A METHOD FOR PREPARING MESOPOROUS MICROPOROUS CRYSTALLINE MATERIALS INVOLVING A RECOVERABLE AND RECYCLABLE MESOPORE-TEMPLATING AGENT

Abstract

A method for preparing mesoporous microporous crystalline material involving at least one mesopore-templating agent, said mesopore-templating agent being soluble under the form of unimers and able to generate a micellization with temperature increase so that unimers assemble to form micellar aggregates, and the micellization being reversible with temperature change.

Claims

1.-15. (canceled)

16. A method for preparing a mesoporous microporous crystalline material, the method comprising: (a) preparing a basic aqueous solution comprising a parent material comprising a microporous crystalline material, the microporous crystalline material comprising (i) an aluminosilicate or seeds thereof, (ii) precursors of (i), or (iii) a combination of materials from (i) and (ii); and at least one mesopore-templating agent, the mesopore-templating agent being soluble under a form of one or more unimers in the basic aqueous solution, able to generate a micellization with a temperature increase so that the unimers assemble to form micellar aggregates, the micellization being reversible when decreasing temperature; (b) subjecting the solution of step (a) to one or more hydrothermal conditions, the micellization of the mesopore-templating agent in solution occurring at a temperature lower than the temperature of the hydrothermal conditions; (c) stopping the treatment of step (b) by cooling down the solution as obtained in (b) so as to dissociate the micellar aggregates of the mesopore-templating agent and optionally neutralizing the system with an acid-containing solution; (d) recovering the mesoporous microporous crystalline material of step (c) and recovering at least a part of the mesopore-templating agent; and (e) optionally, placing the mesoporous microporous crystalline material of step (d) in contact, with an ion exchange solution.

17. The method according to claim 16, wherein the parent material is (i) an aluminosilicate selected among Y zeolite, being in protonated form and having a FAU structure and a bulk Si/Al ratio above or equal to 12, and which may be obtained, by applying to a parent Y zeolite at least one dealumination treatment, or ZSM-5, mordenite, ferrierite and zeolite Beta, or (ii) the precursors of materials of (i) comprising an inorganic source of silicon selected among precipitated silica, pyrogenic silica (fumed silica), and an aqueous colloidal suspension of silica; or an organic source of silicon, preferably a tetraalkyl orthosilicate; and comprising a metal source selected from metal oxide, metal salt, and metal alkoxide, wherein the metal is selected among aluminium, boron, iron, gallium and titanium.

18. The method according to claim 16, wherein the mesopore templating agent contains an oligomeric or polymeric chain bearing at least one ionic function and rendered amphiphilic upon the effect of the variation of a physico-chemical parameter, preferably chosen among pH, temperature and ionic strength.

19. The method according to claim 16, wherein the mesopore templating agent comprises: an LCST above 15 C., more preferably above 20 C., most preferably above 30 C. and below 200 C., more preferably below 120 C., more preferably below 100 C. or; a statistical copolymer of ethylene and propylene functionalized by a quaternary ammonium salt, the molecular size of which ranges from 140 to 5000 g/mol and the ethylene oxide/propylene oxide molar ratio of which ranges from 0.01 to 5; or a Jeffamine comprising Jeffamine M600 or Jeffamine M2005 wherein the amino group of the mesopore-templating agent is quaternized.

20. The method of claim 19, wherein the quaternary ammonium salt comprises one or more Jeffamines, wherein the Jeffamines is quaternized on a primary amine wherein the amino group of the mesopore-templating agent is quaternized with chloride or bromide or hydroxide

21. The method according to claim 16, wherein the unimers have a hydrodynamic diameter of 0.1 to 5 nm at room temperature and the micellar aggregates have a hydrodynamic diameter of 10 nm to 2 m at a temperature ranging from 40 to 90 C. respectively.

22. The method according to claim 16, wherein the basic aqueous solution in step (a) comprises a base, the base selected from the group consisting of alkali hydroxide, alkaline earth hydroxide, tetraalkylammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium citrate, potassium citrate, ammonium citrate, NH.sub.4OH, and combinations thereof.

23. The method according to claim 22, wherein the basic aqueous solution in step (a) comprises a base, wherein the base is a tetramethylammonium hydroxide solution.

24. The method according to claim 16, wherein the mesopore templating agent/Si ratio in step (a) ranges from 0.01 to 0.5, preferably from 0.041 to 0.3, more preferably from 0.08 to 0.165.

25. The method according to claim 16, wherein in step (b), the basic aqueous solution as prepared in step (a) is submitted to mild hydrothermal conditions the hydrothermal conditions comprising: a temperature of 90 to 200 C., for about 5 to 30 hours; and an autogeneous pressure from 1 to 20 bara.

26. The method according to claim 16, wherein recovering the mesoporous microporous crystalline material in step (d) comprises: (d1) filtration, (d2) optionally washing, in sequential or continuous mode, of the mesoporous microporous crystalline material so as to extract the mesopore-templating agent at least in part, with a washing solution, (d3) drying, and (d4) optionally calcination.

27. The method of claim 26, wherein the washing solution comprises (i) demineralized water or (ii) a water solution containing nitric acid, ammonia or ammonium nitrate, or (iii) pure methanol.

28. The method according to claim 16, wherein in step (d) the mesoporous microporous crystalline material is recovered by filtration and the filtrate is recovered and recycled as a basic aqueous solution at step (a) in another mesoporization processing, after being adjusted to a basic pH, the mesoporization processing being repeated at least one more time.

29. The method according to claim 16, leading to mesoporous microporous crystalline silicates or aluminosilicates comprising one or more of the following characteristics: a homogenous vermicular mesoporous phase in the solid crystalline silicate or aluminosilicate; mesopores having a narrow size distribution centered between about 3 nm and about 50 nm; micropores and mesopores which are connected.

30. A mesopore-templating agent comprising an organic cationic product having (i) a molecular weight between 250 and 3000 g/mol, (ii) an optionally branched hydrocarbon chain comprising from 12 to 150 carbon atoms and from 5 to 45 oxygen atoms which are inserted within the hydrocarbon chain and wherein each oxygen is bound with two distinct carbon atoms to obtain ether bonds, (iii) a terminal quaternary ammonium moiety ({[N(R4)(R5)](R6).sub.n}H).sup.+, wherein R4 and R5 are each selected among C.sub.1-C.sub.10 alkyl, R6 is (CH.sub.2).sub.m with .sub.m=1 to 10 and .sub.n is 1, 2 or 3, preferably 1.

31. A mesopore templating agent according to claim 30, having the general structure [R1O(R2O).sub.a(R3).sub.bN(R4)(R5)(R6)].sup.+, X.sup.; wherein: (.sub.a) and (.sub.b) are each independently comprised between 0 and 75, and the sum of (.sub.a) and (.sub.b) is not above 75; and R1, R2, R3, R4, R5, R6 are each independently chosen among C.sub.1-C.sub.6 alkyl, where R1 is methyl, R2, R3, are each ethyl, propyl or isopropyl, wherein R4, R5, R6 are each independently chosen among C.sub.1-C.sub.3 alkyl; and X.sup. is an anion comprising Cl, Br or OH.

Description

LEGEND OF THE FIGURES

[0094] FIG. 1: SEM images of parent zeolite HY15 (left) and of recrystallized zeolite in presence of CTAB HY15-TMAOH-20 (Solid A) (right)

[0095] FIG. 2: TEM images of the parent zeolite HY15

[0096] FIG. 3: TEM images of recrystallized zeolite in presence of CTAB HY15-TMAOH-20 (Solid A)

[0097] FIG. 4: N.sub.2 adsorption-desorption isotherms of parent zeolite HY15 and of recrystallized zeolite HY15-TMAOH-20 (Solid A)

[0098] FIG. 5: Pore size distribution(taken from adsorption branch) of parent zeolite HY15 and of recrystallized zeolite HY15-TMAOH-20 (Solid A)

[0099] FIG. 6: Ar adsorption-desorption isotherms at 196 C. of parent zeolite HY15 and of recrystallized zeolite HY15-TMAOH-20 (Solid A)

[0100] FIG. 7: Large angle X-Ray diffractograms of parent zeolite HY15 and of recrystallized zeolite HY15-TMAOH-20 (Solid A)

[0101] FIG. 8: Small angles X-Ray diffractogram of parent zeolite HY15 and recrystallized zeolite HY15-TMAOH-20 (Solid A)

[0102] FIG. 9: Distribution of the hydrodynamic diameter (Dh) as a function of temperature determined by DLS for a solution of quaternized Jeff M600-Cl (1% wt) at a pH of 12.3

[0103] FIG. 10: TEM images of the zeolite recrystallized in presence of quaternized Jeffamine Jeff M600-Cl (Solid B)

[0104] FIG. 11: SEM images of the zeolite recrystallized in presence of quaternized Jeffamine Jeff M600-Cl (Solid B)

[0105] FIG. 12: X-Ray diffractograms of zeolites recrystallized in presence of Jeff M600-Cl at 100 C. (Solid D), 120 C. (Solid C) and 150 C. (Solid B)

[0106] FIG. 13: N.sub.2 adsorption-desorption isotherms of zeolites recrystallized in presence of Jeff M600-Cl at 100 C. (Solid D), 120 C. (Solid C) and 150 C. (Solid B) (left) and their corresponding pore size distribution (right)

[0107] FIG. 14: X-Ray diffractograms of recrystallized zeolites in presence of quaternized Jeff M600-Cl 120 C. with a Jeffamine/Si molar ratio of 0.082 (Solid C) and 0.164 (Solid E)

[0108] FIG. 15: N.sub.2 adsorption-desorption isotherms of recrystallized zeolites in presence of quaternized Jeff M600-Cl at 120 C. with a Jeffamine/Si molar ratio of 0.082 (Solid C) and 0.164 (Solid E) (left) and their corresponding pore size distribution (right)

[0109] FIG. 16: TEM images of the zeolite recrystallized using a Jeffamine/Si ratio of 0.164 (Solid E)

[0110] FIG. 17: X-Ray diffractograms of recrystallized zeolites in presence of the different quaternized Jeffamines M600-Cl (Solid B), M1000-Cl (Solid F), M2005-Cl (Solid G)

[0111] FIG. 18: N.sub.2 adsorption-desorption isotherms of recrystallized zeolites in presence of different quaternized Jeffamines M600-Cl (Solid B), M1000-Cl (Solid F), M2005-Cl (Solid G) (left) and their corresponding pore size distribution (right)

[0112] FIG. 19: N.sub.2 adsorption-desorption isotherms of recrystallized zeolites obtained by recycling of the quaternized Jeffamine M600 (left) and their corresponding pore size distribution (right)

[0113] FIG. 20: X-Ray Diffractograms of parent HY15 zeolite, of the recrystallized Y using M600 Jeffamine (solid I) and of the recrystallized Y using quaternized M600 Jeffamine (solid B)

[0114] FIG. 21: N2 adsorption and desorption isotherms of parent HY15 zeolite, of the recrystallized Y using M600 Jeffamine (solid I) and of the recrystallized Y using quaternized M600-Cl Jeffamine (solid B)

[0115] FIG. 22: top: TEM images of the recrystallized Y using M600 Jeffamine (solid I) [0116] Bottom: TEM images of the recrystallized Y using quaternized M600 Jeffamine (solid B)

[0117] FIG. 23: N2 physisorption isotherms of the CTAB recristallized Y zeolite before (solid J) and after (solid A) calcination

[0118] The following Examples illustrate the present invention without limiting its scope.

[0119] In these Examples, the following abbreviations are used: [0120] CTAB: hexadecyltrimethylammonium bromide [0121] TAMOH: tetramethylammonium hydroxide [0122] PEO: poly(ethylene oxide) [0123] PPO: poly(propylene oxide) [0124] EO: ethylene oxide [0125] PO: propylene oxide [0126] DLS: dynamic light scattering [0127] LCST: lower critical solution temperature ( C.) [0128] SEM: scanning electron microscopy [0129] TEM: transmission electron microscopy [0130] S.sub.BET: apparent surface area (specific surface area) [0131] V.sub.micro: micropore volume (mL/g) [0132] V.sub.meso: mesopore volume (mL/g) [0133] S.sub.mic: micropore surface area (m.sup.2/g) [0134] S.sub.mes: mesopore surface area (m.sup.2/g) [0135] V.sub.tot: total pore volume (mL/g) [0136] V.sub.large meso: volume of the large mesopores (above 10 nm) [0137] LOI: loss on ignition (% wt)

Zeolites:

[0138] (a) Parent Zeolite [0139] HY15: a commercial Y zeolite in protonated form having the FAU structure and a Si/Al ratio of 15 (CBV720 post-treated by dealumination, Zeolyst)

[0140] The main characteristics of HY15 parent zeolite are gathered in the table below

TABLE-US-00001 Nitrogen adsorption V large LOI.sup.a Vmicro V meso meso V tot S BET Dpores.sup.c Solids (% wt) Si/Al.sup.b (ml/g) (ml/g) (ml/g) (ml/g) (m.sup.2/g) (nm) HY15 3 16.1 0.218 0.164 0.086 0.468 814 25

[0141] To be stressed, the presence of disordered mesopores already present in the zeolite crystals. [0142] (b) Recrystallized zeolite [0143] Solid A: the solid obtained by the recrystallization of HY15 using CTAB as organic template [0144] Solids B to H: the solids obtained by the recrystallization of HY15 using mesopore templating agent according to the present invention.

[0145] A polymer group, called Jeffamine, are statistic copolymers of PEO and PPO. Different types of functionnalization (mono-, di-, tri-primary amines) are proposed. All these polymers are cheap commercially available polymers.

[0146] The size of the PEO and PPO chain may vary as well as the relative proportion of the PEO/PPO ratio, leading to a large variety of commercially available Jeffamines, the molecular size of which varying from 140 to 5000 g/mol. The relative proportion of EO and PO units in the polymer chain is of key importance as it determines the hydrophilic/hydrophobic balance as well as the LCST. Jeffamines are thermosensitive copolymers.

TABLE-US-00002 TABLE 1 Characteristics of the Jeffamine used Approximative EO/PO Hydrophilic/ molecular molar hydrophobic Reference weight (g/mol) ratio balance [00001] Jeffamine M600 600 1/9 2 [00002] Jeffamine M1000 1000 19/3 17 [00003] Jeffamine M2005 2000 6/29 2.8

Characterization Techniques:

[0147] The powder X-ray diffraction patterns were measured on a Bruker D8 Advance diffractometer (weighted mean CuK radiation at =1.541838 ) with a Bragg-Brentano geometry and equipped with a Bruker Lynx Eye detector. The data were recorded in the range 0.5-6 and 5-35 2 with an angular step size of 0.0197 and a counting time of 0.1 s per step.

[0148] The SEM observations were performed by using a Hitachi S4800 microscope with a resolution of 1 nm. The samples were first covered with platinum.

[0149] The TEM experiments were performed by using a JEOL 1200 EX II electron microscope operated at 100 kV with a resolution of 0.5 nm. The samples were prepared by dispersion in ethanol and deposition onto a carbon-coated copper grid. The observations of thin slices of 70 nm thickness were also obtained by ultramicrotomy of the sample embedded in a polymer resin (LR White) then deposited on a copper grid.

[0150] The N.sub.2 and Ar adsorption-desorption isotherms were measured at 196 C. on a Micromeritics TriStar 3000 instrument and an ASAP 2020 instrument. Prior to each measurement, the samples were outgassed in vacuum at 250 C. for at least 6 hours (for N.sub.2) and at least 12 hours (for Ar).

[0151] The apparent surface areas (S.sub.BET) were determined according to the BET model from the adsorption branches. The micro- and mesopore volumes (Vmic, Vmes) together with the micro- and mesopore surface areas (Smic, Smes) for nitrogen and argon were calculated using the .sub.s-plot method, with the non porous silica Aerosil 200 as a reference adsorbent. The total pore volumes (Vtot) were evaluated from the amount adsorbed at a relative pressure of about 0.99 using the liquid nitrogen (or argon) density at 77K.

[0152] The Dynamic Light Scattering (DLS) measurements were performed with a Zetasizer Nano ZS apparatus from Malvern Instruments equipped with a helium-neon laser of 4 mW at 632.8 nm and a backscatter detector located at 173 to the incident beam. The temperature can be set from 5 to 90 C. with precision (+/0.1 C.) using thermoelectric Peltier cells. The samples were filtered through nylon syringe filter 0.2 m, directly into the quartz measurement cell (1 cm) previously dried. The cell is closed with a Teflon stopper and stabilized at the desired temperature for 2 minutes. Parameters such as the number of accumulations or the depth measurement in the vessel are automatically optimized by the device. This technique allows determining the size of objects in solution based on their Brownian motion by studying the distribution of a coherent monochromatic incident beam (laser). These objects may be nano particles or polymers in solution, assembled or not in the form of micelles or aggregates.

EXAMPLE 1

Preparation of Chloride-Quaternized Jeffamine M600

(a) Preparation of Iodide Quaternized Jeffamine

[0153] The quaternization of the primary amine of the Jeffamine has been performed by reacting an excess of iodomethane CH.sub.3I according to the synthesis protocol of Cope et al. [A. C. Cope, JACS, 1960, 82, 4651-4655].

[0154] In a 500 ml vessel equipped with a cooler, 41.5 g (0.07 mol) of Jeffamine M600 are dissolved in 300 ml of methanol in presence of 34 g (0.4 mol) of sodium bicarbonate. 30 g (0.21 mol) of iodomethane CH.sub.3I are added under stirring before heating under reflux during 72 hours away from light. After 24 hours, 30 g (0.21 mol) of additional iodomethane CH.sub.3I are added to the reaction medium. After complete cooling, the water traces are removed by adding anhydrous magnesium sulfate and the solution is filtered to remove the precipitated salts. The filtrate is evaporated at 80 C. under vacuum to obtain a visqueous ambarino yellow liquid, containing precipitated salts. A small amount of chloroform is added to dissolve the polymer and insoluble salts are removed by cold filtration. The solvent is then evaporated to recover the Jeffamine iodide quaternized M600.

[0155] The yield of the quaternization is 95% for the iodide quaternized Jeffamine M600.

(b) Preparation of Chloride Quaternized Jeffamine

[0156] 20 g (0.026 mol) of iodide quaternized Jeffamine from step (a) were dissolved in 200 ml of water. 20 ml of Amberlyst IRA400 resin (1.4 meq/ml) under chloride form were first washed with water before adding the solution of iodide quaternized Jeffamine. The reactional medium is then heated up to 50 C. under stirring during 24 hours. After cooling down, the suspension is filtered and the filtrate is subsequently processed with a flowrate of 2 ml/min on a column loaded with 20 ml of Amberlyst IRA400 resin previously washed. The recovered solution is evaporated at 90 C. under vacuum to remove water. The remaining chloride quaternized Jeffamine is then dissolved in absolute ethanol to remove any water traces by azeotropic evaporation under vacuum. The obtained chloride quaternized Jeffamine is a white waxy solid.

(c) Micellar Behavior of Chloride-Quaternized Jeffamine in Basic Medium

[0157] The polymeric chain of Jeffamine is thermosensitive. At low temperature, the quaternized Jeffamine M600 is soluble under the form of unimer (1 nm) in solution. Starting from 50 C., the hydrophobicity of the polymer chain is high enough to generate a surfactant behavior so that unimers assemble to form small objects. With temperature increase, the chain becomes more and more hydrophobic and micelles turn into aggregates of around 50 nm from 50 C. up to 530 nm at 90 C. as determined by DLS. No precipitation is observed as micelles are stabilized by their positive charged corona. The micelles formation is reversible as by decreasing the temperature back below 50 C. the Jeffamine unimers are completely dissociated in solution.

[0158] For the quaternized Jeffamine M600, micelles are formed from 75 C. and the size of the micelles grows from 75 C. up to 90 C.

EXAMPLE 2 (Comparative)

Preparation of Solid A by Recrystallization of HY15 Zeolite using CTAB as Organic Template

[0159] The recrystallization of the parent sample HY15 zeolite has been performed according to the synthesis protocol described by Ying. et al. [J. Y. Ying, US2007244347]: 1.67 g of the HY15 zeolite are mixed together at room temperature with 50 ml of a 0.09M TMAOH solution under vigourous stirring in a 120 ml autoclave. 0.83 g of CTAB are then added to the suspension maintained under stirring during 20 min. The mixture has a CTAB/Si molar ratio of 0.082. The autoclave is then hermetically closed and the reactional medium submitted to static hydrothermal conditions at 150 C. under autogeneous pressure during 20 hours. After quick cooling down of the autoclave in a water bath, the solid is recovered by filtration and washed using demineralized water until a neutral pH is reached. The solid is then dried overnight in an oven at 80 C. The whole solid porosity is recovered by complete calcination of the contained organic species (CTAB and TMAOH) in a tubular oven at 550 C. (1 C./min) during 8 hours under air (200 ml/h).

[0160] The characteristics of the parent zeolite Solid A as obtained are reported in Table 2.

TABLE-US-00003 TABLE 2 Characteristics of parent zeolite HY15 and recrystallized zeolite in presence of CTAB (Solid A) Cristallite LOI.sup.a size.sup.b Nitrogen adsorption Samples (%) (nm) Si/Al.sup.c V.sub.micro V.sub.meso.sup.d V.sub.largemeso V.sub.tot S.sub.BET HY15 3 57 16.1 0.218 0.164 0.086 0.468 814 Solid A 34 53 15.0 0.094 0.529 0.014 0.636 818 .sup.adetermined by ATG between 150 and 900 C.; .sup.bdetermined by XRD; .sup.cdetermined by EDX; .sup.dbetween 2 and 10 nm.

[0161] The recrystallization of zeolite HY15 in the presence of the CTAB is efficient to generate mesoporosity inside the zeolite, while preserving the initial crystal shape. The recrystallized materials possess a hierarchical structure with long range zeolite crystallinity and a high mesoscopic order of the mesopores located in the same crystals (FIG. 1 and FIG. 3). A bimodal interconnected pore system was obtained with narrow size distributions of micropores (0.74 mm-7.4 ) and mesopores (4.3 mm-43 ) (FIGS. 4 et 5).

EXAMPLE 3

Preparation of Solid B by Recrystallization of HY15 Zeolite using Chloride Quaternized Jeffamine M600 as Organic Template

(a) Preparation of the Reaction Mixture

[0162] 0.462 g (0.682 mmol) of chloride quaternized Jeffamine M600 is dissolved under stirring at room temperature in 15 ml of 0.09M TMAOH solution during 10 min in a 20 ml autoclave.

[0163] 0.5 g of HY15 are then added to the solution under stirring during 20 min. The amount of quaternized Jeffamine M600 has been determined by keeping a N.sup.+/Si ratio of 0.082.

(b) Preparation of Solid B

[0164] The autoclave is then hermetically closed and the reactional medium submitted to static hydrothermal conditions at 150 C. under autogeneous pressure during 20 hours. After quick cooling down of the autoclave in a water bath, the solid is recovered by filtration and washed using demineralized water until a neutral pH is reached. The solid is then dried overnight in an oven at 80 C. The solid porosity is recovered by washing or calcination of the contained organic matter in a tubular oven at 550 C. (1 C./min) during 8 hours under air (200 ml/h).

(c) Characterization of Solid B

[0165] The characteristics of the Solid B are reported in Table 3.

[0166] In FIG. 12, large-angles XRD clearly shows that the Y zeolitic structure is preserved; using small-angles XRD, the presence of a shoulder at around 12 indicates that the recrystallized solid is mesostructured. Such a mesostructure is confirmed on N.sub.2 adsorption isotherms (FIG. 13) exhibiting a strong adsorption at a relative pressure comprised between 0.5 and 0.7. The corresponding mesopores have a narrow distribution centered around 5.9 nm, representing a volume of 0.274 ml/g, corresponding to an increase of 67% of the mesoporous volume compared to the parent HY15 zeolite. These results are confirmed by TEM images showing the formation of a homogeneous vermicular mesoporous phase in the solid (FIG. 10). Microporosity and mesoporosity are intimately connected suggesting an excellent interconnectivity between the two pore systems and bringing the proof of the true hierarchical porosity of the recrystallized zeolite crystals. The MEB images (FIG. 11) show that the typical crystalline shape and size of the precursor zeolite Y are maintained after the recrystallization treatment, thus confirming also the pseudomorphic character of the recrystallization.

EXAMPLE 4

Preparation of Solid C by Recrystallization of Y Zeolite using Chloride Quaternized Jeffamine M600 as Organic Template

(a) Preparation of the Reaction Mixture

[0167] The procedure is the same as in Example 3 (a).

(b) Preparation of Solid C

[0168] The procedure is the same as in Example 3 (b) except that the reaction mixture was subjected to 120 C. instead of 150 C.

(c) Characterization of Solid C

[0169] The characteristics of the Solid C are reported in Table 3.

[0170] As for Solid B, the same conclusions can be drawn: conservation of the structure of the parent zeolite Y; formation of a homogeneous vermicular mesoporous phase in the solid; mesopores have a narrow distribution centered around 5.5 nm; microporosity and mesoporosity are intimately connected suggesting an excellent interconnectivity between the two pore systems and bringing the proof of the true hierarchical porosity of the recrystallized zeolite crystals.

EXAMPLE 5

Preparation of Solid D by Recrystallization of HY15 Zeolite using Chloride Quaternized Jeffamine M600 as Organic Template

(a) Preparation of the Reaction Mixture

[0171] The procedure is the same as in Example 3 (a).

(b) Preparation of Solid D

[0172] The procedure is the same as in Example 3 (b) except that the reaction mixture was subjected to 100 C. instead of 150 C.

(c) Characterization of Solid D

[0173] The characteristics of the Solid D are reported in Table 3.

[0174] As for Solid B and C, the same conclusions can be drawn: conservation of the structure of the parent zeolite Y; formation of a homogeneous vermicular mesoporous phase in the solid; mesopores have a narrow distribution centered around 5.5 nm; microporosity and mesoporosity are intimately connected suggesting an excellent interconnectivity between the two pore systems and bringing the proof of the true hierarchical porosity of the recrystallized zeolite crystals.

EXAMPLE 6

Preparation of Solid E by Recrystallization of Y Zeolite using Chloride Quaternized Jeffamine M600 as Organic Template

(a) Preparation of the Reaction Mixture

[0175] 0.924 g (1.36 mmol) of chloride quaternized Jeffamine M600 is dissolved under stirring at room temperature in 15 ml of 0.09M TMAOH solution during 10 min in a 20 ml autoclave. 0.5 g of HY15 zeolite are then added to the solution under stirring during 20 min. The amount of quaternized Jeffamine M600 has been determined by keeping a N.sup.+/Si ratio of 0.164.

(b) Preparation of Solid E

[0176] The procedure is the same as in Example 4 (b).

(c) Characterization of Solid E

[0177] The characteristics of the Solid E are reported in Table 3.

[0178] As for Solid B, C and D, the same conclusions can be drawn: conservation of the structure of the parent zeolite Y; formation of a homogeneous vermicular mesoporous phase in the solid; conservation of the Y zeolitic structure; mesopores have a narrow distribution centered around 5.5 nm; microporosity and mesoporosity are intimately connected suggesting an excellent interconnectivity between the two pore systems and bringing the proof of the true hierarchical porosity of the recrystallized zeolite crystals.

EXAMPLE 7

Preparation of Solid F by Recrystallization of HY15 Zeolite using Chloride Quaternized Jeffamine M1000 as Organic Template

(a) Preparation of Reaction Mixture

[0179] 0.74 g (0.682 mmol) of chloride quaternized Jeffamine M1000 is dissolved under stirring at room temperature in 15 ml of 0.09M TMAOH solution during 10 min in a 20 ml autoclave. 0.5 g of HY15 zeolite are then added to the solution under stirring during 20 min. The amount of quaternized Jeffamine M1000 has been determined by keeping a N.sup.+/Si ratio of 0.082.

(b) Preparation of Solid F

[0180] The autoclave is then hermetically closed and the reactional medium submitted to static hydrothermal conditions at 150 C. under autogeneous pressure during 20 hours. After quick cooling down of the autoclave in a water bath, the solid is recovered by filtration and washed using demineralized water until a neutral pH is reached. The solid is then dried overnight in an oven at 80 C. The solid porosity is recovered by washing or calcination of the organic matter contained in a tubular oven at 550 C. (1 C./min) during 8 hours under air (200 ml/h).

(c) Characterization of Solid F

[0181] The characteristics of the Solid F are reported in Table 3. The use of chloride quaternized Jeffamine M1000 does not allow to create a mesostructure in the HY15 zeolite: the N2 isotherms of solid F present the same trend as the one of the parent HY15, indicating a similar pore size distribution. The Jeffamine M1000 having a high hydrophilic/hydrophobic balance, its corresponding LCST is not fitting with the recrystallization conditions used.

EXAMPLE 8

Preparation of Solid G by Recrystallization of HY15 Zeolite using Quaternized Jeffamine M2005 as Organic Template

(a) Preparation of the Reaction Mixture

[0182] 1.42 g (0.682 mmol) of chloride quaternized Jeffamine M2005 is dissolved under stirring at room temperature in 15 ml of 0.09M TMAOH solution during 10 min in a 20 ml autoclave. 0.5 g of HY15 zeolite are then added to the solution under stirring during 20 min. The amount of quaternized Jeffamine M2005 has been determined by keeping a N.sup.+/Si ratio of 0.082.

(b) Preparation of Solid G

[0183] The procedure is the same as in Example 5 (b).

(c) Characterization of Solid G

[0184] The characteristics of the Solid G are reported in Table 3.

[0185] Here again, the formation of a true hierarchical porosity of the recrystallized zeolite crystals is confirmed having the following characteristics: conservation of the structure of the parent zeolite Y; formation of a homogeneous vermicular mesoporous phase in the solid; the distribution of mesopores is this time larger than for Solid B with two main contributions centered respectively around 8 and 15 nm; microporosity and mesoporosity are intimately connected. It is also the proof that even by using recyclable structuring agents, it is possible to tune the size of the mesopores of the mesostructure by an accurate choice of the structuring agent.

EXAMPLE 9

Preparation of Solids H to Hviii by Recrystallization of HY15 Zeolite using Chloride Guaternized Jeffamine M600 and Different Extraction Conditions

(a) Preparation of the Reaction Mixture

[0186] 0.924 g (1.36 mmol) of chloride quaternized Jeffamine M600 is dissolved under stirring at room temperature in 15 ml of 0.09M TMAOH solution during 10 min in a 20 ml autoclave. 0.5 g of HY15 zeolite are then added to the solution under stirring during 20 min. The amount of chloride quaternized Jeffamine M600 has been determined by keeping a N.sup.+/Si ratio of 0.164.

(b) Preparation of the Solids H to Hviii

[0187] The autoclave is then hermetically closed and the reactional medium submitted to static hydrothermal conditions at 120 C. under autogeneous pressure during 20 hours. After quick cooling down of the autoclave in a water bath, different routes have been investigated: [0188] Solid H: the solid is recovered by filtration and washed using demineralized water until a neutral pH is reached. The solid is then dried overnight in an oven at 80 C. The solid porosity is recovered by calcination of the contained organic matter in a tubular oven at 550 C. (1 C./min) during 8 hours under air (200 ml/h). [0189] Solid Hi: the solid is recovered by filtration at 25 C. without washing. The solid is then dried overnight in an oven at 80 C. and its characteristics are reported in Table 4. [0190] Solid Hii to Hiv: the solids are recovered by filtration at 25 C. followed by a washing step performed respectively at 0 C., 27 C. and 40 C. The washing step is performed by introducing 100 mg of solid in 15 ml of demineralized water in a batch under stirring during 24 hours respectively at 0 C., 27 C. and 40 C. The recovered solids are then dried overnight in an oven at 80 C. and their characteristics are reported in Table 4. [0191] Solid Hv to Hvii: the solids are recovered by filtration at 25 C. followed by a washing step performed at 27 C. The washing step is performed by introducing in a batch under stirring during 24 hours 100 mg of solid in 15 ml of solutions containing respectively 0.1M of HNO.sub.3 (nitric acid), NH.sub.4OH (ammonium hydroxyde), NH.sub.4NO.sub.3 (ammonium nitrate). The recovered solids are then dried overnight in an oven at 80 C. and their characteristics are reported in Table 4. [0192] Solid Hviii: the solids are recovered by filtration at 25 C. followed by a washing step performed at 27 C. The washing step is performed by introducing in a batch under stirring during 24 hours 100 mg of solid in 15 ml of pure methanol. The recovered solids are then dried overnight in an oven at 80 C. and their characteristics are reported in Table 4.

TABLE-US-00004 TABLE 3 Characteristics of HY15, the parent zeolite and recrystallized Y using chloride quaternized Jeffamines under different synthesis conditions Nitrogen adsorption V.sub.micro V.sub.meso V.sub.large meso V.sub.tot S.sub.BET D.sub.pores.sup.c Solids LOI.sup.a (% wt) Si/Al.sup.b (ml/g) (ml/g) (ml/g) (ml/g) (m.sup.2/g) (nm) HY15 3 16.1 0.218 0.164 0.086 0.468 814 25 B 16 16.1 0.114 0.274 0.084 0.472 486 5.9 C 18 16.2 0.159 0.285 0.076 0.52 645 5.5 D 19 21.2 0.191 0.252 0.079 0.522 723 5.3 E 19 16.7 0.163 0.301 0.038 0.502 656 5.3 F 15 0.098 0.058 0.104 0.260 303 10 G 34 0.094 0.146 0.222 0.462 378 8-15 .sup.adetermined by ATG between 150 and 900 C. .sup.bdetermined by EDX .sup.cdiameter of main pores

TABLE-US-00005 TABLE 4 Characteristics of recrystallized zeolite in presence of quaternized Jeffamine M600 treated with different solutions to remove the organic structuring agent Treatment Weight Nitrogen adsorption T LOI.sup.b proportion.sup.c (%) V.sub.micro V.sub.meso.sup.e V.sub.large meso V.sub.tot S.sub.BET D.sub.pores Solids Conditions ( C.) (%) Carbon Nitrogen (ml/g) (ml/g) (ml/g) (ml/g) (m.sup.2/g) (nm) H Calcination 550 4 0 0 0.163 0.301 0.038 0.502 656 5.3 Hi Filtration.sup.a 25 29 16.1 1.6 0 0.056 0.018 0.074 44 4.5 Hii Water 0 21 11 1.2 0 0.173 0.031 0.204 122 4.9 Hiii Water 27 20 10.7 1.2 0 0.183 0.034 0.217 128 5.2 Hiv Water 40 21 11.4 1.1 0 0.179 0.036 0.215 125 5.2 Hv HNO.sub.3 0.1M 27 17 9.2 0.8 0.021 0.233 0.031 0.285 225 5.3 Hvi NH.sub.4OH 0.1M 27 19 10.3 1.1 0 0.186 0.050 0.237 134 5.4 Hvii NH.sub.4NO.sub.3 0.1M 27 19 9.8 1.2 0 0.189 0.036 0.225 138 5.3 Hviii CH.sub.3OH 27 22 13.3 1.1 0.009 0.202 0.027 0.228 148 5.3 .sup.afiltration without washing; .sup.bdetermined by ATG between 150 and 900 C.; .sup.cdetermined by elemental analysis; .sup.ddetermined by EDX; .sup.emesopores <10 nm;

[0193] After recrystallization of the zeolite, during the cooling down of the solution, micelles of chloride quaternized Jeffamine M600 disassemble within the mesopores of the material.

[0194] A single filtration at room temperature without washing (Solid Hi) allows extracting 30% of the structuring agent present in the recrystallized zeolite.

[0195] A washing by water at room temperature allows to extract 30% additional structuring agent (Solid Hii), bringing to 60% the total amount of extracted quaternized M600 Jeffamine from the material. 73% of the mesoporous volume is then recovered in mild conditions without calcining the material. The temperature of the water used during the washing does not seem to have a strong impact on the amount of organic material extracted (Table 5).

[0196] The use of an acid solution (Solid Hv) improves furthermore the extraction by exchanging TMA.sup.+ cations with H.sup.+: by 90% of the mesoporous volume by 15% of the microporous volume become accessible.

[0197] The results obtained with methanol as washing solvent (Solid Hviii) are better than those obtained using NH.sub.4OH (Solid Hvi) or NH.sub.4NO.sub.3 (Solid Hvii) containing solution, but remain not so good as with HNO.sub.3 solution (Solid Hv).

[0198] The results obtained here clearly show the feasibility of the extraction of the structuring agents from the porosity of the mesoporized zeolites.

TABLE-US-00006 TABLE 5 Accessible volumes (recalculated per gram of aluminosilicate) of the different solids expressed in % versus the reference material (Solid H) Accessible volume (%) Solids V.sub.micro V.sub.meso V.sub.large meso V.sub.tot H: Calcined 100 100 100 100 Hi: Filtrated at 25 C. 0 25 64 20 Hii: Water 0 C. 0 70 99 49 Hiii: Water 27 C. 0 73 107 52 Hiv: Water 40 C. 0 72 115 52 Hv: HNO.sub.3 0.1M 15 90 94 66 Hvi: NH.sub.4OH 0.1M 0 73 156 56 Hvii: NH.sub.4NO.sub.3 0.1M 0 74 112 53 Hviii: CH.sub.3OH 7 83 87 56

EXAMPLE 10

Recycling of Guaternized Jeffamine in other Recrystallization Synthesis According to the Invention(Recrist.1./Recrist.2/Recrist.3/Recrist.4)

[0199] The same recrystallization protocol as for Solid H was used (Example 9).

[0200] After cooling down in an ice bath, the suspension is filtered at room temperature and the solid is rinsed with 3 ml of demineralized water. The solid is dried at 80 C. (Recrist.1).

[0201] The filtrate is recovered and before being reused in further recrystallization experiences, the pH of the filtrate is adjusted to 13, corresponding to the pH of the initial recrystallization solution before the hydrothermal treatment by adding drops of TMAOH (25% solution). The parent zeolite HY15 is then added and the system is stirred during 20 minutes followed by the hydrothermal treatment at 120 C. After cooling down and filtration at room temperature, the second solid is recovered (Recrist.2). The recycling/recrystallization protocol is repeated two more times using the same solution of quaternized Jeffamine M600. Two additional recrystallized zeolite samples are obtained (Recrist.3/ Recrist.4).

[0202] The recrystallization yields are high comprised between 92 and 94%.

[0203] The characteristics of the recrystallized zeolites are gathered Table 6 and FIG. 19. These results clearly show that the recycling of the solution containing the quaternized Jeffamine-Cl is possible without any intermediate purification. According to the present invention, it is demonstrated that the use of recoverable and recycled structuring agents under mild conditions leads to the synthesis of hierarchical zeolite materials having the following characteristics: [0204] conservation of the structure of the parent zeolite Y; [0205] formation of a homogeneous vermicular mesoporous phase in the solid; [0206] mesopores have a narrow distribution centered around 5.5 nm; [0207] microporosity and mesoporosity are intimately connected.

TABLE-US-00007 TABLE 6 Characteristics of the recrystallized zeolite obtained by recycling of quaternized Jeffamine M600 solution Weight proportion.sup.b (%) LOI.sup.a Jeff Nitrogen adsorption Solid (%) M600-Cl TMAOH Si/Al.sup.c V.sub.micro V.sub.meso.sup.d V.sub.largemeso V.sub.tot S.sub.BET D.sub.pores HY15 3 0 0 16.1 0.218 0.164 0.086 0.468 814 25 Recrist. 1 25 18.4 5.6 16.2 0.171 0.259 0.056 0.486 658 5.3 Recrist. 2 20 10.5 7.2 18.4 0.147 0.261 0.051 0.459 590 5.4 Recrist. 3 19 7.4 8.6 17.0 0.120 0.245 0.056 0.421 504 5.7 Recrist. 4 19 6.4 9.1 17.4 0.107 0.229 0.051 0.387 455 5.8 .sup.adetermined by ATG between 150 and 900 C.; .sup.bdetermined by elemental analysis; .sup.cdetermined by EDX; .sup.dmesopores <10 nm

EXAMPLE 11

Preparation of Solid I by Recrystallization of HY15 Zeolite using non Quaternized Jeffamine M600 as Organic Template-Comparative

(a) Preparation of the Reaction Mixture

[0208] 0.421 g (0.682 mmol) of Jeffamine M600 is dissolved under stirring at room temperature in 15 ml of 0.09M TMAOH solution during 10 min in a 20 ml autoclave.

[0209] 0.5 g of HY15 are then added to the solution under stirring during 20 min. The amount of Jeffamine M600 has been determined by keeping a NH.sub.2/Si ratio of 0.082.

(c) Preparation of Solid I

[0210] The autoclave is then hermetically closed and the reactional medium submitted to static hydrothermal conditions at 150 C. under autogeneous pressure during 20 hours. After quick cooling down of the autoclave in a water bath, the solid is recovered by filtration and washed using demineralized water until a neutral pH is reached. The solid is then dried overnight in an oven at 80 C. The solid porosity is recovered by washing or calcination of the contained organic matter in a tubular oven at 550 C. (1 C./min) during 8 hours under air (200 ml/h).

(d) Characterization of Solid I

[0211] The characteristics of the Solid I are reported in Table 7.

TABLE-US-00008 TABLE 7 Characteristics of the parent zeolite HY15, the recrystallized Y using M600 Jeffamine (solid I) and the recrystallized Y using quaternized M600 Jeffamine (solid B) LOI N2 adsorption Sample (%) Si/Al.sup.b V.sub.micro V.sub.meso V.sub.gdmeso V.sub.tot S.sub.BET D.sub.pores.sup.c HY15 (parent) 3 16.1 0.218 0.164 0.086 0.468 814 25 HY15-JeffM600 13 16.1 0.084 0.114 0.118 0.316 331 7.4 (solid I) HY15-JeffM600- 16 16.1 0.114 0.274 0.084 0.472 486 5.9 CI (ex 3 - solid B) .sup.adetermined by ATG between 150 and 900 C. .sup.bdetermined by EDX .sup.cdiameter of main pores
In solid I, large-angles XRD clearly exhibits a sharp decrease of the cristallinity compared to the parent HY15 zeolite and compared to solid B, whereas a large peak between 15 to 30 2 assigned to an amorphous aluminosilica phase is present (FIG. 20left).
Using small-angles XRD (FIG. 20right). the XRD spectrum of solid I is similar to the one of the parent HY15 zeolite, indicating that no organized mesostructure has been formed, which is also confirmed in TEM images (FIG. 22).
Those results are consistent with the textural properties of solid I as measured by N2 adsorption and desorption isotherms (FIG. 21 and table 7): more than half of the microporous volume has been lost (62%) with the presence of large mesopores (>10 nm); the pore size distribution in solid I is large from 3 to 40 nm and centered at around 7.4 nm.
All these results indicate that a controlled mesoporization is not possible with not quaternized Jeffamine M600 in the considered synthesis conditions (high alkaline medium). A large part of the zeolite structure is destroyed, together with the formation of large mespores and macropores in the material.

EXAMPLE 12

Preparation of Solid J by Recrystallization of HY15 Zeolite in Presence of CTAB Recovered after Filtration and not CalcinedComparative

[0212] 1.67 g of the HY15 zeolite are mixed together at room temperature with 50 ml of a 0.09M TMAOH solution under vigourous stirring in a 120 ml autoclave.
0.83 g of CTAB are then added to the suspension maintained under stirring during 20 min. The mixture has a CTAB/Si molar ratio of 0.082.
The autoclave is then hermetically closed and the reactional medium submitted to static hydrothermal conditions at 150 C. under autogeneous pressure during 20 hours. After quick cooling down of the autoclave in a water bath, the solid is recovered by filtration at 25 C. and washed using demineralized water until a neutral pH is reached. The solid is then dried overnight in an oven at 80 C. (solid J).
By calcining solid J in a tubular oven at 550 C. (1 C./min) during 8 hours under air (200 ml/h), solid A is then recovered.
CTAB is a surfactant conserving its amphiphilic properties whatever the temperature or pH conditions are. The N2-physisorption measurements (FIG. 23) clearly show that CTAB remains trapped in the mesopores and cannot be removed by a temperature decrease followed by filtration. A calcination step is necessary to recover the whole porosity of the material (solid A).