocrystal aggregates|
    KR1020177005121A| KR102010676B1|2014-09-12|2015-09-10|Zeolite nanocrystal aggregates|
    US15/504,241| US10300455B2|2014-09-12|2015-09-10|Zeolite nanocrystal aggregates|
    JP2017508651A| JP6577571B2|2014-09-12|2015-09-10|Zeolite nanocrystal aggregates|
    PCT/FR2015/052412| WO2016038307A1|2014-09-12|2015-09-10|Zeolite nanocrystal aggregates|
    JP2019057740A| JP2019142765A|2014-09-12|2019-03-26|Zeolite nanocrystal aggregates|
    [返回顶部]