POST-SYNTHETIC DOWNSIZING ZEOLITE-TYPE CRYSTALS AND/OR AGGLOMERATES THEREOF TO NANOSIZED PARTICLES

Abstract

The present invention relates to a method of post-synthetic downsizing zeolite-type crystals and/or agglomerates thereof to nanosized particles, and in particular a heating-free and chemical-free method. The present invention also relates to nanosized particles of zeolite-type material capable of being obtained by the method of the invention and to the use of such particles as a catalyst or catalyst support for heterogeneous catalyst, or as molecular sieve, or as a cation exchanger.

Claims

1. Method of post-synthetic downsizing zeolite-type crystals and/or agglomerates thereof to nanosized particles of zeolite or zeolite-like, consisting of a heating-free and chemical-free application of a static pressure to said zeolite crystals and/or agglomerates, wherein the pressure is comprised between 1 MPa and 2000 MPa and the duration of the pressing is comprised between 1 and 60 minutes.

2. Method according to claim 1, wherein the pressure is 980 MPa.

3. Method according to claim 1, wherein the duration of the pressing is 10 minutes.

4. Method according to claim 1, wherein the pressure is isostatically applied to said zeolite crystals from all directions.

5. Method according to claim 1, wherein the pressing is generated by ramping up the pressure.

6. Method according to claim 1, wherein the zeolite-type particles are needle-like crystals of zeolite or zeolite-like material.

7. Method according to claim 1, wherein the zeolite or the zeolite-like materials are selected in the group consisting of ZSM-22, ZSM-23, ZSM-5, Mordenite, zeolite A, zeolite L, zeolite Y, and SAPO-34.

8. Nanosized particles of zeolite or zeolite-like material capable of being obtained by the method as defined according to claim 1.

9. Use of the nanosized particles of zeolite-type material capable of being obtained by the method as defined according to claim 1, as a heterogeneous catalyst.

10. Use of the nanosized particles of zeolite-type material capable of being obtained by the method as defined according to claim 1, as a molecular sieve.

11. Use of the nanosized particles of zeolite-type material capable of being obtained by the method as defined according to claim 1, as a cation exchanger.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0026] Other advantages and features of the present invention will result from the following description given by way of non-limiting example and made with reference to the accompanying drawings:

[0027] FIG. 1 shows an XRD pattern of the parent (i.e. not pressed) and its 10 T pressed ZSM-22 derivative (Pressure of about 1000 MPa).

[0028] FIGS. 2a to 2f show SEM images of (a) parent and (b) 10 T pressed ZSM-22; TEM micrographs of (c, d) parent and (e, f) 10 T pressed ZSM-22 (Pressure of about 1000 MPa).

[0029] FIG. 3 shows Nitrogen adsorption isotherms (77K) of parent and 10 T pressed ZSM-22 (Pressure of about 1000 MPa).

[0030] FIG. 4 is a .sup.27Al MAS NMR spectra of the parent and 10 T treated ZSM-22.

[0031] FIGS. 5a to 5c show In-situ IR of parent ZSM-22 and its 10 T pressed derivative after (a) activation, (b) acetonitrile and (c) 2,6-lutidine adsorption.

[0032] FIG. 6a to 6c show monobranched isomerization yields as a function of conversion for (a) Parent and (b) 10 T samples (T 523 K, P 5 MPa and W/F.sup.° 30-71 kg.Math.s.Math.mol. (c) Yields of monobranched (mbC.sub.8), dibranched (dbC.sub.8) at maximum conversion.

[0033] FIG. 7 shows the XRD pattern of the parent (left) and 251 treated (right) ZSM-22. A decrease in the intensity of XRD peaks of treated material can be observed.

[0034] FIG. 8 shows the N.sub.2 adsorption-desorption isotherms of the parent and the 251 treated ZSM-22. The chances in the isotherm reveal a decrease the micropore volume and increase in the mesopore volume, the later being a consequence of the agglomeration of broken nanosized particles.

[0035] FIG. 9 shows an XRD pattern of the parent modernite (i.e. not pressed) and its 10 T pressed modernite (Pressure of about 1000 MPa).

[0036] FIGS. 10A and 10B show SEM images of (a) parent and (b) 10 T modernite.

[0037] FIG. 11 shows Nitrogen adsorption isotherms of parent and 10 T pressed mordenite (Pressure of about 1000 MPa).

[0038] FIG. 12 shows an XRD pattern of the parent modernite (i.e. not pressed) and its 5 T pressed modernite (Pressure of about 600 MPa).

[0039] FIGS. 13A and 13B show SEM images of (a) parent and (b) 5 T modernite.

[0040] FIG. 14 shows Nitrogen adsorption isotherms of parent and 5 T pressed mordenite (Pressure of about 600 MPa).

[0041] FIG. 15 shows an XRD pattern of the parent zeolite Y (i.e. not pressed) and its 10 T pressed zeolite Y (Pressure of about 980 MPa).

[0042] FIGS. 16A and 16B show SEM images of (a) parent and (b) 10 T zeolite Y.

[0043] FIG. 17 shows Nitrogen adsorption isotherms of parent and 10 T pressed zeolite Y (Pressure of about 980 MPa).

[0044] FIG. 10 shows an XRD pattern of the parent zeolite Y (i.e. not pressed) and its 5 T pressed zeolite Y (Pressure of about 590 MPa).

[0045] FIGS. 19A and 19B show SEM images of (a) parent and (b) 5 T zeolite Y.

[0046] FIG. 20 shows Nitrogen adsorption isotherms of parent and 5 T pressed zeolite Y (Pressure of about 590 MPa).

[0047] FIG. 21 shows an XRD pattern of the parent zeolite A (i.e. not pressed) and its 10 T pressed zeolite A (Pressure of about 980 MPa).

[0048] FIGS. 22A and 22B show SEM images of (a) parent and (b) 10 T zeolite A.

[0049] FIG. 23 shows Nitrogen adsorption isotherms of parent and 10 T pressed zeolite A (Pressure of about 980 MPa).

[0050] FIG. 24 shows an XRD pattern of the parent zeolite A (i.e. not pressed), and its 5 T pressed zeolite A (Pressure of about 590 MPa).

[0051] FIGS. 25A and 25B show SEM images of (a) parent and (b) 5 T zeolite A.

[0052] FIG. 26 shows Nitrogen adsorption isotherms of parent and 5 T pressed zeolite A (Pressure of about 590 MPA).

[0053] FIG. 27 shows an XRD pattern of the parent zeolite L (i.e. not pressed) and its 10 T pressed zeolite L (Pressure of about 980 MPa).

[0054] FIGS. 28A and 28B show SEM images of (a) parent and (b) 10 T zeolite L.

[0055] FIG. 29 shows Nitrogen adsorption isotherms of parent and 10 T pressed zeolite L (Pressure of about 980 MPa).

[0056] FIG. 30 shows an XRD pattern of the parent zeolite L (i.e. not pressed) and its 5 T pressed zeolite L (Pressure of about 590 MPa).

[0057] FIGS. 31A and 31B show SEM images of (a) parent and (b) 5 T zeolite L.

[0058] FIG. 32 shows Nitrogen adsorption isotherms of parent and 5 T pressed zeolite L (Pressure of about 590 MPa).

EXAMPLES

[0059] Products: [0060] zeolite ZSM-22 (TON-type) in the form of pellets of substantially circular shape and having an external planar surface of about 2 cm.sup.2. ZSM-22 (TON-type) exhibits 1-dimensional channel system with elliptical pores (0.48×0.57 nm). The as synthesized ZSM-22 is characterized by long prismatic crystals (along the c-axis) where the 1-dimensional channels run with abundant intergrowths along the 001 plane. These features increase the diffusion path length of molecules and limit, the number of pore mouths. [0061] Mordenite pellets with a surface area of 2.01 cm.sup.2 and a thickness of 1 mm. [0062] Zeolite Y pellet with a surface area of 2.01 cm.sup.2 and a thickness of 1 mm. [0063] Zeolite A pellet with a surface area of 2.01 cm.sup.2 and a thickness of 1 mm. [0064] Zeolite L pellet with a surface area of 2.01 cm.sup.2 and a thickness of 1 mm.

[0065] Press: hydraulic manual press Atlas™ (Specac).

Example 1: Downsizing Zeolite ZSM-22 (980 MPa)

Pressing

[0066] We prepare a zeolite ZSM-22 (TON-type) pellet with a surface area of 2.01 cm.sup.2 and a thickness of 1 mm, which was subjected to a pressure of about 1000 MPa for 10 min.

[0067] Preliminary experiments have optimized the pressure (980 MPa) and time (10 min) of the treatment of the pellets in the hydraulic laboratory press.

[0068] Some of the as synthesized ZSM-22 pellets are not submitted to the method of the invention, while some of the pallets are subjected to a 10 tons pressing (corresponding to a pressure of about 1000 MPa.

[0069] The as-synthesized ZSM-22 that has not been subjected to pressing is hereinafter called parent P: it is pure and fully crystalline (see FIG. 1). XRD analysis of the treated sample shows a well-preserved crystallinity as shown in FIG. 1.

[0070] The as-synthesized ZSM-22 that has been subjected to pressing is hereinafter called 10 T. The 10 T pressed ZSM-22 derivative also shows a well-preserved crystallinity as shown by 1

Analysis of the Morphology

[0071] An SEM inspection shows that the parent zeolite P exhibits a long-prismatic morphology with crystal length between 0.5 and 2 micrometer (FIG. 2a). After pressing, only short-prismatic crystallites with a length of 50-200 nm are observed (FIG. 2b). More detailed information about the treatment (pressing) and its influence on the morphology of ZSM-22 is brought by TEN: Aggregates of parallel and randomly intergrown long prismatic crystals are observed in the parent P zeolite (FIG. 2c).

[0072] A closer look indicates that the long prismatic crystals consist of segments ranging from 50 to several hundred nanometers (FIG. 2d).

[0073] TEM analysis confirms that after pressing, only short prismatic crystals are present (FIGS. 2e, 2f). They agglomerate along the long crystal axis, and almost all individual crystals have disappeared. It is worth noting that the crystals are stacked along their prismatic face, free of pore opening, and thus their agglomeration does not have a negative impact on their pore mouth accessibility.

Determination of the Surface and Textural Properties

[0074] The surface and textural properties of the parent (P) and pressed (10 T) ZSM-22 samples are measured by nitrogen physisorption. The samples were degassed under vacuum at 573 K for 15 hours prior to the measurement. The analysis was performed at 77K using Micrometrics ASAP 2020 volumetric adsorption analyser.

[0075] The parent (P) ZSM-22 sample exhibits the typical (type 1) isotherm of microporous materials (as shown by FIG. 3). The slight inclination of the isotherm and the hysteresis loop at high relative pressure indicates the presence of mesoporosity.

[0076] The isotherm of its 10 T pressed derivative is similar except for a much larger hysteresis loop; its mesopore volume almost doubles, from 0.13 to 0.25 cm.sup.3g.sup.−1 as shown by Table below,

TABLE-US-00001 TABLE 1 Physiochemical properties of parent and treated samples Si/Al.sup.a Pt.sup.b S.sub.BET.sup.c V.sub.mic.sup.c V.sub.meso.sup.c Sample (wt. %) (%) (m.sup.2g.sup.−1) (cm.sup.3g.sup.−1) (cm.sup.3g.sup.−1) P 336 0.50 290 0.120 0.13 10T 339 0.49 280 0.115 0.25 .sup.aICP-AES; .sup.bPlatinum dispersion measured by CO adsorption; .sup.cN.sub.2 adsorption: BET and t-plot methods.

[0077] Thus a 10 T pressing of the micron-sized zeolite crystals produces heavily aggregated nanoparticles. The H1 type hysteresis loop indicates the presence of a narrow range textural mesoporosity.sup.[31], which is a consequence of the alignment of nanosized particles along their long axis. The physisorption analysis fully confirms the TEM observations and indicates that the intrinsic characteristics of ZSM-22 are preserved. The negligible loss of micropore volume, from 0-0.120 to 0.115 cm.sup.3g.sup.−1 (see Table 1) is in the range of experimental error and confirms the XRD conclusion that crystalline structure is preserved.

[0078] The impact of pressing on the short-range order in the zeolite structure and inure precisely on its active sites (due to the presence of tetrahedrally coordinated aluminum atoms) is best studied by .sup.27Al MAS NMR (FIG. 4). Both, the parent (P) and its pressed derivative (10 T) exhibit a single peak at 55 ppm, characteristic of tetrahedrally coordinated aluminum (AlO.sub.4). However, a slight peak broadening is observable in the treaded sample. This broadening is assigned to distorted tetrahedrally coordinated Al caused by minor framework alterations such as Al—O—Si angle or quadrupolar interactions.sup.[32]. This effect may be attributed to an increased fraction of pore openings due to the segmentation of crystals perpendicular to their c axis and/or the surface interactions between pressed nanoparticles. In both cases, the ZSM-22 does not posses any visible octahedral Al, another indication that crystal structure is barely affected by the pressing.

In-situ IR spectroscopy of probe molecules is used to evaluate their accessibility to the active sites in the parent ZSM-22 and its 10 T pressed derivative.sup.[34, 35]. The IR spectra of the bare zeolites after activation (prior to the adsorption of probe molecules) show the expected surface silanols (3746 cm.sup.−1) and acidic bridged hydroxyls (3604 cm.sup.−1) (see FIG. 5a). The intensity of the silanols is similar in the two samples, while the bridged hydroxyls concentration slightly increases after the post-synthetic modification (from 94 μmol g.sup.−1 to 109 μmol g.sup.−1), indicating an increased concentration of Brøensted acid sites in the 10 T sample. The overall acidity is assessed by monitoring the adsorption of deuterated acetonitrile (Figure b). This small molecule easily accesses all Brøensted (2298 cm.sup.−1) and Lewis (2326 cm.sup.−1) acid sites. A higher number of active sites (BAS=279 μmol g.sup.−1, LAS=163 μmol g.sup.−1) is measured on the treated ZSM-22 than on its parent (BAS=235 μmolg.sup.−1 and LAS=151 μmol g.sup.−1). The increased accessibility is not accompanied by the formation of Lewis acid sites, in agreement with the absence of octahedral species in .sup.27Al NMR. The bulky and sterically hundred lutidine probes only the Brøensted sites (1642 cm.sup.−1) located on the outer surface and the pore mouths. (Figure c).

[0079] These data indicate that the eternal acidity in the 10 tons pressed ZSM-22 (88 μmol g.sup.−1) is slightly higher than its parent sample (77 μmol g.sup.−1).

Evaluation of the Catalytic Performances

[0080] The effect of this post-synthetic modification on the catalytic performances of ZSM-22, is evaluated in hydroisomerization of n-octane (n-C.sub.8). 0.5 wt % Pt is impregnated on the two zeolites using Pt(NH.sub.3).sub.4(NO.sub.3).sub.2 as a Pt source. The Pt dispersions are similar (ca. 52%) for both samples providing that only the number of Brøensted acid sites determines catalytic activity.sup.[36].

[0081] The platinum loaded ZSM-22, Pt-P, and Pt-10 T for the parent ZSM-22 and its 10 T pressed derivative, have both a high conversion in the n-C.sub.8 hydroisomerization (FIG. 6a,b). The activity of the Pt-10 T catalyst, 67%, is however higher than its parent Pt-P, 44%. This 23% increase in conversion takes place without barely any cracking (1.94%) and no changes in branching selectivity; yields of mono-methyl branched isomers, under identical operating conditions, thus increase from 43% (parent) to a remarkable 65% (10 T derivative), FIG. 6c.

[0082] Similar yields of mono-branched isomers were reported earlier, albeit at different experimental conditions (temperature, total pressure and space time).sup.[29,36]. The high isomerization yields and low cracking of the pressed SM-22 confirm that, this process improves the key physical properties, increases the number of pore mouths, of optimal catalyst design. In the case of ZSM-22, it does so without some of the drawbacks of caustic leaching, where i) 40 to 8.0% of ZSM-22 are dissolved without any great increase in mesoporous surface, in contrast to other 3-dimensional zeolites (MFI, FER), and ii) caustic leaching needs to be followed by a (mild) acid leaching to solubilize Al species blocking access to the micropores.

Example 2: Comparative Example Zeolite ZSM-22

Pressing

[0083] We prepare a zeolite ZSM-22 pellet with a surface area of 2.01 cm.sup.2 and a thickness of 1 mm, which was subjected to a pressure of about 2452 MPa (25 T) for 10 min.

Analysis of the Morphology and Properties

[0084] XRD analysis of the treated sample snows a decrease of crystallinity as shown in FIG. 7. N.sub.2 physisorption analysis confirmed the results of XRD study showing a decrease in the uptake a low relative pressure, Which is due to the amorphisation and loose of a part (˜15%) of the micropore volume as can be seen in FIG. 8.

Example 3: Downsizing Mordenite (980 MPa)

Pressing

[0085] We prepare a Mordenite pellet with a surface area of 2.01 cm.sup.2 and a thickness of 1 mm, which was subjected to a pressure of about 980 MPa for 10 min.

[0086] The as-synthesized Mordenite that has not been subjected to pressing is hereinafter called parent P: it is pure and fully crystalline (see FIG. 9). The as-synthesized Mordenite that has been subjected to pressing is hereinafter called 10 T. The 10 T pressed Mordenite derivative also shows a well-preserved crystallinity as shown in FIG. 9.

Analysis of the Morphology and Properties

[0087] The SEM inspection of the parent and treated mordenite showed the difference in the particle size. The treated sample exhibit smaller crystals, which are a consequence of breaking the Mordenite crystals during pressure treatment (see FIGS. 10A and 10B).

[0088] The porous characteristics of initial and treated Mordenite were evaluated by N.sub.2 physisorption. No substantial differences in the physisorption isotherms where observed (see FIG. 11).

Example 4: Downsizing Mordenite (590 MPa)

Pressing

[0089] We prepare a Mordenite pellet with a surface area of 2.01 cm.sup.2 and a thickness of 1 mm, which was subjected to a pressure of about 590 MPa for 10 min.

[0090] The as-synthesized Mordenite that has not been subjected to pressing is hereinafter called parent P: it is pure and fully crystalline (see FIG. 12). The as-synthesized Mordenite that has been subjected to pressing is hereinafter called 5 T. The 5 T pressed Mordenite derivative also snows a well-preserved crystallinity as shown in FIG. 12.

Analysis of the Morphology and Properties

[0091] The SEM inspection of the parent and treated mordenite showed the difference in the particle size. The treated sample exhibit smaller crystals which are a consequence of breaking the Mordenite crystals during pressure treatment (see FIGS. 13A and 13B).

[0092] The porous characteristics of initial and treated Mordenite were evaluated by N.sub.2 physisorption. No substantial differences in the physisorption isotherms where observed (see FIG. 14).

Example 5: Downsizing Zeolite Y (980 MPa)

Pressing

[0093] We prepare a zeolite Y pellet with a surface area of 2.01 cm.sup.2 and a thickness of 1 mm, which was subjected to a pressure of about 980 MPa for 10 min.

[0094] The as-synthesized zeolite Y that has not been subjected to pressing is hereinafter called parent P: it is pure and fully crystalline (see FIG. 15). The as-synthesized zeolite Y that has been subjected to pressing is hereinafter called 10 T. The 10 T pressed zeolite Y derivative also shows a well-preserved crystallinity as shown in FIG. 15.

Analysis of the Morphology and Properties

[0095] The SEM inspection of the parent and treated mordenite showed the difference in the particle size. The treated sample exhibit smaller crystals which are a consequence of breaking the zeolite Y crystals during pressure treatment (see FIGS. 16A and 16B).

[0096] The porous characteristics of initial and treated zeolite Y were evaluated by N.sub.2 physisorption. No substantial differences in the physisorption isotherms where observed (see FIG. 17).

Example 6: Downsizing Zeolite Y (590 MPa)

Pressing

[0097] We prepare a zeolite Y pellet with a surface area of 2.01 cm.sup.2 and a thickness of 1 mm, which was subjected to a pressure of about 590 MPa for 10 min.

[0098] The as-synthesized zeolite Y that has not been subjected to pressing is hereinafter called parent P: it is pure and fully crystalline (see FIG. 18). The as-synthesized zeolite Y that has been subjected to pressing is hereinafter called 5 T. The 5 T pressed zeolite Y derivative also shows a well-preserved crystallinity as shown in FIG. 18.

Analysis of the Morphology and Properties

[0099] The SEM inspection of the parent and treated mordenite showed the difference in the particle size. The treated sample exhibit smaller crystals which are a consequence of breaking the zeolite Y crystals during pressure treatment (see FIGS. 19A and 19B).

[0100] The porous characteristics of initial and treated zeolite Y were evaluated by N.sub.2 physisorption. No substantial differences in the physisorption isotherms where observed (see FIG. 20).

Example 7: Downsizing Zeolite A (980 MPa)

Pressing

[0101] We prepare a zeolite A pellet with a surface area or 2.01 cm.sup.2 and thickness of 1 mm, which was subjected to pressure of about 980 MPS for 10 min.

[0102] The as-synthesized zeolite A that has not been subjected to pressing is hereinafter called parent P: it is pure and fully crystalline (see. FIG. 21). The as-synthesized zeolite A that has been subjected to pressing is hereinafter called 10 T. The 10 T pressed zeolite Y derivative also shows a well-preserved crystallinity as shown in FIG. 21.

Analysis of the Morphology and Properties (Physisorption)

[0103] The SEM inspection of the parent and treated mordenite showed the difference in the particle size. The treated sample exhibit smaller crystals which are a consequence of breaking the zeolite A crystals during pressure treatment (see FIGS. 22A and 22B).

[0104] The porous characteristics of initial and treated zeolite A were evaluated by N.sub.2 physisorption. No substantial differences in the physisorption isotherms where observed (see FIG. 23).

Example 8: Downsizing Zeolite A (590 MPa)

Pressing

[0105] We prepare a zeolite A pellet with a surface area of 2.01 cm.sup.2 and a thickness of 1 mm, which was subjected to a pressure of about 590 MPa for 10 min.

[0106] The as-synthesized zeolite A that has not been subjected to pressing is hereinafter called parent P: it is pure and fully crystalline (see FIG. 24). The as-synthesized zeolite A that has been subjected to pressing is hereinafter called 5 T. The 5 T pressed zeolite Y derivative also shows a well-preserved crystallinity as shown in FIG. 24.

Analysis of the Morphology and Properties

[0107] The SEM inspection of the parent and treated mordenite showed the difference in the particle size. The treated sample exhibit smaller crystals, which are a consequence of breaking the zeolite A crystals during pressure treatment (see FIGS. 25A and 25B).

[0108] The porous characteristics of initial and treated zeolite A were evaluated by N.sub.2 physisorption. No substantial differences in the physisorption isotherms where observed (see FIG. 26).

Example 9: Downsizing Zeolite L (980 MPa)

Pressing

[0109] We prepare a zeolite L pellet with a surface area of 2.01 cm.sup.2 and a thickness or 1 mm, which was subjected to a pressure of about 980 MPa for 10 min.

[0110] The as-synthesized zeolite L that has not been subjected to pressing is hereinafter called parent P: it is pure and fully crystalline (see FIG. 27). The as-synthesized zeolite L that has been subjected to pressing is hereinafter called 10 T. The 10 T pressed zeolite L derivative also shows a well-preserved crystallinity as shown in FIG. 27.

Analysis of the Morphology and Properties

[0111] The SEM inspection of the parent and treated mordenite showed the difference in the particle size. The treated sample exhibit smaller crystals which are a consequence of breaking the zeolite A crystals during pressure treatment (see FIGS. 28A and 28B).

[0112] The porous characteristics of initial and treated zeolite L were evaluated by N.sub.2 physisorption. No substantial differences in the physisorption isotherms where observed (see FIG. 29).

Example 10: Downsizing Zeolite L (590 MPa)

Pressing

[0113] We prepare a zeolite L pellet with a surface area or 2.01 cm.sup.2 and a thickness of 1 mm, which was subjected to a pressure of about 590 MPa for 10 min.

[0114] The as-synthesized zeolite L that has not been subjected to pressing is hereinafter called parent P: it is pure and fully crystalline (see FIG. 30). The as-synthesized zeolite L that has been subjected to pressing is hereinafter called 5 T. The 5 T pressed zeolite L derivative also shows a well-preserved crystallinity as shown in FIG. 30.

Analysis of the Morphology and Properties

[0115] The Sty inspection of the parent and treated mordenite showed the difference in the particle size. The treated sample exhibit smaller crystals which are a consequence of breaking the zeolite A crystals during pressure treatment (see FIGS. 31A and 31B).

[0116] The porous characteristics of initial and treated zeolite L were evaluated by N.sub.2 physisorption. No substantial differences in the physisorption isotherms where observed (see FIG. 32).

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