WO2015059175A1 - Powder or granulate for a zeolitic material and process for its production - Google Patents
Powder or granulate for a zeolitic material and process for its production Download PDFInfo
- Publication number
- WO2015059175A1 WO2015059175A1 PCT/EP2014/072614 EP2014072614W WO2015059175A1 WO 2015059175 A1 WO2015059175 A1 WO 2015059175A1 EP 2014072614 W EP2014072614 W EP 2014072614W WO 2015059175 A1 WO2015059175 A1 WO 2015059175A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- powder
- granulate
- zeolitic material
- comprised
- binders
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 201
- 239000000843 powder Substances 0.000 title claims abstract description 152
- 239000008187 granular material Substances 0.000 title claims abstract description 134
- 238000000034 method Methods 0.000 title claims abstract description 129
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 91
- 239000000725 suspension Substances 0.000 claims abstract description 48
- 239000002904 solvent Substances 0.000 claims abstract description 46
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000000634 powder X-ray diffraction Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 57
- 239000003054 catalyst Substances 0.000 claims description 36
- 238000004400 29Si cross polarisation magic angle spinning Methods 0.000 claims description 35
- 229910052752 metalloid Inorganic materials 0.000 claims description 32
- 150000002738 metalloids Chemical class 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 229910044991 metal oxide Inorganic materials 0.000 claims description 27
- 150000004706 metal oxides Chemical class 0.000 claims description 27
- 150000002739 metals Chemical class 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- 229910052750 molybdenum Inorganic materials 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 22
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 125000002091 cationic group Chemical group 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 229910052712 strontium Inorganic materials 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000003463 adsorbent Substances 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 91
- 229910001868 water Inorganic materials 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 239000000377 silicon dioxide Substances 0.000 description 31
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 26
- 229920002050 silicone resin Polymers 0.000 description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 24
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 19
- 239000008119 colloidal silica Substances 0.000 description 17
- 230000010354 integration Effects 0.000 description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 16
- 239000000126 substance Substances 0.000 description 14
- -1 polysiloxane Polymers 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 229920001296 polysiloxane Polymers 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 229910021485 fumed silica Inorganic materials 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- 150000001298 alcohols Chemical class 0.000 description 9
- 150000001735 carboxylic acids Chemical class 0.000 description 9
- 239000000395 magnesium oxide Substances 0.000 description 8
- 150000002894 organic compounds Chemical class 0.000 description 8
- 239000003586 protic polar solvent Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005388 cross polarization Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 238000010485 C−C bond formation reaction Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002577 pseudohalo group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
Definitions
- the present invention relates to a process for the preparation of a powder or granulate contain- ing a zeolitic material and a binder, and to a powder or granulate which is obtainable by such a process.
- the present invention further relates to a powder or granulate per se containing a zeolitic material and a binder, as well as to the use of said powder or granulate in specific applications, and in particular in catalytic processes.
- zeolitic materials Due to the crystallinity of zeolitic materials in general, it is common in the art to produce powders or granulates thereof using a binder not only for ease of handling but also for avoiding physical deterioration of the zeolitic materials in applications in which these are used, and in particular in applications requiring a certain operation resistance due to physical wear of the materials in specific process steps where the zeolitic materials as such would be subject to agitation. In particular, a specific abrasion resistance is required in cases wherein the zeolitic material is employed in processes employing a fluidized-bed technology.
- powders or granulates of zeolitic materials containing a binder are often required in catalytic processes wherein a dilution of the zeolitic materials is further required for better control of the catalytic activity by avoiding heat buildup which may occur when using a high concentration of the zeolitic material.
- the use of powders or granulates of zeolitic materials containing a binder plays an important role for providing catalytically active zeolitic materials in a physical state in which optimal control of their activity by proper dilution in a specific volume coupled with heat dissipation means in the case of exothermic reactions allows for the fine- tuning of the catalytic process.
- the object of the present invention to provide a process for the production of a powder or granulate which may employ a wider variety of zeolitic materials.
- the present invention relates to a process for the production of a powder or granulate, comprising
- step (II) suspending the zeolitic material provided in step (I) in a solvent system
- step (III) mixing the suspension obtained in step (II) with one or more binders;
- step (V) calcining of the dried material obtained in step (IV);
- zeolitic material provided in step (I) has an MFI-type framework structure comprising YO2 and optionally comprising X2O3,
- said material having an X-ray diffraction pattern comprising at least the following reflections:
- the zeolitic material which may be employed in the inventive process provided that it displays the aforementioned X- ray diffraction pattern.
- the intensity of the first reflection comprised in the range of 7.88° - 8.16° 2 ⁇
- the intensity of said reflection is comprised in the range of from 15 - 45, more preferably of from 16 - 30, and even more preferably of from 17 - 23.
- the intensity of the second reflection comprised in the range of 8.83° - 9.13° 2 ⁇
- the intensity of said reflection is comprised in the range of from 12 - 30, more preferably of from 13 - 25, more preferably of from 14 - 23, and even more preferably of from 15 - 21 .
- the synthetic zeolitic material having an MFI-type framework structure used in the inventive process has an X-ray diffraction pattern comprising at least the following reflections:
- the zeolitic material having an MFI-type framework structure used in the inventive process has an X-ray diffraction pattern comprising at least the following reflections:
- the intensity of the first reflection comprised in the range of 7.95° - 8.09° 2 ⁇ it is preferred according to the present invention that the intensity of said reflection is comprised in the range of from 17 - 30, more prefera- bly of from 17 - 25, and even more preferably of from 17 - 23.
- the intensity of the second reflection comprised in the range of 8.91 ° - 9.05° 2 ⁇ it is preferred according to the present invention that the intensity of said reflection is comprised in the range of from 15 - 24, more preferably of from 14 - 22, and even more preferably of from 15 - 21.
- the solvent system which may be employed in the inventive process
- the solvent system may comprise one or more solvents, wherein it is preferred according to the present inven- tion that the solvent system comprises one or more solvents.
- the solvent system comprises one or more hydro- philic solvents, the hydrophilic solvents preferably being selected from the group consisting of polar solvents, more preferably from the group consisting of polar protic solvents.
- the polar protic solvents preferably comprised in the solvent system, again no particu- lar restriction applies as to the number or further physical and chemical properties thereof provided that a suspension may be obtained in step (II) of the inventive process.
- the solvent system comprises one or more polar protic solvents selected from the group consisting of water, alcohols, car- boxylic acids, and mixtures of two or more thereof, more preferably from the group consist- ing of water, C1 -C5 alcohols, C1 -C5 carboxylic acids, and mixtures of two or more thereof, more preferably from the group consisting of water, C1 -C4 alcohols, C1 -C4 carboxylic acids, and mixtures of two or more thereof, and more preferably from the group consisting of water, C1 -C3 alcohols, C1 -C3 carboxylic acids, and mixtures of two or more thereof.
- polar protic solvents selected from the group consisting of water, alcohols, car- boxylic acids, and mixtures of two or more thereof, more preferably from the group consist- ing of water, C1 -C5 alcohols, C1 -C5 carboxylic acids, and mixtures of two or more thereof, more preferably from the group consisting of water, C
- substituted preferably refers to the substitution of one or more hydrogen atoms of the alkyl group inde- pendently from one another by one or more monovalent moieties, and more preferably by a halide or pseudohalide, more preferably by a halide, and even more preferably by a halide selected from the group consisting of F, CI, and Br, and yet more preferably by F or CI.
- the one or more polar protic solvents preferably comprised in the solvent system used in step (II) of the inventive process comprises unsubstituted polar protic solvents, and preferably unsubstituted polar pro- tic solvents selected from the group consisting of water, methanol, ethanol, propanol, formic acid, acetic acid, and mixtures of two or more thereof, more preferably from the group consisting of water, ethanol, acetic acid, and mixtures of two or more thereof, wherein more preferably the solvent system comprises water and/or ethanol.
- the solvent system employed in step (II) comprises water, wherein it is yet further preferred that the solvent system does not contain any further solvents besides water, such that in such cases the solvent system employed in step (II) consists of water.
- the zeolitic material employed in the inventive process displays an X-ray diffraction pattern as according to any of the particular and preferred embodiments of the inventive process.
- This applies also with respect to the morphology of the zeolitic material involved such that in principle zeolitic materials with any suitable morphology, and in particular any suitable shapes or sizes may be used. It is, however, preferred according to the present invention that the zeolitic material displays a particle size which may be well dispersed in the solvent system employed, and in particular in the solvent system employed according to the particular and preferred embodiments of the inventive process.
- the zeolitic materials display a small particle size and in particular that the zeolitic material is employed in a microcrystalline state. According to the present invention it is thus particularly preferred that the zeolitic material displays a particle size D90 ranging from 0.05 to 20 ⁇ , and more preferably from 0.1 to 10 ⁇ , more preferably from 0.5 to 5 ⁇ , more preferably from 0.8 to 4 ⁇ , more preferably from 1 to 3.5 ⁇ , and more pref- erably from 1.3 to 2.9 ⁇ . According to the inventive process it is however particularly pre- - - ferred that the particle size D90 of the zeolitic material employed in the inventive process ranges from 1.5 to 2.5 ⁇ .
- said particle size D90 of the zeolitic material employed in the inventive process refers to the zeolitic material at any stage of the inventive process, such that it may designate the particle size D90 of the zeolitic material as it is provided in step (I) of the inventive process, or may also designate the particle size D90 of the zeolitic material after having suspended the same in the solvent system according to step (II) of the in- ventive process, the initial particle size D90 having been larger prior to step (II) of suspending the zeolitic material in the solvent system.
- a zeolitic material having a larger particle size D90 is provided in step (I) of the inventive process, the particle size then being reduced in step (II) of the inventive process during step (II) of suspending the zeolitic material in the solvent system, and in particular wherein the particle size D90 is reduced in step (II) to a particle size comprised in any of the particular and preferred ranges of particle sizes D90 as defined in the foregoing.
- step (II) of the inventive process there is no particular restriction as to how or to what extent a reduction of the particle size D90 is achieved.
- a reduction in the particle size D90 may be achieved by abrasion of the particles against one another during the suspending of the zeolitic material, wherein the duration of the procedure for preparing the suspension may accordingly be chosen in function of the particle size D90 which is desired.
- a step of milling the zeolitic material is performed prior to or during step (II) of suspending the zeolitic material in the solvent system in step, wherein preferably the zeolitic material is milled during the course of step (II), an more preferably wet-milled, and even more preferably wet-milled using the solvent system in which the zeolite is suspended in step (II).
- step (III) of the inventive process the suspension obtained in step (II) according to any of the aforementioned particular and preferred embodiments is mixed with one or more binders.
- the conditions employed for the mixing process in step (III) no restrictions whatsoever apply according to the present invention, such that in principle any conceivable procedure may be employed using any suitable type of apparatus under any suitable condi- tions, provided that a homogenous mixture is obtained as a result of the mixing procedure in step (III).
- the mixing procedure may be conducted at any suitable temperature, wherein it is preferred according to the present invention that the mixing in step (III) is conducted at an elevated temperature with respect to room temperature (25°C), wherein more preferably the mixing in step (III) is performed at a temperature ranging from 30 to 150°C, more preferably from 35 to 130°C, more preferably from 40 to 1 10°C, and more preferably from 45 to 90°C. According to the present invention it is particularly preferred that the mixing in step (III) is performed at a temperature comprised in the range of from 50 to 70°C.
- step (III) As regards the one or more binders which in step (III) are mixed with the suspension obtained in step (II), there is no particular restriction neither with respect to the type, nor with respect to the number of different binders which may be employed to this effect provided that one or more of the binders may adhere to the zeolitic material in that step and/or during the further course of the inventive process for obtaining a powder or granulate containing binder adhered to the zeolitic material.
- any suitable binder or combination of binders may be employed to this effect, wherein it is however preferred that the one or more binders used in step (III) are selected from the group consisting of inorganic binders and derivatives thereof.
- the term "derivative" as used for defining the one or more inorganic binders preferably refers to any inorganic binder which has been treated with an organic substance and/or contains organic moieties which may be removed from the inorganic binder derivative preferably by combustion thereof at elevated temperatures, and in particular by combustion of the organic substance and/or moiety.
- the one or more binders preferably comprise one or more sources of a metal oxide and/or of a metalloid oxide, and more preferably one or more sources of a metal oxide and/or of a metalloid oxide selected from the group consisting of silica, alumina, titania, zirconia, lanthana, magnesia, and mixtures and/or mixed oxides of two or more thereof.
- the one or more binders preferably comprise one or more sources of a metal oxide and/or of a metalloid oxide selected from the group consisting of silica, alumina, titania, zirconia, magnesia, silica-alumina mixed oxides, silica-titania mixed oxides, silica-zirconia mixed oxides, silica-lanthana mixed oxides, silica-zirconia- lanthana mixed oxides, alumina-titania mixed oxides, alumina-zirconia mixed oxides alumi- na-lanthana mixed oxides, alumina-zirconia-lanthana mixed oxides, titania-zirconia mixed oxides, and mixtures and/or mixed oxides of two or more thereof, more preferably from the group consisting of silica, alumina, silica-alumina mixed oxides and mixtures of two or more thereof.
- a metalloid oxide selected from the group consisting of silica, a
- the one or more binders comprises one or more sources of a metalloid oxide, wherein even more preferably the one or more binders comprise one or more sources of silica.
- the one or more binders consists of one or more - - sources of a metalloid oxide and that in particular the one or more binder consists of one or more sources of silica.
- the one or more sources of silica preferably comprised in the one or more bind- ers according to any of the particular and preferred embodiments of the present invention and more preferably the one or more sources silica of which the one or more binders consist of, there is no particular restriction according to the present invention neither with respect to the specific type nor concerning the number of different sources which may be employed to this effect.
- the one or more sources of silica preferably used in the present invention may comprise one or more compounds selected from the group consisting of fumed silica, colloidal silica, silica-alumina, colloidal silica-alumina, and mixtures of two or more thereof, wherein more preferably the one or more compounds selected from the group consisting of fumed silica, colloidal silica, and mixtures thereof.
- the one or more binders consists of fumed silica and/or colloidal silica, wherein it is yet further preferred that the one or more binders consist of colloidal silica.
- the one or more binders further comprise one or more hydrolysable derivatives of one or more metal oxide and/or metalloid oxide, and preferably one or more hydrolysable resins based on the one or more metal oxide and/or metalloid oxide preferably comprised in the binder.
- hydrolysable as employed with respect to the derivatives of one or more metal oxide and/or metalloid oxide preferably further comprised in the one or more binders, said term preferably refers to the capacity of said derivatives to react with water, and more preferably to the capacity of said derivatives to react with water under standard temperature and pressure.
- hydrolysable derivatives of one or more metal oxide and/or metalloid oxide preferably further comprised in the binder
- any suitable hydrolysable resin based on silica may be employed, provided that it contains one or more chemical moieties which may react with water, and preferably one or more chemical moieties which may react with water under standard temperature and pressure.
- the one or more binders fur- ther comprise one or more hydrolysable silicone resins, more preferably one or more silicone resins containing one or more hydrolysable functional groups.
- the one or - - more hydrolysable groups which may be contained in the one or more silicone resins which are particularly preferred, no particular restrictions apply provided that these react with water, and preferably react with water at standard temperature and pressure, wherein the one or more binders preferably further comprise one or more alkoxy functionalized silicone resins, and more preferably one or more C1 -C5 alkoxy functionalized silicone resins, more preferably one or more C1 -C3 alkoxy functionalized silicone resins, more preferably one or more ethoxy and/or methoxy functionalized silicone resins, more preferably one or more methoxy functionalized silicone resins, wherein the functionalized silicone resin is preferably a functionalized alkyl oligo- and/or polysiloxane, more preferably a functionalized C1
- any suitable amount may be employed depending on the application for which the powder or granulate is intended to be used.
- the binder further comprises one or more hydrolysable derivatives of one or more metal oxide and/or metalloid oxide, such that again any suitable amount of both the one or more binders and the one or more hydrolysable derivatives may be employed depending on the intended use of the resulting powder or granulate.
- the weight ratio of the one or more hydrolysable derivatives of one or more metal and/or metalloid oxide to the one or more binder used in said preferred embodiments such that, by way of ex- ample, the weight ratio of the one or more hydrolysable derivatives of one or more metal oxide and/or metalloid oxide further comprised in the inorganic binder to the one or more sources of a metal oxide and/or of a metalloid oxide (hydrolysable derivatives : metal oxide and/or of a metalloid oxide) may range anywhere from (0.1 - 10) : 1 , wherein preferably the weight ratio ranges from (0.2 - 5) : 1 , more preferably from (0.5 - 3) : 1 , more preferably from (1 - 2.5) : 1 , more preferably from (1.3 - 2.2) : 1 , and more preferably from (1.5 - 2) : 1.
- the hydrolysable derivatives : metal oxide and/or of a metalloid oxide weight ratio is comprised in the range of (1.6 - 1.8) : 1.
- the weight ratio of the zeolitic material to the one or more binders to (zeolitic material : binder) may range anywhere from (1 - 20) : 1 , wherein preferably the zeolitic material : binder weight ratio ranges from (2 - 10) : 1 , more preferably from (3 - 8) : 1 , more preferably from (3.5 - 6) : 1 , more preferably from (4 - 5.5) : 1 , more preferably from (4.3 - 5.2) : 1 , and more preferably from (4.5 - 5) : 1.
- the zeolitic material it is however particularly preferred that the zeolitic material :
- the solid content of the suspension obtained from step (II) in wt.-% of the total weight of the suspension may range anywhere from 5 to 80%
- the solid content of the suspension obtained from step (II) is comprised in the range of from 10 to 60%, and more preferably from 15 to 50%, more preferably from 20 to 40%, and more preferably from 25 to 35%.
- the solid content of the suspension obtained from step (II) in wt.-% of the total weight of the suspension is comprised in the range of from 28 to 32%.
- step (IV) of the inventive process the suspension obtained in step (III) is dried.
- the drying step may be performed at any suitable temperature for any suitable duration, provided that the suspension is effectively dried.
- any conceivable means of drying can be used. Drying procedures preferably include heat- ing and/or applying vacuum to the suspension obtained in step (III), wherein preferably the suspension obtained in step (III) is heated for achieving drying thereof.
- the temperature at which drying of the suspension is preferably performed it may for example lie in the range of anywhere from 25 to 160°C, wherein preferably in step (IV) the suspension obtained in step (III) is dried at a temperature ranging from 60 to 150°C, more prefera- bly of from 80 to 140°C, more preferably in the range of from 100 to 135°C, and even more preferably in the range of from 120 to 130°C.
- the duration of drying preferably lies in the range of from 2 to 60 h, more preferably in the range of 6 to 48 hours, and even more preferably of from 12 to 24 h, wherein in general any suitable duration of drying may be chosen provided that the desired grade of drying of the suspension of obtained in step (III) is achieved.
- the drying may in principle be conducted in any suitable fashion using any conceivable apparatus.
- the suspension may simply be dried by heating and/or by applying vacuum to the suspension to be dried.
- the step of drying is performed such that the form of the dried material is suited for a given application in which it is intended to be used.
- drying may be performed under a particular type of agitation of the suspension such as to influence the characteristics of the powder or granulate.
- the suspension is constantly stirred and/or that the vessel in which the suspension obtained from step - -
- step (II) is to be dried is constantly rotated during the drying procedure, wherein more preferably the rate of stirring and/or rotating is chosen in function of the desired characteristics of the resulting powder or granulate.
- the suspension obtained in step (II) is subject in step (III) to a spray drying procedure for obtained a spray-dried powder, or alternatively to a spray-granulation procedure for obtaining a granulate. Therefore, it is particularly preferred according to the present invention that the suspension obtained in step (II) is spray-dried or spray-granulated, wherein preferably the suspension obtained in step (II) is spray-dried.
- step (V) of the inventive process the dried material obtained in step (IV) is calcined.
- said calcination may be conducted under at any suitable temperature and conditions, provided that it is sufficient for the thermal treatment of the material and in particular for allowing for the removal of any unwanted organic residues still present in the dried material obtained in step (IV).
- the temperature is however preferably chosen such that it causes no substantial damage to the powder or granulate obtained from the inventive process and in particular does not cause any substantial degradation of the framework structure of the zeolitic material.
- any suitable temperature may be chosen for conducting the calcination step such that by way of example the temperature at which the calcination in step (V) is conducted may range anywhere from 350 to 850°C, and preferably at a tempera- ture ranging from 400 to 700°C, more preferably from 450 to 650°C, and more preferably from 475 to 600°C. According to the present invention it is however particularly preferred that the calcination in step (V) is conducted at a temperature ranging from 500 to 550°C.
- the powder or granulate obtained from the inventive process may be further subject to any suitable work-up procedure and/or further treatment steps depending on the specific application in which it is intended to be used.
- the powder or granulate obtained in step (V) is intended for use in a specific catalytic application, it is preferred that the powder or granulate is further treated to load one or more metals thereon.
- inventive process and in particular the inventive process according to any of the particular and preferred embodiments defined in the foregoing, further comprises
- step (VI) supporting one or more metals onto the calcined material obtained in step (V) as non- framework elements
- step (VII) optionally drying the material obtained in step (VI);
- step (VIII) optionally calcining the material obtained in step (VI) or (VII).
- step (V) As regards the one or more metals supported onto the calcined material obtained in step (V), no particular restriction applies according to the present invention such that in principle any suitable metal or combination of two or more metals may be supported depending on - - the intended application of the metal loaded powder or granulate.
- the one or more metals supported on the calcined material obtained in step (V) may be selected from the group consisting of Mg, Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, wherein preferably the one or more metals are selected from the group consisting of Mg, Sr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, and more preferably from the group consisting of Mg, Cr, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof.
- the one or more metals supported onto the calcined material obtained in step (V) comprise Mo and/or Ni, and preferably comprise both Mo and Ni, in particular in cases wherein the resulting powder or granulate is intended for application in a process such a for the conversion of methane to benzene.
- Mo and Ni are the only metals which are supported onto the calcined powder or granulate obtained in step (V) as non-framework elements.
- the loading of the calcined material with one or more metals may by achieved by any suitable impregnation method as well as by any suitable method of ion-exchange wherein extra-framework ions present in the zeolitic material contained in the powder or granulate obtained in step (V) is exchanged against one or more of the one or more metals to be supported onto the powder or granulate.
- the impregnation method which may be employed, again no particular restriction applies neither with respect to the solvent system which may be employed, nor with respect to the metal compound dissolved in the solvent system, provided that the metal may be supported onto the calcined material as non-framework element. Same applies with respect to the amounts of the solvent system employed and the concentration of the metal compound contained therein, wherein it is particularly preferred according to the present invention that the im- pregnation step is performed according to an incipient wetness technique, wherein the volume of the solvent system for impregnation containing the metal compound is equal to or less than the pore volume of the calcined powder or granulate obtained in step (V) which is to be impregnated.
- any suitable amount may be supported depending on the intended application, such that by way of example the amount of the one or more metals supported onto the calcined material may range anywhere from 0.1 to 25 wt.-% calculated as the one or more elements and based on 100 wt.-% of the material obtained in step (VI), and preferably based on 100 wt.-% of the material obtained in step (VII), and more preferably based on 100 wt.-% of the material obtained in step (VIII), wherein it is preferred accord- - - ing to the present invention that the amount of the one or more metals supported onto the calcined material ranges from 0.5 to 20 wt.-%, and more preferably from 1 to 15 wt.-%, more preferably from 3 to 12 wt.-%, more preferably from 4 to 10 wt.-%, more preferably from 5 to 9 w
- the amount of the one or more metals supported on the calcined material obtained in step (V) in step (VI) ranges from 6.5 to 7.5 wt.-% calculated as the one or more elements and based on 100 wt.-% of the material obtained in step (VI), and preferably based on 100 wt.-% of the material obtained in step (VII), and more preferably based on 100 wt.-% of the material obtained in step (VIII).
- the zeolitic material which may be employed in the inventive process provided that it displays the aforementioned X-ray diffraction pattern.
- said ratio is not particularly limited such that by way of example it may range anywhere from 1 to 500, wherein according to the present invention the YO2 : X2O3 molar ratio preferably ranges from from 5 to 200, more preferably from 10 to 150, more preferably from 20 to 100, more preferably from 40 to 70, and more preferably from 45 to 60.
- the YO2 : X2O3 molar ratio in the MFI-type framework structure of the zeolitic material ranges from 50 to 55.
- the zeolitic material having an MFI-type framework structure employed in the inventive process comprises YO2.
- Y stands for any conceivable tetravalent element, Y standing for either or several tetravalent elements.
- Preferred tetravalent elements according to the present invention include Si, Sn, Ti, Zr, and Ge, and combinations thereof. More preferably, Y stands for Si, Ti, or Zr, or any combination of said tetravalent elements, even more preferably for Si, and/or Sn. According to the present invention, it is particularly preferred that Y stands for Si.
- X may in principle stand for any conceivable trivalent element, wherein X stands for one or several trivalent elements.
- Preferred trivalent elements according to the present invention include Al, B, In, and Ga, and combinations there- of. More preferably, X stands for Al, B, or In, or any combination of said trivalent elements, even more preferably for Al and/or B. According to the present invention, it is particularly preferred that X stands for Al.
- any conceivable material may be employed provided that it displays the aforementioned X-ray diffraction pattern according to any of the particular or preferred embodiments defined in the present appli- - 4 - cation.
- the zeolitic material provided in step (I) comprises ZSM-5, wherein even more preferably the zeolitic material provided in step (I) consists of ZSM-5.
- the 29 Si MAS NMR of the zeolitic material employed in the inventive process according to embodiments wherein Y includes Si or is preferably Si there is no particular restriction as to the number and/or respective ppm values and/or relative intensities of the signals displayed in the NMR spectrum. According to preferred embodiments of the present invention, however, the 29 Si MAS NMR comprises
- a first peak (P1) comprised in the range of from -1 10.4 to -1 14.0 ppm and
- a second peak (P2) comprised in the range of from -101.4 to -106.8 ppm
- the first peak is comprised in the range of from -1 10.8 to -113.4 ppm and the second peak is comprised in the range of from -101.6 to -106.5 ppm.
- the first peak (P1 ) is comprised in the range of from -1 1 1.2 to -1 12.8 ppm and the second peak (P2) is comprised in the range of from -101.8 to -106.2 ppm.
- the 29 Si CP MAS NMR of the zeolitic material employed in the inventive process as obtained from ( 1 H - 29 Si) cross polari- zation experiments comprises a first peak (P1) comprised in the range of from -1 10.80 to -1 11.30 ppm and a second peak (P2) comprised in the range of from -101.00 to -103.50 ppm, wherein preferably the integration of the first and second peaks in the 29 Si CP-MAS NMR of the zeolitic material offers a ratio of the integration values P1 : P2 of 1 : (1.40-2.50).
- the first peak (P1 ) is comprised in the range of from -1 11.00 to -1 12.10 ppm and the second peak (P2) is comprised in the range of from -101.50 to -103.00 ppm wherein the integration of the first and second peaks in the 29 Si CP-MAS NMR of the zeolitic material preferably offers a ratio of the integration values P1 : P2 of 1 : (1.45 - 2.20), and more preferably of 1 : (1.50 - 2.10).
- the first peak (P1 ) is comprised in the range of from -1 11.20 to -1 11.95 ppm and the second peak (P2) is comprised in the range of -101.70 to -102.60 ppm, wherein the integration of the first and second peaks offers a ratio of the integration values P1 : P2 of 1 : (1.55 - 2.00), and more preferably of 1 : (1.60 - 1.95).
- the first peak (P1 ) is comprised in the range of from -1 1 1.30 to -1 11.85 ppm and the second peak (P2) is comprised in the range of from -101.95 to -102.40 ppm, wherein the integration of the first and second peaks in the 29 Si CP-MAS NMR of the zeolitic material preferably offers a ratio of the integration values P1 : P2 of 1 : (1.65 - 1.90).
- the deconvoluted 29 Si MAS NMR spectrum of the zeolitic material employed in the inventive process comprises a further peak comprised in the range of from -1 13.2 to -1 15.2 ppm, wherein more preferably said - 5 - additional peak is comprised in the range of from -1 13.5 to -1 14.9 ppm.
- the zeolitic materials comprise a further peak in the deconvoluted 29 Si MAS NMR spectrum comprised in the range of from -1 13.8 to -1 14.7 ppm.
- any suitable method may be employed for deconvolution thereof provided that said method is able to identify a further peak in the 29 Si MAS NMR spectrum of the zeolitic materials of the present invention.
- the deconvolution is performed using DM Fit (Massiot et al., Magnetic Resonance in Chemistry, 40 (2002) pp. 70-76).
- the fitting model is comprised of three Gaussian functions, with starting positions at -103 ppm, -1 12 ppm and -114 ppm.
- both peak position and line width are left unrestrained, with the consequence that the fit peaks are not fixed at a certain position.
- the standard used in the 29 Si MAS NMR experiments for obtaining the respective values for the chemical shift in ppm in the 29 Si MAS NMR spectra according to particular and preferred embodiments of the present invention, wherein preferably an external standard is used.
- the external standard used in the 29 Si MAS NMR experiment is the polymer Q8M8 as an extenal secondary standard in the 29 Si MAS NMR experiment, wherein the resonance of the trimethylsilyl M group is set to 12.5 ppm.
- the present invention further relates to a powder or granulate per se which is obtainable by the in- ventive process and in particular according to any of the particular and preferred embodiments thereof as defined in the foregoing. Furthermore, the inventive process relates to a powder or granulate per se independently of the process by which it may be obtained.
- the present invention further relates to a powder or granulate, preferably obtaina- ble and/or obtained by the inventive process and in particular according to any of the particular and preferred embodiments of the inventive process defined in the foregoing, wherein said powder or granulate comprises a zeolitic material having an MFI-type framework structure comprising Y0 2 and optionally comprising X2O3,
- said material having an X-ray diffraction pattern comprising at least the following reflections:
- the powder or granulate further comprises one or more binders.
- the zeolitic material which may be employed in the inventive powder or granulate it is not particularly restricted provided that it displays the X-ray diffraction pattern as defined in the present application, and in particular according to any of the particular and preferred embodiments defined herein. According to the present invention, there is no particular restriction as to the zeolitic material which may be employed in the inventive process provided that it displays the aforementioned X- ray diffraction pattern.
- the intensity of the first reflection comprised in the range of 7.88° - 8.16° 2 ⁇
- the intensity of said reflection is comprised in the range of from 15 - 45, more preferably of from 16 - 30, and even more preferably of from 17 - 23.
- the intensity of the second reflection comprised in the range of 8.83° - 9.13° 2 ⁇
- the intensity of said reflection is comprised in the range of from 12 - 30, more preferably of from 13 - 25, more preferably of from 14 - 23, and even more preferably of from 15 - 21.
- the zeolitic material having an MFI-type framework structure comprised in the inventive powder or granulate has an X-ray diffraction pattern comprising at least the following reflections:
- the zeolitic material having an MFI-type framework structure comprised in the inventive powder or granulate has an X-ray diffraction pattern comprising at least the following reflections: - 7 -
- the intensity of the first reflection comprised in the range of 7.95° - 8.09° 2 ⁇ it is preferred according to the present invention that the intensity of said reflection is comprised in the range of from 17 - 30, more preferably of from 17 - 25, and even more preferably of from 17 - 23.
- the intensity of the second reflection comprised in the range of 8.91 ° - 9.05° 2 ⁇ it is preferred according to the present invention that the intensity of said reflection is comprised in the range of from 15 - 24, more prefera- bly of from 14 - 22, and even more preferably of from 15 - 21.
- the 29 Si MAS NMR of the zeolitic material comprised in the inventive powder or granulate according to embodiments wherein Y includes Si or is preferably Si there is no particular restriction as to the number and/or respective ppm values and/or relative intensities of the signals displayed in the NMR spectrum. According to preferred embodiments of the present invention, however, the 29 Si MAS NMR comprises
- a first peak (P1) comprised in the range of from -1 10.4 to -1 14.0 ppm and
- a second peak (P2) comprised in the range of from -101.4 to -106.8 ppm
- the first peak is comprised in the range of from -1 10.8 to -113.4 ppm and the second peak is comprised in the range of from -101.6 to -106.5 ppm.
- the first peak (P1 ) is comprised in the range of from -1 1 1.2 to -1 12.8 ppm and the second peak (P2) is comprised in the range of from -101.8 to -106.2 ppm.
- the 29 Si CP MAS NMR of the zeolitic material comprised in the inventive powder or granulate as obtained from ( 1 H - 29 Si) cross polarization experiments comprises a first peak (P1) comprised in the range of from -1 10.80 to -1 11.30 ppm and a second peak (P2) comprised in the range of from -101.00 to -103.50 ppm, wherein preferably the integration of the first and second peaks in the 29 Si CP-MAS NMR of the zeolitic material offers a ratio of the integration values P1 : P2 of - -
- the first peak (P1 ) is comprised in the range of from -1 11.00 to -1 12.10 ppm and the second peak (P2) is comprised in the range of from -101.50 to -103.00 ppm wherein the integration of the first and second peaks in the 29 Si CP-MAS NMR of the zeolitic material preferably offers a ratio of the integration values P1 : P2 of 1 : (1.45 - 2.20), and more preferably of 1 : (1.50 - 2.10).
- the first peak (P1 ) is comprised in the range of from -1 11.20 to -1 11.95 ppm and the second peak (P2) is comprised in the range of -101.70 to -102.60 ppm, wherein the integration of the first and second peaks offers a ratio of the integration values P1 : P2 of 1 : (1.55 - 2.00), and more preferably of 1 : (1.60 - 1.95).
- the first peak (P1) is comprised in the range of from -1 1 1.30 to -1 11.85 ppm and the second peak (P2) is comprised in the range of from -101.95 to -102.40 ppm, wherein the integration of the first and second peaks in the 29 Si CP-MAS NMR of the zeolitic material preferably offers a ratio of the integration values P1 : P2 of 1 : (1.65 - 1.90).
- the deconvoluted 29 Si MAS NMR spectrum of the zeolitic material comprised in the inventive powder or granulate comprises a further peak comprised in the range of from -1 13.2 to -1 15.2 ppm, wherein more prefera- bly said additional peak is comprised in the range of from -1 13.5 to -1 14.9 ppm.
- the zeolitic materials comprise a further peak in the deconvoluted 29 Si MAS NMR spectrum comprised in the range of from -1 13.8 to -1 14.7 ppm.
- the zeolitic material which may be comprised in the inventive powder or granulate provided that it displays the aforementioned X-ray diffraction pattern.
- said ratio is not par- ticularly limited such that by way of example it may range anywhere from 1 to 500, wherein according to the present invention the YO2 : X2O3 molar ratio preferably ranges from from 5 to 200, more preferably from 10 to 150, more preferably from 20 to 100, more preferably from 40 to 70, and more preferably from 45 to 60.
- the YO2 : X2O3 molar ratio in the MFI-type framework structure of the zeolitic material ranges from 50 to 55.
- the zeolitic material having an MFI-type framework structure comprised in the inventive powder or granulate comprises YO2.
- Y stands for any conceivable tetravalent element, Y standing for either or several tetravalent elements.
- Preferred tetravalent elements according to the present invention include Si, Sn, Ti, Zr, and Ge, and combinations thereof. More preferably, Y stands for Si, Ti, or Zr, or any - - combination of said tetravalent elements, even more preferably for Si, and/or Sn. According to the present invention, it is particularly preferred that Y stands for Si.
- X may in principle stand for any conceivable trivalent element, wherein X stands for one or several trivalent elements.
- Preferred trivalent elements according to the present invention include Al, B, In, and Ga, and combinations thereof. More preferably, X stands for Al, B, or In, or any combination of said trivalent elements, even more preferably for Al and/or B. According to the present invention, it is par- ticularly preferred that X stands for Al.
- any conceivable material may be employed provided that it displays the aforementioned X-ray diffraction pattern according to any of the particular or preferred embodiments defined in the present application.
- the zeolitic material comprised in the inventive powder or granulate comprises ZSM-5, wherein even more preferably the zeolitic material comprised in the inventive powder or granulate consists of ZSM-5.
- said zeolitic material preferably further contains one or more types of non-framework elements which do not constitute the framework structure and are accordingly present in the pores and/or cavities formed by the framework structure and typical for zeolitic material in general.
- non-framework elements which may be contained in the zeolitic material, nor with respect to the amount in which they may be present therein.
- the zeolitic material comprised in the inventive powder or granule comprises one or more cation and/or cationic elements as ionic non-framework elements, wherein again no particular restriction applies as to the type or number of different types of ionic non-framework elements which may be present in the zeolitic material, nor as to their respective amount.
- the ionic non-framework elements preferably comprise one or more cations and/or cationic elements selected from the group consisting of H + , ⁇ 4 + , Mg, Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, wherein more preferably these are selected from the group consisting of H + , NH 4 + , Mg, Sr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably from the group consisting of H + , N H4 + , Mg, Cr, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, and more preferably selected from the group consisting of Mg, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof.
- the ionic non-framework elements comprise Mo and/or Ni as ionic non-framework ele- ments, preferably Mo and Ni, wherein even more preferably the zeolitic material comprises Mo and/or Ni as ionic non-framework elements, and preferably both Mo and Ni. - -
- the amount in which the one or more cations and/or cationic elements may be contained in the zeolitic material comprised in the inventive powder or granulate no particular restriction applies such that in principle any suitable amount may be contained therein, in particular depending on the application for which the powder or granulate is intended for.
- the amount of the one or more cations and/or cationic elements may range anywhere from 0.5 to 20 wt.-% calculated as the one or more elements and based on 100 wt.-% of the calcined powder or granulate, wherein preferably the amount of the one or more cations and/or cationic elements ranges from 1 to 15 wt.-%, more preferably from 3 to 12 wt.-%, more preferably from 4 to 10 wt.-%, more preferably from 5 to 9 wt.- %, and more preferably from 6 to 8 wt.-%. According to the present invention it is particularly preferred that the amount of the one or more cations and/or cationic elements is comprised in the range of from 6.5 to 7.5 wt.-%.
- any suitable further materials may be contained therein, wherein according to the present invention the inventive powder or granulate further comprises one or more binders in addition to the zeolitic material.
- the type or number of binders which is further comprised in the inventive powder or granulate again no particular restriction applies, such that by way of example the powder or granulate may further comprise one or more binders selected from the group of inorganic and organic binders, including mixtures of two or more thereof.
- the one or more binders comprise one or more inorganic binders, wherein preferably the one or more binders comprise one or more sources of a metal oxide and/or of a metalloid oxide, and more preferably one or more sources of a metal oxide and/or of a metalloid oxide selected from the group consisting of silica, alumina, titania, zirconia, lanthana, magnesia, and mixtures and/or mixed oxides of two or more thereof, more preferably from the group consisting of silica, alumina, titania, zirconia, magnesia, silica-alumina mixed oxides, silica-titania mixed oxides, silica-zirconia mixed oxides, silica-lanthana mixed oxides, silica-zirconia-lanthana mixed oxides, alumina- titania mixed oxides, alumina-zirconia mixed oxides alumina-lanthana mixed oxides,
- the binder consists of one or more sources of silica, wherein the one or more sources of silica preferably comprise one or more compounds selected from the group consisting of fumed silica, colloidal silica, silica-alumina, colloidal silica-alumina, calcined silicone resin, and mixtures of two or more thereof, more preferably one or more com- pounds selected from the group consisting of fumed silica, colloidal silica, calcined silicone resin, and mixtures thereof.
- the one or more binders consists of colloidal silica and/or calcined silicone resin, and more preferably of both colloidal silica and calcined silicone resin.
- the surface may range anywhere from 50 to 700 m 2 /g, wherein preferably the surface area of the powder or granulate is comprised in the range of from 100 to 500 m 2 /g, wherein more preferably the surface area ranges from 150 to 475 m 2 /g, more preferably from 200 to 450 m 2 /g, more preferably from 250 to 425 m 2 /g, and more preferably from 300 to 400 m 2 /g.
- the inventive powder or granulate displays a specific surface area ranging from 325 to 375 m 2 /g.
- the term "specific surface area” preferably refers to the specific surface area of the materials described when determined according to DIN 66131.
- the inventive powder or granulate may have, no particular restriction applies.
- the size and morphology thereof may be accordingly chosen or adapted to the given requirements of the specific application.
- the powder or granulate of the present invention is obtained from spray- drying or from spray-granulation, and more preferably from spray-drying such that accord- ing to the present invention it is particularly preferred that the inventive powder or granulate is a spray-dried powder or spray-granulate, respectively, wherein a spray-dried powder is yet further preferred according to the present invention.
- the inventive powder or granulate described above can be used in any suitable ap- plication such as by way of example as a molecular sieve, adsorbent, catalyst, or catalyst support.
- the inventive powder or granulate according to any of the particular and preferred embodiments of the present invention can be used as molecular sieve to dry gases or liquids, for selective molecular separation, e.g. for the separation of hydrocarbons or amines; as ion exchanger; as chemical carrier; as adsorbent, in particular as adsorbent for the separation of hydrocarbons or amines; or as a catalyst.
- the inventive powder or granulate is used as a catalyst and/or as a catalyst support.
- the inventive powder or granulate is used in a catalytic process, and preferably as a catalyst and/or catalyst support, and more preferably as a catalyst.
- the inventive powder or granulate can be used as a catalyst and/or catalyst support in any conceivable catalytic process, wherein processes involving the conversion of at least one organic compound is preferred, more preferably of organic compounds comprising at least one carbon - carbon and/or carbon - oxygen and/or carbon - nitrogen bond, more preferably of organic compounds comprising at least one carbon - carbon and/or carbon - oxygen bond, and even more preferably of organic compounds comprising at least one carbon - carbon bond.
- inventive powder or granulate is used as a molecular trap for organic compounds.
- any type of organic compound may be trapped in the zeolitic materials, wherein it is preferred that the compound is re- versibly trapped, such that it may be later released from the inventive powder or granulate, preferably wherein the organic compound is released - preferably without conversion thereof - by an increase in temperature and/or a decrease in pressure.
- the inventive powder or granulate is used to trap organic compounds of which the dimensions allow them to penetrate the microporous system of the molecular structure of the zeolitic material contained in the inventive powder or granulate.
- the trapped compounds are released under at least partial conversion thereof to a chemical derivative and/or to a decomposition product thereof, and preferably to a thermal decomposition product thereof.
- the inventive powder or granulate may be used in any conceivable way, wherein it is preferably used as a catalyst, catalyst support, adsorbent, or for ion exchange, wherein preferably the powder or granulate is used as a catalyst and/or catalyst support, more preferably as a catalyst and/or catalyst support in a reaction involving C-C bond formation and/or conversion, and preferably as a catalyst and/or catalyst support in an isomerization reaction, in an ammoxidation reaction, in a hy- drocracking reaction, in an alkylation reaction, in an acylation reaction, in a reaction for the conversion of alkanes to olefins and/or aromatics, or in a reaction for the conversion of one or more oxygenates to olefins and/or aromatics, wherein more preferably the powder or granulate is used in a process for the conversion of alkanes to aromatics, preferably in a methane to benzene
- the present invention includes the following embodiments, wherein these include the specific combinations of embodiments as indicated by the respective interdependencies defined therein:
- a process for the production of a powder or granulate comprising
- step (II) suspending the zeolitic material provided in step (I) in a solvent system
- step (III) mixing the suspension obtained in step (II) with one or more binders;
- step (V) calcining of the dried material obtained in step (IV);
- zeolitic material provided in step (I) has an MFI-type framework structure comprising YO2 and optionally comprising X2O3,
- said material having an X-ray diffraction pattern comprising at least the following reflections:
- the solvent system comprises one or more solvents
- the solvent system comprises one or more hydrophilic solvents
- the hydrophilic solvents preferably being selected from the group consisting of polar solvents, more preferably from the group consisting of polar protic solvents
- more preferably the solvent system comprises one or more polar protic solvents selected from the group consisting of water, alcohols, carboxylic acids, and mixtures of two or more thereof, more preferably from the group consisting of water, C1 -C5 alcohols, C1 -C5 carboxylic acids, and mixtures of two or more thereof, more preferably from the group consisting of water, C1 -C4 alcohols, C1 -C4 carboxylic acids, and mixtures of two or more thereof, more preferably from the group consisting of water, C1 -C3 alcohols, C1 -C3 carboxylic acids, and mixtures of two or more thereof, more preferably from the group consisting of water, methanol, ethanol,
- step (II) wherein the zeolitic material in the suspension obtained in step (II) displays a particle size D90 ranging from 0.05 to 20 ⁇ , preferably from 0.1 to 10 ⁇ , more preferably from 0.5 to 5 ⁇ , more preferably from 0.8 to 4 ⁇ , more preferably from 1 to 3.5 ⁇ , more preferably from 1.3 to 2.9 ⁇ , and more preferably from 1 .5 to 2.5 ⁇ .
- step (III) mixing in step (III) is conducted under heating, wherein preferably the mixing is performed at a temperature ranging from 30 to 150°C, preferably from 35 to 130°C, more preferably from 40 to 1 10°C, more preferably from 45 to 90°C, more preferably from 50 to 70°C.
- the one or more binders further comprise one or more hydrolysable derivatives of one or more metal oxide and/or metalloid oxide, preferably one or more hydrolysable resins based on the one or more metal oxide and/or metalloid oxide, more preferably one or more hydrolysable resins based on one or more metalloid oxides, more preferably one or more hydrolysable resins based on silica, more preferably one or more hydrolysable silicone resins, more preferably one or more silicone resins containing one or more hydrolysable functional groups, more preferably one or more alkoxy functionalized silicone resins, more preferably one or more C1 -C5 alkoxy function- alized silicone resins, more preferably one or more C1 -C3 alkoxy functionalized silicone resins, more preferably one or more ethoxy and/or methoxy functionalized silicone resins, more preferably one or more methoxy functionalized silicone resins, wherein the functionalized silicone resin is preferably a functionalized alkyl
- step (III) the weight ratio of the zeo- litic material to the one or more binders to (zeolitic material : binder) ranges from (1 - 20) : 1 , preferably from (2 - 10) : 1 , more preferably from (3 - 8) : 1 , more preferably from (3.5 -
- step (VI) supporting one or more metals onto the calcined material obtained in step (V) as non-framework elements
- step (VII) optionally drying the material obtained in step (VI);
- step (VIII) optionally calcining the material obtained in step (VI) or (VII).
- the one or more metals comprise one or more selected from the group consisting of Mg, Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Sr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Cr, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, wherein more preferably the one or more metals comprise Mo and/or Ni, preferably Mo and Ni, wherein even more preferably Mo and Ni are supported onto the calcined material obtained in step (V) as non-framework elements.
- the amount of the one or more metals supported onto the calcined material ranges from 0.5 to 20 wt.-%, more preferably from 1 to 15 wt.-%, more preferably from 3 to 12 wt.-%, more preferably from 4 to 10 wt- %, more preferably from 5 to 9 wt.-%, more preferably from 6 to 8 wt.-%, and more preferably from 6.5 to 7.5 wt.-%.
- a second peak (P2) in the range of from -101 .4 to -106.8 ppm, preferably of from -101 .6 to -106.5 ppm, and even more preferably of from -101 .8 to -106.2 ppm.
- Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof, Y preferably being Si.
- X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof, X preferably being Al and/or B, and more preferably being Al.
- step (I) comprises ZSM-5, wherein preferably the zeolitic material provided in step (I) consists of ZSM-5.
- said material having an X-ray diffraction pattern comprising at least the following reflections:
- the powder or granulate further comprises one or more binders.
- a second peak (P2) in the range of from -101 .4 to -106.8 ppm, preferably of from -101 .6 to -106.5 ppm, and even more preferably of from -101 .8 to -106.2 ppm.
- any of embodiments 22 to 24, wherein the YO2 : X2O3 molar ratio of the zeolitic material having an MFI-type framework structure ranges from 1 to 500, preferably from 5 to 200, more preferably from 10 to 150, more preferably from 20 to 100, more preferably from 40 to 70, more preferably from 45 to 60, and even more preferably from 50 to 55.
- Al and/or B and more preferably being Al.
- the zeolitic material comprises one or more cations and/or cationic elements as ionic non-framework elements, said one or more cations and/or cationic elements preferably comprising one or more selected from the group consisting of H + , NH 4 + , Mg, Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, more preferably from the group consisting of H + , NH 4 + , Mg, Sr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably from the group consisting of H + , NH 4 + , Mg, Cr, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more
- a powder or granulate according to any of embodiments 21 to 33 as a catalyst, catalyst support, adsorbent, or for ion exchange, wherein preferably the powder or granulate is used as a catalyst and/or catalyst support, more preferably as a catalyst and/or catalyst support in a reaction involving C-C bond formation and/or conversion, and preferably as a catalyst and/or catalyst support in an isomerization reaction, in an ammoxidation reaction, in a hydrocracking reaction, in an alkylation reaction, in an acylation reaction, in a reaction for the conversion of alkanes to olefins and/or aromatics, or in a reaction for the conversion of one or more oxygenates to olefins and/or aromatics, wherein more preferably the powder or granulate is used in a process for the conversion of alkanes to aromatics, preferably in a methane to benzene process.
- Figure 1 displays the X-ray diffraction pattern (measured using Cu K alpha-1 radiation) of the crystalline material obtained according to Reference Example 1.
- the angle 2 theta in ° is shown along the abscissa and the intensities are plotted along the ordinate.
- Figure 2 displays the scanning electron microscope (SEM) image obtained from the sample of the crystalline product obtained according to Reference Example 1 . - -
- Figure 3 shows the 29 Si MAS NMR obtained from the sample obtained according to Reference Example 1 .
- the values in ppm are plotted along the abscissa, wherein the exact ppm values are indicated above the respective peaks and shoulders, including the integration of the peaks in % indicated below the re- spective peaks.
- the values plotted along the ordinate indicate the intensity of the NMR signal for given values of the chemical shift in ppm.
- Figure 4 shows the deconvoluted 29 Si MAS NMR obtained from the sample obtained according to Reference Example 1 .
- the values in ppm are plotted along the abscissa, wherein the relative intensities in % of the peaks identified by deconvolution is indicated next to the respective deconvoluted peak.
- Figure 5 displays the results from catalytic testing in the conversion of methane to benzene (MTB).
- the duration of the catalytic testing (cycles) in hours is plotted along the abscissa.
- the ordinate to the left indicates the selectivity of the reaction in % towards a particular product as indicated in the graph, whereas the right ordinate displays the conversion rate of methane in the MTB-reaction in %.
- Reference Example 1 Synthesis of ZSM-5 with allyltripropylammonium hydroxide (ATPAOH) using aluminum triisoproylate 12.2 kg allyltripropylammonium hydroxide (20.2 wt-% in H2O) were mixed together with 0.125 kg NaOH (solid). Afterwards 0.448 kg aluminum triisopropylate was added under stirring to the reaction mixture until the solid was completely dissolved. Finally, 8.253 kg Ludox® AS 40 (40 wt-% colloidal S1O2 in H20) is added to the reaction mixture. The dispersion was then filled in an autoclave which was then heated under stirring within 7h to 170°C and then held at that temperature for 72h.
- Example 1 Preparation of a spray-dried powder
- 2.4 kg of polymethoxysiloxane (Silres® MSE 100, Wacker Silicon) and 1 .4 kg of colloidal silica (Nalco® DVSZN006, Nalco Company) were then slowly mixed into the aqueous zeolite suspension. The resulting suspension was then further mixed and heated to 50-70°C for 1 h.
- the suspension was then spray dried using a spray-dryer from Niro with a single-substance nozzle (0.6 mm diameter) employing nitrogen gas as the sprayer gas.
- the temperature used in the drying procedure ranged from 120 to 130°C.
- the resulting spray-dried powder was then dried over night at 120°C and subsequently calcined in air for 4h at 500 to 550°C.
- the BET surface area of the final powder was determined to 355 m 2 /g via N2 sorption according to DIN 66131 .
- Example 2 Catalytic testing in conversion of methane to benzene (MTB)
- MTB tests with 100 g samples of the catalyst powder obtained according to Example 1 were performed in a fluidized-bed reactor. Prior to catalytic testing, methane was conducted at a rate of 100 Nl/h (normliters per hour) through the reactor, until the reaction temperature was reached. The flow rate was calculated for standard pressure and temperature. The reaction was then initiated at a temperature of 700°C and 2.5 bar and was conducted using a mixture of methane and helium with a CH4 : He ratio of (90 : 10) at a flow rate of 20 Nl/h. During testing, the catalyst samples were regenerated at regular intervals by conducting hydrogen gas into the - - reactor for 5 h at 4 bar and a temperature of 750°C. Each reaction cycle was conducted for a period of 10 h.
- the inventive catalyst powders display a high selectivity towards the conversion of methane to benzene and an accordingly low selectivity towards the generation of ethene and coke as by-products. Accordingly, the inventive catalyst powder displays a high selectivity towards benzene when employed in the MTB reaction.
Abstract
A process for the production of a powder or granulate, comprising (I) providing a zeolitic material; (II) suspending the zeolitic material provided in step (I) in a solvent system; (III) mixing the suspension obtained in step (II) with one or more binders; (IV) drying the suspension obtained in step (III); and (V) calcining of the dried material obtained in step (IV); wherein the zeolitic material provided in step (I) has an MFI-type framework structure comprising YO2 and optionally comprising X2O3, wherein Y is a tetravalent element, and X is a trivalent element, said material having an X-ray diffraction pattern comprising at least the following reflections: (I) wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern, as well as to a powder or granulate per se and to its use.
Description
Powder or Granulate for a Zeolitic Material and Process for its Production
The present invention relates to a process for the preparation of a powder or granulate contain- ing a zeolitic material and a binder, and to a powder or granulate which is obtainable by such a process. The present invention further relates to a powder or granulate per se containing a zeolitic material and a binder, as well as to the use of said powder or granulate in specific applications, and in particular in catalytic processes.
INTRODUCTION
Due to the crystallinity of zeolitic materials in general, it is common in the art to produce powders or granulates thereof using a binder not only for ease of handling but also for avoiding physical deterioration of the zeolitic materials in applications in which these are used, and in particular in applications requiring a certain operation resistance due to physical wear of the materials in specific process steps where the zeolitic materials as such would be subject to agitation. In particular, a specific abrasion resistance is required in cases wherein the zeolitic material is employed in processes employing a fluidized-bed technology. Furthermore, powders or granulates of zeolitic materials containing a binder are often required in catalytic processes wherein a dilution of the zeolitic materials is further required for better control of the catalytic activity by avoiding heat buildup which may occur when using a high concentration of the zeolitic material. Thus, in the field of catalysis, the use of powders or granulates of zeolitic materials containing a binder plays an important role for providing catalytically active zeolitic materials in a physical state in which optimal control of their activity by proper dilution in a specific volume coupled with heat dissipation means in the case of exothermic reactions allows for the fine- tuning of the catalytic process.
Thus, a large variety of catalyzed reactions is known in which the use of specific powders or granulates containing the catalytically active zeolitic materials plays a crucial role for optimal control of the reaction parameters. The known processes for the production of powders or granulates containing zeolitic materials however tend to show a relatively narrow tolerance with respect to the catalytically active components which may be incorporated in said powders or granulates such that they are generally restricted to the use of zeolites and materials of which the physical properties are comparable to those typically found in zeolitic materials. In particular, already small variations in the zeolitic materials physical properties may already lead to an intolerance relative to the binder such as to prevent the production of powders or granulates of zeolitic materials according to conventional means. A need therefore exists for the provision of powders or granulates of zeolitic materials and processes for their preparation which are adapted to zeolitic materials having different physical properties than those generally observed in zeolites, in particular for allowing the production of powders or granulates containing novel and yet unknown zeolitic materials for use in catalytic
- - applications necessitating the use of powders or granulates, or for which the use of powders or granulates would prove advantageous for providing an improved environment for the zeolitic species, in particular relative to their catalytic activity and abrasion resistance. This applies in particular since the use of powders or granulates in a variety of catalyzed reactions allow for the gradual variation and thus for the optimization of the chemical and physical properties of the powders or granulates containing zeolitic materials for making it possible to fine-tune the resulting product in function of the specific requirements needed for a given application.
DETAILED DESCRIPTION
It is therefore the object of the present invention to provide a process for the production of a powder or granulate which may employ a wider variety of zeolitic materials. In particular, it is the object of the present invention to provide a methodology for the preparation of powders or gran- ulates of zeolitic materials which due to their particular physical and chemical properties either could not be processed to binder containing materials using the methodologies known in the art, or which only displayed poor results in catalysis after having been processed to a powder or granulate compared to their catalytic properties when employed as such in zeolitic form. Consequently, the present invention also aims to improve the catalytic performance of zeolitic mate- rials which due to their physical and chemical particular properties may not be suited for use in powders or granulates presently known in the art.
Therefore, the present invention relates to a process for the production of a powder or granulate, comprising
(I) providing a zeolitic material;
(II) suspending the zeolitic material provided in step (I) in a solvent system;
(III) mixing the suspension obtained in step (II) with one or more binders;
(IV) drying the suspension obtained in step (III); and
(V) calcining of the dried material obtained in step (IV);
wherein the zeolitic material provided in step (I) has an MFI-type framework structure comprising YO2 and optionally comprising X2O3,
wherein Y is a tetravalent element, and X is a trivalent element,
said material having an X-ray diffraction pattern comprising at least the following reflections:
Intensity (%) Diffraction angle 2θ/° [Cu K(alpha 1 )]
15 - 55 7.88 - 8.16
1 1 - 35 8.83 - 9.13
100 23.04 - 23.46
27 - 40 23.68 - 23.89
- -
wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern. It is herewith noted that within the meaning of the present invention, and in particular with respect to the particular and preferred embodiments defined in the present application, the term "comprising" is alternatively used as meaning "consisting of", i.e. as specifically and explicitly disclosing corresponding embodiments wherein the subject-matter defined as comprising specific features actually consists of said specific features. According to the present invention, however, the term "comprising" is preferably employed according to its common definition as not limiting the subject-matter to the sole feature or features which it is explicitly stated as comprising.
According to the present invention, there is no particular restriction as to the zeolitic material which may be employed in the inventive process provided that it displays the aforementioned X- ray diffraction pattern. As regards the intensity of the first reflection comprised in the range of 7.88° - 8.16° 2Θ, it is preferred according to the present invention that the intensity of said reflection is comprised in the range of from 15 - 45, more preferably of from 16 - 30, and even more preferably of from 17 - 23. Furthermore or in addition thereto, and preferably in addition thereto, as regards the intensity of the second reflection comprised in the range of 8.83° - 9.13° 2Θ, it is preferred according to the present invention that the intensity of said reflection is comprised in the range of from 12 - 30, more preferably of from 13 - 25, more preferably of from 14 - 23, and even more preferably of from 15 - 21 . According to the present invention, it is further preferred that the synthetic zeolitic material having an MFI-type framework structure used in the inventive process has an X-ray diffraction pattern comprising at least the following reflections:
Intensity (%) Diffraction angle 2Θ/0 [Cu K(alpha 1 )]
17 - 45 7.95 - 8.09
15 - 25 8.91 - 9.05
100 23.14 - 23.35
30 - 36 23.74 - 23.86
33 - 55 23.95 - 24.14
28 - 38 24.40 - 24.61
wherein again 100 % relates to the intensity of the maximum peak in the X-ray powder diffraction pattern. According to the present invention it is yet further preferred that the zeolitic material having an MFI-type framework structure used in the inventive process has an X-ray diffraction pattern comprising at least the following reflections:
According to said preferred embodiments, as regards the intensity of the first reflection comprised in the range of 7.95° - 8.09° 2Θ, it is preferred according to the present invention that the intensity of said reflection is comprised in the range of from 17 - 30, more prefera- bly of from 17 - 25, and even more preferably of from 17 - 23. Furthermore or in addition thereto, and preferably in addition thereto, as regards the intensity of the second reflection comprised in the range of 8.91 ° - 9.05° 2Θ, it is preferred according to the present invention that the intensity of said reflection is comprised in the range of from 15 - 24, more preferably of from 14 - 22, and even more preferably of from 15 - 21.
As regards the solvent system which may be employed in the inventive process, no particular restriction applies such that in principle any suitable solvent system may be employed provided that the zeolitic material may be suspended therein. In general, the solvent system may comprise one or more solvents, wherein it is preferred according to the present inven- tion that the solvent system comprises one or more solvents. Furthermore, it is preferred according to the present invention that the solvent system comprises one or more hydro- philic solvents, the hydrophilic solvents preferably being selected from the group consisting of polar solvents, more preferably from the group consisting of polar protic solvents. As regards the polar protic solvents preferably comprised in the solvent system, again no particu- lar restriction applies as to the number or further physical and chemical properties thereof provided that a suspension may be obtained in step (II) of the inventive process.
According to the present invention it is however preferred that the solvent system comprises one or more polar protic solvents selected from the group consisting of water, alcohols, car- boxylic acids, and mixtures of two or more thereof, more preferably from the group consist-
ing of water, C1 -C5 alcohols, C1 -C5 carboxylic acids, and mixtures of two or more thereof, more preferably from the group consisting of water, C1 -C4 alcohols, C1 -C4 carboxylic acids, and mixtures of two or more thereof, and more preferably from the group consisting of water, C1 -C3 alcohols, C1 -C3 carboxylic acids, and mixtures of two or more thereof.
Concerning the specific compounds among the aforementioned alcohols and carboxylic acids, these may principally be branched or unbranched and/or may be substituted or un- substituted wherein within the meaning of the present invention the term "substituted" preferably refers to the substitution of one or more hydrogen atoms of the alkyl group inde- pendently from one another by one or more monovalent moieties, and more preferably by a halide or pseudohalide, more preferably by a halide, and even more preferably by a halide selected from the group consisting of F, CI, and Br, and yet more preferably by F or CI.
It is, however, preferred according to the present invention, that the one or more polar protic solvents preferably comprised in the solvent system used in step (II) of the inventive process comprises unsubstituted polar protic solvents, and preferably unsubstituted polar pro- tic solvents selected from the group consisting of water, methanol, ethanol, propanol, formic acid, acetic acid, and mixtures of two or more thereof, more preferably from the group consisting of water, ethanol, acetic acid, and mixtures of two or more thereof, wherein more preferably the solvent system comprises water and/or ethanol. According to the present invention it is particularly preferred that the solvent system employed in step (II) comprises water, wherein it is yet further preferred that the solvent system does not contain any further solvents besides water, such that in such cases the solvent system employed in step (II) consists of water.
As noted above, there is no particular as to the chemical and physical characteristics of the zeolitic material employed in the inventive process provided that it displays an X-ray diffraction pattern as according to any of the particular and preferred embodiments of the inventive process. This applies also with respect to the morphology of the zeolitic material involved such that in principle zeolitic materials with any suitable morphology, and in particular any suitable shapes or sizes may be used. It is, however, preferred according to the present invention that the zeolitic material displays a particle size which may be well dispersed in the solvent system employed, and in particular in the solvent system employed according to the particular and preferred embodiments of the inventive process. In general, it is preferred that the zeolitic materials display a small particle size and in particular that the zeolitic material is employed in a microcrystalline state. According to the present invention it is thus particularly preferred that the zeolitic material displays a particle size D90 ranging from 0.05 to 20 μιη, and more preferably from 0.1 to 10 μιη, more preferably from 0.5 to 5 μιη, more preferably from 0.8 to 4 μιη, more preferably from 1 to 3.5 μιη, and more pref- erably from 1.3 to 2.9 μιη. According to the inventive process it is however particularly pre-
- - ferred that the particle size D90 of the zeolitic material employed in the inventive process ranges from 1.5 to 2.5 μιη.
As concerns the particle size D90 of the zeolitic material employed in the inventive process, said particle size according to any of the particular and preferred embodiments of the present invention refers to the zeolitic material at any stage of the inventive process, such that it may designate the particle size D90 of the zeolitic material as it is provided in step (I) of the inventive process, or may also designate the particle size D90 of the zeolitic material after having suspended the same in the solvent system according to step (II) of the in- ventive process, the initial particle size D90 having been larger prior to step (II) of suspending the zeolitic material in the solvent system. Thus according to the present invention it is particularly preferred that a zeolitic material having a larger particle size D90 is provided in step (I) of the inventive process, the particle size then being reduced in step (II) of the inventive process during step (II) of suspending the zeolitic material in the solvent system, and in particular wherein the particle size D90 is reduced in step (II) to a particle size comprised in any of the particular and preferred ranges of particle sizes D90 as defined in the foregoing.
Regarding the particular and preferred embodiments of the present invention wherein the particle size D90 of the zeolitic material is reduced in step (II) of the inventive process, there is no particular restriction as to how or to what extent a reduction of the particle size D90 is achieved. Thus, by way of example, a reduction in the particle size D90 may be achieved by abrasion of the particles against one another during the suspending of the zeolitic material, wherein the duration of the procedure for preparing the suspension may accordingly be chosen in function of the particle size D90 which is desired. It is, however, further preferred according to the present invention that a step of milling the zeolitic material is performed prior to or during step (II) of suspending the zeolitic material in the solvent system in step, wherein preferably the zeolitic material is milled during the course of step (II), an more preferably wet-milled, and even more preferably wet-milled using the solvent system in which the zeolite is suspended in step (II). Concerning the milling procedure employed in any of said preferred embodiments of the inventive process, no specific restriction applies such that any suitable milling procedure or apparatus may be employed, wherein it is preferred according to the present invention that a ball mill is employed for reducing the particle size D90 or the zeolitic material to a value as defined in any of the particular and preferred em- bodiments of the present application.
In step (III) of the inventive process, the suspension obtained in step (II) according to any of the aforementioned particular and preferred embodiments is mixed with one or more binders. As regards the conditions employed for the mixing process in step (III), no restrictions whatsoever apply according to the present invention, such that in principle any conceivable procedure may be employed using any suitable type of apparatus under any suitable condi-
tions, provided that a homogenous mixture is obtained as a result of the mixing procedure in step (III). Thus, in principle, the mixing procedure may be conducted at any suitable temperature, wherein it is preferred according to the present invention that the mixing in step (III) is conducted at an elevated temperature with respect to room temperature (25°C), wherein more preferably the mixing in step (III) is performed at a temperature ranging from 30 to 150°C, more preferably from 35 to 130°C, more preferably from 40 to 1 10°C, and more preferably from 45 to 90°C. According to the present invention it is particularly preferred that the mixing in step (III) is performed at a temperature comprised in the range of from 50 to 70°C.
As regards the one or more binders which in step (III) are mixed with the suspension obtained in step (II), there is no particular restriction neither with respect to the type, nor with respect to the number of different binders which may be employed to this effect provided that one or more of the binders may adhere to the zeolitic material in that step and/or during the further course of the inventive process for obtaining a powder or granulate containing binder adhered to the zeolitic material. Thus, in principle, any suitable binder or combination of binders may be employed to this effect, wherein it is however preferred that the one or more binders used in step (III) are selected from the group consisting of inorganic binders and derivatives thereof. Within the meaning of the present invention, the term "derivative" as used for defining the one or more inorganic binders preferably refers to any inorganic binder which has been treated with an organic substance and/or contains organic moieties which may be removed from the inorganic binder derivative preferably by combustion thereof at elevated temperatures, and in particular by combustion of the organic substance and/or moiety.
Thus, by way of example, the one or more binders preferably comprise one or more sources of a metal oxide and/or of a metalloid oxide, and more preferably one or more sources of a metal oxide and/or of a metalloid oxide selected from the group consisting of silica, alumina, titania, zirconia, lanthana, magnesia, and mixtures and/or mixed oxides of two or more thereof. More preferably, the one or more binders preferably comprise one or more sources of a metal oxide and/or of a metalloid oxide selected from the group consisting of silica, alumina, titania, zirconia, magnesia, silica-alumina mixed oxides, silica-titania mixed oxides, silica-zirconia mixed oxides, silica-lanthana mixed oxides, silica-zirconia- lanthana mixed oxides, alumina-titania mixed oxides, alumina-zirconia mixed oxides alumi- na-lanthana mixed oxides, alumina-zirconia-lanthana mixed oxides, titania-zirconia mixed oxides, and mixtures and/or mixed oxides of two or more thereof, more preferably from the group consisting of silica, alumina, silica-alumina mixed oxides and mixtures of two or more thereof. According to the present invention it is further preferred that the one or more binders comprises one or more sources of a metalloid oxide, wherein even more preferably the one or more binders comprise one or more sources of silica. According to the present invention it is particularly preferred that the one or more binders consists of one or more
- - sources of a metalloid oxide and that in particular the one or more binder consists of one or more sources of silica.
As regards the one or more sources of silica preferably comprised in the one or more bind- ers according to any of the particular and preferred embodiments of the present invention and more preferably the one or more sources silica of which the one or more binders consist of, there is no particular restriction according to the present invention neither with respect to the specific type nor concerning the number of different sources which may be employed to this effect. Thus, by way of example, the one or more sources of silica preferably used in the present invention may comprise one or more compounds selected from the group consisting of fumed silica, colloidal silica, silica-alumina, colloidal silica-alumina, and mixtures of two or more thereof, wherein more preferably the one or more compounds selected from the group consisting of fumed silica, colloidal silica, and mixtures thereof. According to the present invention it is however particularly preferred that the one or more binders consists of fumed silica and/or colloidal silica, wherein it is yet further preferred that the one or more binders consist of colloidal silica.
According to the present invention it is yet further preferred that the one or more binders further comprise one or more hydrolysable derivatives of one or more metal oxide and/or metalloid oxide, and preferably one or more hydrolysable resins based on the one or more metal oxide and/or metalloid oxide preferably comprised in the binder. With respect to the term "hydrolysable" as employed with respect to the derivatives of one or more metal oxide and/or metalloid oxide preferably further comprised in the one or more binders, said term preferably refers to the capacity of said derivatives to react with water, and more preferably to the capacity of said derivatives to react with water under standard temperature and pressure.
Concerning the one or more hydrolysable derivatives of one or more metal oxide and/or metalloid oxide preferably further comprised in the binder, there is no particular restriction as to the type or number of the hydrolysable derivatives which may be employed, wherein preferably one or more hydrolysable resins based on one or more metalloid oxides is further comprised in the binder, and even more preferably one or more hydrolysable resins based on silica. Again, as regards the one or more hydrolysable resins based on silica which are particularly preferably further comprised in the binder, any suitable hydrolysable resin based on silica may be employed, provided that it contains one or more chemical moieties which may react with water, and preferably one or more chemical moieties which may react with water under standard temperature and pressure.
According to the present invention it is however preferred that the one or more binders fur- ther comprise one or more hydrolysable silicone resins, more preferably one or more silicone resins containing one or more hydrolysable functional groups. As regards the one or
- - more hydrolysable groups which may be contained in the one or more silicone resins which are particularly preferred, no particular restrictions apply provided that these react with water, and preferably react with water at standard temperature and pressure, wherein the one or more binders preferably further comprise one or more alkoxy functionalized silicone resins, and more preferably one or more C1 -C5 alkoxy functionalized silicone resins, more preferably one or more C1 -C3 alkoxy functionalized silicone resins, more preferably one or more ethoxy and/or methoxy functionalized silicone resins, more preferably one or more methoxy functionalized silicone resins, wherein the functionalized silicone resin is preferably a functionalized alkyl oligo- and/or polysiloxane, more preferably a functionalized C1 -C5 alkyl oli- go- and/or polysiloxane, more preferably a functionalized C1 -C3 alkyl oligo- and/or polysiloxane, more preferably a functionalized ethyl and/or methyl oligo- and/or polysiloxane, more preferably a functionalized methyl oligo- and/or polysiloxane, and more preferably a functionalized methyl polysiloxane. Concerning the amount of the one or more binders which may be mixed with the suspension obtained in step (II) of the inventive process, in principle any suitable amount may be employed depending on the application for which the powder or granulate is intended to be used. This accordingly applies to the particular and preferred embodiments of the present invention wherein the binder further comprises one or more hydrolysable derivatives of one or more metal oxide and/or metalloid oxide, such that again any suitable amount of both the one or more binders and the one or more hydrolysable derivatives may be employed depending on the intended use of the resulting powder or granulate. This also applies to the ratio of the one or more hydrolysable derivatives of one or more metal and/or metalloid oxide to the one or more binder used in said preferred embodiments such that, by way of ex- ample, the weight ratio of the one or more hydrolysable derivatives of one or more metal oxide and/or metalloid oxide further comprised in the inorganic binder to the one or more sources of a metal oxide and/or of a metalloid oxide (hydrolysable derivatives : metal oxide and/or of a metalloid oxide) may range anywhere from (0.1 - 10) : 1 , wherein preferably the weight ratio ranges from (0.2 - 5) : 1 , more preferably from (0.5 - 3) : 1 , more preferably from (1 - 2.5) : 1 , more preferably from (1.3 - 2.2) : 1 , and more preferably from (1.5 - 2) : 1. According to the present invention it is particularly preferred that the hydrolysable derivatives : metal oxide and/or of a metalloid oxide weight ratio is comprised in the range of (1.6 - 1.8) : 1. As regards the ratio of the zeolitic material to the one or more binders used in step (III) of the inventive process, on the other hand, the weight ratio of the zeolitic material to the one or more binders to (zeolitic material : binder) may range anywhere from (1 - 20) : 1 , wherein preferably the zeolitic material : binder weight ratio ranges from (2 - 10) : 1 , more preferably from (3 - 8) : 1 , more preferably from (3.5 - 6) : 1 , more preferably from (4 - 5.5) : 1 , more preferably from (4.3 - 5.2) : 1 , and more preferably from (4.5 - 5) : 1. According to the pe-
- - sent invention it is however particularly preferred that the zeolitic material : binder weight ratio is comprised in the range of from (4.7 - 4.9) : 1.
Depending on the amounts and types of the zeolitic material and the solvent system used for producing the suspension obtained in step (II), it may display a wide variation relative to the solid content contained therein. Although there is no particular restriction as to the solid content of the suspension obtained from step (II) in wt.-% of the total weight of the suspension which by way of example may range anywhere from 5 to 80%, it is preferred according to the present invention that the solid content of the suspension obtained from step (II) is comprised in the range of from 10 to 60%, and more preferably from 15 to 50%, more preferably from 20 to 40%, and more preferably from 25 to 35%. According to the present invention it is however particularly preferred that the solid content of the suspension obtained from step (II) in wt.-% of the total weight of the suspension is comprised in the range of from 28 to 32%.
In step (IV) of the inventive process the suspension obtained in step (III) is dried. According to the present invention, the drying step may be performed at any suitable temperature for any suitable duration, provided that the suspension is effectively dried. Thus, in general, any conceivable means of drying can be used. Drying procedures preferably include heat- ing and/or applying vacuum to the suspension obtained in step (III), wherein preferably the suspension obtained in step (III) is heated for achieving drying thereof. Thus, as regards the temperature at which drying of the suspension is preferably performed, it may for example lie in the range of anywhere from 25 to 160°C, wherein preferably in step (IV) the suspension obtained in step (III) is dried at a temperature ranging from 60 to 150°C, more prefera- bly of from 80 to 140°C, more preferably in the range of from 100 to 135°C, and even more preferably in the range of from 120 to 130°C. The duration of drying preferably lies in the range of from 2 to 60 h, more preferably in the range of 6 to 48 hours, and even more preferably of from 12 to 24 h, wherein in general any suitable duration of drying may be chosen provided that the desired grade of drying of the suspension of obtained in step (III) is achieved.
As concerns the drying of the suspension obtained in step (II) in step (III), said drying may in principle be conducted in any suitable fashion using any conceivable apparatus. Thus, by way of example, the suspension may simply be dried by heating and/or by applying vacuum to the suspension to be dried. According to the present invention, it is however preferred that the step of drying is performed such that the form of the dried material is suited for a given application in which it is intended to be used. Accordingly, besides simply drying the suspension to afford a powder or granulate, drying may be performed under a particular type of agitation of the suspension such as to influence the characteristics of the powder or granulate. Thus, according to the present invention it is further preferred that the suspension is constantly stirred and/or that the vessel in which the suspension obtained from step
- -
(II) is to be dried is constantly rotated during the drying procedure, wherein more preferably the rate of stirring and/or rotating is chosen in function of the desired characteristics of the resulting powder or granulate. According to the present invention it is however particularly preferred that the suspension obtained in step (II) is subject in step (III) to a spray drying procedure for obtained a spray-dried powder, or alternatively to a spray-granulation procedure for obtaining a granulate. Therefore, it is particularly preferred according to the present invention that the suspension obtained in step (II) is spray-dried or spray-granulated, wherein preferably the suspension obtained in step (II) is spray-dried. In step (V) of the inventive process, the dried material obtained in step (IV) is calcined. In principle, said calcination may be conducted under at any suitable temperature and conditions, provided that it is sufficient for the thermal treatment of the material and in particular for allowing for the removal of any unwanted organic residues still present in the dried material obtained in step (IV). The temperature is however preferably chosen such that it causes no substantial damage to the powder or granulate obtained from the inventive process and in particular does not cause any substantial degradation of the framework structure of the zeolitic material. Thus, in principle, any suitable temperature may be chosen for conducting the calcination step such that by way of example the temperature at which the calcination in step (V) is conducted may range anywhere from 350 to 850°C, and preferably at a tempera- ture ranging from 400 to 700°C, more preferably from 450 to 650°C, and more preferably from 475 to 600°C. According to the present invention it is however particularly preferred that the calcination in step (V) is conducted at a temperature ranging from 500 to 550°C.
According to the present invention, the powder or granulate obtained from the inventive process may be further subject to any suitable work-up procedure and/or further treatment steps depending on the specific application in which it is intended to be used. Thus, by way of example, when the powder or granulate obtained in step (V) is intended for use in a specific catalytic application, it is preferred that the powder or granulate is further treated to load one or more metals thereon.
Therefore, it is preferred according to the present invention that the inventive process, and in particular the inventive process according to any of the particular and preferred embodiments defined in the foregoing, further comprises
(VI) supporting one or more metals onto the calcined material obtained in step (V) as non- framework elements;
(VII) optionally drying the material obtained in step (VI); and
(VIII) optionally calcining the material obtained in step (VI) or (VII).
As regards the one or more metals supported onto the calcined material obtained in step (V), no particular restriction applies according to the present invention such that in principle any suitable metal or combination of two or more metals may be supported depending on
- - the intended application of the metal loaded powder or granulate. Thus, by way of example, the one or more metals supported on the calcined material obtained in step (V) may be selected from the group consisting of Mg, Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, wherein preferably the one or more metals are selected from the group consisting of Mg, Sr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, and more preferably from the group consisting of Mg, Cr, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof. According to the present invention it is however particularly preferred that the one or more metals supported onto the calcined material obtained in step (V) comprise Mo and/or Ni, and preferably comprise both Mo and Ni, in particular in cases wherein the resulting powder or granulate is intended for application in a process such a for the conversion of methane to benzene. According to the present invention it is yet further preferred that Mo and Ni are the only metals which are supported onto the calcined powder or granulate obtained in step (V) as non-framework elements.
Concerning the supporting of the one or more metals onto the calcined material obtained in step (V) in step (VI), no particular restriction applies as to the methods which may be used, provided that the one or more metals are supported as non-framework elements onto the calcined material. Thus, in principle, the loading of the calcined material with one or more metals may by achieved by any suitable impregnation method as well as by any suitable method of ion-exchange wherein extra-framework ions present in the zeolitic material contained in the powder or granulate obtained in step (V) is exchanged against one or more of the one or more metals to be supported onto the powder or granulate. As regards the impregnation method which may be employed, again no particular restriction applies neither with respect to the solvent system which may be employed, nor with respect to the metal compound dissolved in the solvent system, provided that the metal may be supported onto the calcined material as non-framework element. Same applies with respect to the amounts of the solvent system employed and the concentration of the metal compound contained therein, wherein it is particularly preferred according to the present invention that the im- pregnation step is performed according to an incipient wetness technique, wherein the volume of the solvent system for impregnation containing the metal compound is equal to or less than the pore volume of the calcined powder or granulate obtained in step (V) which is to be impregnated. With respect to the amount of the one or more metals supported onto the calcined material obtained in step (V) in step (VI), any suitable amount may be supported depending on the intended application, such that by way of example the amount of the one or more metals supported onto the calcined material may range anywhere from 0.1 to 25 wt.-% calculated as the one or more elements and based on 100 wt.-% of the material obtained in step (VI), and preferably based on 100 wt.-% of the material obtained in step (VII), and more preferably based on 100 wt.-% of the material obtained in step (VIII), wherein it is preferred accord-
- - ing to the present invention that the amount of the one or more metals supported onto the calcined material ranges from 0.5 to 20 wt.-%, and more preferably from 1 to 15 wt.-%, more preferably from 3 to 12 wt.-%, more preferably from 4 to 10 wt.-%, more preferably from 5 to 9 wt.-%, and more preferably from 6 to 8 wt.-%. According to the present invention it is however particularly preferred that the amount of the one or more metals supported on the calcined material obtained in step (V) in step (VI) ranges from 6.5 to 7.5 wt.-% calculated as the one or more elements and based on 100 wt.-% of the material obtained in step (VI), and preferably based on 100 wt.-% of the material obtained in step (VII), and more preferably based on 100 wt.-% of the material obtained in step (VIII).
As noted above, there is no particular restriction as to the zeolitic material which may be employed in the inventive process provided that it displays the aforementioned X-ray diffraction pattern. Thus, for example, as regards the Y02 : X2O3 molar ratio in the zeolitic materials according to embodiments wherein the MFI-type framework structure comprises both Y and X as tetravalent and trivalent framework elements, respectively, said ratio is not particularly limited such that by way of example it may range anywhere from 1 to 500, wherein according to the present invention the YO2 : X2O3 molar ratio preferably ranges from from 5 to 200, more preferably from 10 to 150, more preferably from 20 to 100, more preferably from 40 to 70, and more preferably from 45 to 60. According to the present invention it is however par- ticularly preferred that the YO2 : X2O3 molar ratio in the MFI-type framework structure of the zeolitic material ranges from 50 to 55.
According to the present invention, the zeolitic material having an MFI-type framework structure employed in the inventive process comprises YO2. In principle, Y stands for any conceivable tetravalent element, Y standing for either or several tetravalent elements. Preferred tetravalent elements according to the present invention include Si, Sn, Ti, Zr, and Ge, and combinations thereof. More preferably, Y stands for Si, Ti, or Zr, or any combination of said tetravalent elements, even more preferably for Si, and/or Sn. According to the present invention, it is particularly preferred that Y stands for Si.
As regards X2O3 optionally comprised in the MFI-framework structure of the zeolitic material employed in the inventive process, X may in principle stand for any conceivable trivalent element, wherein X stands for one or several trivalent elements. Preferred trivalent elements according to the present invention include Al, B, In, and Ga, and combinations there- of. More preferably, X stands for Al, B, or In, or any combination of said trivalent elements, even more preferably for Al and/or B. According to the present invention, it is particularly preferred that X stands for Al.
As regards the specific type of zeolitic material having the MFI-type framework structure which is comprised in the zeolitic material employed in the inventive process, any conceivable material may be employed provided that it displays the aforementioned X-ray diffraction pattern according to any of the particular or preferred embodiments defined in the present appli-
- 4 - cation. According to the present invention it is however preferred that the zeolitic material provided in step (I) comprises ZSM-5, wherein even more preferably the zeolitic material provided in step (I) consists of ZSM-5. Furthermore, as regards the 29Si MAS NMR of the zeolitic material employed in the inventive process according to embodiments wherein Y includes Si or is preferably Si, there is no particular restriction as to the number and/or respective ppm values and/or relative intensities of the signals displayed in the NMR spectrum. According to preferred embodiments of the present invention, however, the 29Si MAS NMR comprises
a first peak (P1) comprised in the range of from -1 10.4 to -1 14.0 ppm and
a second peak (P2) comprised in the range of from -101.4 to -106.8 ppm,
wherein more preferably the first peak is comprised in the range of from -1 10.8 to -113.4 ppm and the second peak is comprised in the range of from -101.6 to -106.5 ppm. According to particularly preferred embodiments, the first peak (P1 ) is comprised in the range of from -1 1 1.2 to -1 12.8 ppm and the second peak (P2) is comprised in the range of from -101.8 to -106.2 ppm.
According to the present invention it is further preferred, that the 29Si CP MAS NMR of the zeolitic material employed in the inventive process as obtained from (1H - 29Si) cross polari- zation experiments comprises a first peak (P1) comprised in the range of from -1 10.80 to -1 11.30 ppm and a second peak (P2) comprised in the range of from -101.00 to -103.50 ppm, wherein preferably the integration of the first and second peaks in the 29Si CP-MAS NMR of the zeolitic material offers a ratio of the integration values P1 : P2 of 1 : (1.40-2.50). More preferably, the first peak (P1 ) is comprised in the range of from -1 11.00 to -1 12.10 ppm and the second peak (P2) is comprised in the range of from -101.50 to -103.00 ppm wherein the integration of the first and second peaks in the 29Si CP-MAS NMR of the zeolitic material preferably offers a ratio of the integration values P1 : P2 of 1 : (1.45 - 2.20), and more preferably of 1 : (1.50 - 2.10). More preferably, the first peak (P1 ) is comprised in the range of from -1 11.20 to -1 11.95 ppm and the second peak (P2) is comprised in the range of -101.70 to -102.60 ppm, wherein the integration of the first and second peaks offers a ratio of the integration values P1 : P2 of 1 : (1.55 - 2.00), and more preferably of 1 : (1.60 - 1.95). According to the present invention it is particularly preferred that in the 29Si CP MAS NMR of the zeolitic material obtained from ( H - 29Si) cross polarization experiments comprises, the first peak (P1 ) is comprised in the range of from -1 1 1.30 to -1 11.85 ppm and the second peak (P2) is comprised in the range of from -101.95 to -102.40 ppm, wherein the integration of the first and second peaks in the 29Si CP-MAS NMR of the zeolitic material preferably offers a ratio of the integration values P1 : P2 of 1 : (1.65 - 1.90). According to the present invention, it is preferred that the deconvoluted 29Si MAS NMR spectrum of the zeolitic material employed in the inventive process comprises a further peak comprised in the range of from -1 13.2 to -1 15.2 ppm, wherein more preferably said
- 5 - additional peak is comprised in the range of from -1 13.5 to -1 14.9 ppm. According to particularly preferred embodiments of the present invention, the zeolitic materials comprise a further peak in the deconvoluted 29Si MAS NMR spectrum comprised in the range of from -1 13.8 to -1 14.7 ppm. In principle, as regards the deconvoluted 29Si MAS NMR spectrum, any suitable method may be employed for deconvolution thereof provided that said method is able to identify a further peak in the 29Si MAS NMR spectrum of the zeolitic materials of the present invention. According to the present invention it is however preferred that the deconvolution is performed using DM Fit (Massiot et al., Magnetic Resonance in Chemistry, 40 (2002) pp. 70-76). In particular, it is preferred that according to said method the fitting model is comprised of three Gaussian functions, with starting positions at -103 ppm, -1 12 ppm and -114 ppm. Furthermore, it is preferred that both peak position and line width are left unrestrained, with the consequence that the fit peaks are not fixed at a certain position. There is no particular restriction according to the present invention as to the standard used in the 29Si MAS NMR experiments for obtaining the respective values for the chemical shift in ppm in the 29Si MAS NMR spectra according to particular and preferred embodiments of the present invention, wherein preferably an external standard is used. According to particularly preferred embodiments, the external standard used in the 29Si MAS NMR experiment is the polymer Q8M8 as an extenal secondary standard in the 29Si MAS NMR experiment, wherein the resonance of the trimethylsilyl M group is set to 12.5 ppm.
In addition to the process for the production of a powder or granulate as described above, the present invention further relates to a powder or granulate per se which is obtainable by the in- ventive process and in particular according to any of the particular and preferred embodiments thereof as defined in the foregoing. Furthermore, the inventive process relates to a powder or granulate per se independently of the process by which it may be obtained.
In particular, the present invention further relates to a powder or granulate, preferably obtaina- ble and/or obtained by the inventive process and in particular according to any of the particular and preferred embodiments of the inventive process defined in the foregoing, wherein said powder or granulate comprises a zeolitic material having an MFI-type framework structure comprising Y02 and optionally comprising X2O3,
wherein Y is a tetravalent element, and X is a trivalent element,
said material having an X-ray diffraction pattern comprising at least the following reflections:
Intensity (%) Diffraction angle 2Θ/0 [Cu K(alpha 1 )]
15 - 55 7.88 - 8.16
1 1 - 35 8.83 - 9.13
100 23.04 - 23.46
27 - 40 23.68 - 23.89
- -
wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern, and
wherein the powder or granulate further comprises one or more binders. As regards the zeolitic material which may be employed in the inventive powder or granulate, it is not particularly restricted provided that it displays the X-ray diffraction pattern as defined in the present application, and in particular according to any of the particular and preferred embodiments defined herein. According to the present invention, there is no particular restriction as to the zeolitic material which may be employed in the inventive process provided that it displays the aforementioned X- ray diffraction pattern. As regards the intensity of the first reflection comprised in the range of 7.88° - 8.16° 2Θ, it is preferred according to the present invention that the intensity of said reflection is comprised in the range of from 15 - 45, more preferably of from 16 - 30, and even more preferably of from 17 - 23. Furthermore or in addition thereto, and preferably in addition thereto, as regards the intensity of the second reflection comprised in the range of 8.83° - 9.13° 2Θ, it is preferred according to the present invention that the intensity of said reflection is comprised in the range of from 12 - 30, more preferably of from 13 - 25, more preferably of from 14 - 23, and even more preferably of from 15 - 21.
According to the present invention, it is further preferred that the zeolitic material having an MFI-type framework structure comprised in the inventive powder or granulate has an X-ray diffraction pattern comprising at least the following reflections:
According to said preferred embodiments, as regards the intensity of the first reflection comprised in the range of 7.95° - 8.09° 2Θ, it is preferred according to the present invention that the intensity of said reflection is comprised in the range of from 17 - 30, more preferably of from 17 - 25, and even more preferably of from 17 - 23. Furthermore or in addition thereto, and preferably in addition thereto, as regards the intensity of the second reflection comprised in the range of 8.91 ° - 9.05° 2Θ, it is preferred according to the present invention that the intensity of said reflection is comprised in the range of from 15 - 24, more prefera- bly of from 14 - 22, and even more preferably of from 15 - 21.
Furthermore, as regards the 29Si MAS NMR of the zeolitic material comprised in the inventive powder or granulate according to embodiments wherein Y includes Si or is preferably Si, there is no particular restriction as to the number and/or respective ppm values and/or relative intensities of the signals displayed in the NMR spectrum. According to preferred embodiments of the present invention, however, the 29Si MAS NMR comprises
a first peak (P1) comprised in the range of from -1 10.4 to -1 14.0 ppm and
a second peak (P2) comprised in the range of from -101.4 to -106.8 ppm,
wherein more preferably the first peak is comprised in the range of from -1 10.8 to -113.4 ppm and the second peak is comprised in the range of from -101.6 to -106.5 ppm. According to particularly preferred embodiments, the first peak (P1 ) is comprised in the range of from -1 1 1.2 to -1 12.8 ppm and the second peak (P2) is comprised in the range of from -101.8 to -106.2 ppm. According to the present invention it is further preferred, that the 29Si CP MAS NMR of the zeolitic material comprised in the inventive powder or granulate as obtained from (1H - 29Si) cross polarization experiments comprises a first peak (P1) comprised in the range of from -1 10.80 to -1 11.30 ppm and a second peak (P2) comprised in the range of from -101.00 to -103.50 ppm, wherein preferably the integration of the first and second peaks in the 29Si CP-MAS NMR of the zeolitic material offers a ratio of the integration values P1 : P2 of
- -
1 : (1.40-2.50). More preferably, the first peak (P1 ) is comprised in the range of from -1 11.00 to -1 12.10 ppm and the second peak (P2) is comprised in the range of from -101.50 to -103.00 ppm wherein the integration of the first and second peaks in the 29Si CP-MAS NMR of the zeolitic material preferably offers a ratio of the integration values P1 : P2 of 1 : (1.45 - 2.20), and more preferably of 1 : (1.50 - 2.10). More preferably, the first peak (P1 ) is comprised in the range of from -1 11.20 to -1 11.95 ppm and the second peak (P2) is comprised in the range of -101.70 to -102.60 ppm, wherein the integration of the first and second peaks offers a ratio of the integration values P1 : P2 of 1 : (1.55 - 2.00), and more preferably of 1 : (1.60 - 1.95). According to the present invention it is particularly preferred that in the 29Si CP MAS NMR of the zeolitic material obtained from ( H - 29Si) cross polarization experiments comprises, the first peak (P1) is comprised in the range of from -1 1 1.30 to -1 11.85 ppm and the second peak (P2) is comprised in the range of from -101.95 to -102.40 ppm, wherein the integration of the first and second peaks in the 29Si CP-MAS NMR of the zeolitic material preferably offers a ratio of the integration values P1 : P2 of 1 : (1.65 - 1.90).
According to the present invention, it is preferred that the deconvoluted 29Si MAS NMR spectrum of the zeolitic material comprised in the inventive powder or granulate comprises a further peak comprised in the range of from -1 13.2 to -1 15.2 ppm, wherein more prefera- bly said additional peak is comprised in the range of from -1 13.5 to -1 14.9 ppm. According to particularly preferred embodiments of the present invention, the zeolitic materials comprise a further peak in the deconvoluted 29Si MAS NMR spectrum comprised in the range of from -1 13.8 to -1 14.7 ppm. As noted above, there is no particular restriction as to the zeolitic material which may be comprised in the inventive powder or granulate provided that it displays the aforementioned X-ray diffraction pattern. Thus, for example, as regards the Y02 : X2O3 molar ratio in the zeolitic materials according to embodiments wherein the MFI-type framework structure comprises both Y and X as tetravalent and trivalent framework elements, respectively, said ratio is not par- ticularly limited such that by way of example it may range anywhere from 1 to 500, wherein according to the present invention the YO2 : X2O3 molar ratio preferably ranges from from 5 to 200, more preferably from 10 to 150, more preferably from 20 to 100, more preferably from 40 to 70, and more preferably from 45 to 60. According to the present invention it is however particularly preferred that the YO2 : X2O3 molar ratio in the MFI-type framework structure of the zeolitic material ranges from 50 to 55.
According to the present invention, the zeolitic material having an MFI-type framework structure comprised in the inventive powder or granulate comprises YO2. In principle, Y stands for any conceivable tetravalent element, Y standing for either or several tetravalent elements. Preferred tetravalent elements according to the present invention include Si, Sn, Ti, Zr, and Ge, and combinations thereof. More preferably, Y stands for Si, Ti, or Zr, or any
- - combination of said tetravalent elements, even more preferably for Si, and/or Sn. According to the present invention, it is particularly preferred that Y stands for Si.
As regards X2O3 optionally comprised in the MFI-framework structure of the zeolitic material contained in the inventive powder or granulate, X may in principle stand for any conceivable trivalent element, wherein X stands for one or several trivalent elements. Preferred trivalent elements according to the present invention include Al, B, In, and Ga, and combinations thereof. More preferably, X stands for Al, B, or In, or any combination of said trivalent elements, even more preferably for Al and/or B. According to the present invention, it is par- ticularly preferred that X stands for Al.
As regards the specific type of zeolitic material having the MFI-type framework structure which is comprised in the inventive powder or granulate, any conceivable material may be employed provided that it displays the aforementioned X-ray diffraction pattern according to any of the particular or preferred embodiments defined in the present application. According to the present invention it is however preferred that the zeolitic material comprised in the inventive powder or granulate comprises ZSM-5, wherein even more preferably the zeolitic material comprised in the inventive powder or granulate consists of ZSM-5. In addition to the framework elements of the zeolitic material of the present invention comprised in the inventive powder or granulate, said zeolitic material preferably further contains one or more types of non-framework elements which do not constitute the framework structure and are accordingly present in the pores and/or cavities formed by the framework structure and typical for zeolitic material in general. In this respect, there is no particular restriction as to the types of non-framework elements which may be contained in the zeolitic material, nor with respect to the amount in which they may be present therein. It is, however, preferred that the zeolitic material comprised in the inventive powder or granule comprises one or more cation and/or cationic elements as ionic non-framework elements, wherein again no particular restriction applies as to the type or number of different types of ionic non-framework elements which may be present in the zeolitic material, nor as to their respective amount. According to preferred embodiments of the present invention, the ionic non-framework elements preferably comprise one or more cations and/or cationic elements selected from the group consisting of H+, ΝΗ4 +, Mg, Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, wherein more preferably these are selected from the group consisting of H+, NH4 +, Mg, Sr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably from the group consisting of H+, N H4+, Mg, Cr, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, and more preferably selected from the group consisting of Mg, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof. According to particularly preferred embodiments of the present invention, however, the ionic non-framework elements comprise Mo and/or Ni as ionic non-framework ele- ments, preferably Mo and Ni, wherein even more preferably the zeolitic material comprises Mo and/or Ni as ionic non-framework elements, and preferably both Mo and Ni.
- -
As regards the amount in which the one or more cations and/or cationic elements may be contained in the zeolitic material comprised in the inventive powder or granulate, no particular restriction applies such that in principle any suitable amount may be contained therein, in particular depending on the application for which the powder or granulate is intended for. Thus, by way of example, the amount of the one or more cations and/or cationic elements may range anywhere from 0.5 to 20 wt.-% calculated as the one or more elements and based on 100 wt.-% of the calcined powder or granulate, wherein preferably the amount of the one or more cations and/or cationic elements ranges from 1 to 15 wt.-%, more preferably from 3 to 12 wt.-%, more preferably from 4 to 10 wt.-%, more preferably from 5 to 9 wt.- %, and more preferably from 6 to 8 wt.-%. According to the present invention it is particularly preferred that the amount of the one or more cations and/or cationic elements is comprised in the range of from 6.5 to 7.5 wt.-%.
According to the present invention, no particular restriction applies relative to further compo- nents which may be contained in the inventive powder or granulate in addition to the zeolitic material. Thus, in principle, any suitable further materials may be contained therein, wherein according to the present invention the inventive powder or granulate further comprises one or more binders in addition to the zeolitic material. As regards the type or number of binders which is further comprised in the inventive powder or granulate, again no particular restriction applies, such that by way of example the powder or granulate may further comprise one or more binders selected from the group of inorganic and organic binders, including mixtures of two or more thereof. According to the present invention, it is however preferred that the one or more binders comprise one or more inorganic binders, wherein preferably the one or more binders comprise one or more sources of a metal oxide and/or of a metalloid oxide, and more preferably one or more sources of a metal oxide and/or of a metalloid oxide selected from the group consisting of silica, alumina, titania, zirconia, lanthana, magnesia, and mixtures and/or mixed oxides of two or more thereof, more preferably from the group consisting of silica, alumina, titania, zirconia, magnesia, silica-alumina mixed oxides, silica-titania mixed oxides, silica-zirconia mixed oxides, silica-lanthana mixed oxides, silica-zirconia-lanthana mixed oxides, alumina- titania mixed oxides, alumina-zirconia mixed oxides alumina-lanthana mixed oxides, alumi- na-zirconia-lanthana mixed oxides, titania-zirconia mixed oxides, and mixtures and/or mixed oxides of two or more thereof, more preferably from the group consisting of silica, alumina, silica-alumina mixed oxides and mixtures of two or more thereof, wherein more preferably the one or more binders comprise one or more sources of silica, wherein more preferably the binder consists of one or more sources of silica. According to the present invention it is particularly preferred that the binder consists of one or more sources of silica, wherein the one or more sources of silica preferably comprise one or more compounds selected from the group consisting of fumed silica, colloidal silica, silica-alumina, colloidal silica-alumina, calcined silicone resin, and mixtures of two or more thereof, more preferably one or more com- pounds selected from the group consisting of fumed silica, colloidal silica, calcined silicone resin, and mixtures thereof. According to the present invention it is particularly preferred
- - that the one or more binders consists of colloidal silica and/or calcined silicone resin, and more preferably of both colloidal silica and calcined silicone resin.
As regards the specific surface area of the inventive powder or granulate, no particular re- strictions apply such that, by way of example, the surface may range anywhere from 50 to 700 m2/g, wherein preferably the surface area of the powder or granulate is comprised in the range of from 100 to 500 m2/g, wherein more preferably the surface area ranges from 150 to 475 m2/g, more preferably from 200 to 450 m2/g, more preferably from 250 to 425 m2/g, and more preferably from 300 to 400 m2/g. According to the present invention, it is particularly preferred that the inventive powder or granulate displays a specific surface area ranging from 325 to 375 m2/g. As employed in the present application, the term "specific surface area" preferably refers to the specific surface area of the materials described when determined according to DIN 66131.
With respect to the size and morphology which the inventive powder or granulate may have, no particular restriction applies. Thus, depending on the intended use of the powder or granulate, the size and morphology thereof may be accordingly chosen or adapted to the given requirements of the specific application. It is, however, preferred according to the present invention that the powder or granulate of the present invention is obtained from spray- drying or from spray-granulation, and more preferably from spray-drying such that accord- ing to the present invention it is particularly preferred that the inventive powder or granulate is a spray-dried powder or spray-granulate, respectively, wherein a spray-dried powder is yet further preferred according to the present invention.
In general, the inventive powder or granulate described above can be used in any suitable ap- plication such as by way of example as a molecular sieve, adsorbent, catalyst, or catalyst support. For example, the inventive powder or granulate according to any of the particular and preferred embodiments of the present invention can be used as molecular sieve to dry gases or liquids, for selective molecular separation, e.g. for the separation of hydrocarbons or amines; as ion exchanger; as chemical carrier; as adsorbent, in particular as adsorbent for the separation of hydrocarbons or amines; or as a catalyst. Most preferably, the inventive powder or granulate is used as a catalyst and/or as a catalyst support.
According to a preferred embodiment of the present invention, the inventive powder or granulate is used in a catalytic process, and preferably as a catalyst and/or catalyst support, and more preferably as a catalyst. In general, the inventive powder or granulate can be used as a catalyst and/or catalyst support in any conceivable catalytic process, wherein processes involving the conversion of at least one organic compound is preferred, more preferably of organic compounds comprising at least one carbon - carbon and/or carbon - oxygen and/or carbon - nitrogen bond, more preferably of organic compounds comprising at least one carbon - carbon and/or carbon - oxygen bond, and even more preferably of organic compounds comprising at least one carbon - carbon bond.
- -
Furthermore, it is preferred according to the present invention that inventive powder or granulate is used as a molecular trap for organic compounds. In general, any type of organic compound may be trapped in the zeolitic materials, wherein it is preferred that the compound is re- versibly trapped, such that it may be later released from the inventive powder or granulate, preferably wherein the organic compound is released - preferably without conversion thereof - by an increase in temperature and/or a decrease in pressure. Furthermore, it is preferred that the inventive powder or granulate is used to trap organic compounds of which the dimensions allow them to penetrate the microporous system of the molecular structure of the zeolitic material contained in the inventive powder or granulate. According to yet further embodiments of the present invention, it is preferred that the trapped compounds are released under at least partial conversion thereof to a chemical derivative and/or to a decomposition product thereof, and preferably to a thermal decomposition product thereof.
As regards the applications in which the inventive powder or granulate may be employed, it may be used in any conceivable way, wherein it is preferably used as a catalyst, catalyst support, adsorbent, or for ion exchange, wherein preferably the powder or granulate is used as a catalyst and/or catalyst support, more preferably as a catalyst and/or catalyst support in a reaction involving C-C bond formation and/or conversion, and preferably as a catalyst and/or catalyst support in an isomerization reaction, in an ammoxidation reaction, in a hy- drocracking reaction, in an alkylation reaction, in an acylation reaction, in a reaction for the conversion of alkanes to olefins and/or aromatics, or in a reaction for the conversion of one or more oxygenates to olefins and/or aromatics, wherein more preferably the powder or granulate is used in a process for the conversion of alkanes to aromatics, preferably in a methane to benzene process.
The present invention includes the following embodiments, wherein these include the specific combinations of embodiments as indicated by the respective interdependencies defined therein:
A process for the production of a powder or granulate, comprising
(I) providing a zeolitic material;
(II) suspending the zeolitic material provided in step (I) in a solvent system;
(III) mixing the suspension obtained in step (II) with one or more binders;
(IV) drying the suspension obtained in step (III); and
(V) calcining of the dried material obtained in step (IV);
wherein the zeolitic material provided in step (I) has an MFI-type framework structure comprising YO2 and optionally comprising X2O3,
wherein Y is a tetravalent element, and X is a trivalent element,
said material having an X-ray diffraction pattern comprising at least the following reflections:
Intensity (%) Diffraction angle 2θ/° [Cu K(alpha 1 )]
- -
wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern.
The process of embodiment 1 , wherein the solvent system comprises one or more solvents, wherein preferably the solvent system comprises one or more hydrophilic solvents, the hydrophilic solvents preferably being selected from the group consisting of polar solvents, more preferably from the group consisting of polar protic solvents, wherein more preferably the solvent system comprises one or more polar protic solvents selected from the group consisting of water, alcohols, carboxylic acids, and mixtures of two or more thereof, more preferably from the group consisting of water, C1 -C5 alcohols, C1 -C5 carboxylic acids, and mixtures of two or more thereof, more preferably from the group consisting of water, C1 -C4 alcohols, C1 -C4 carboxylic acids, and mixtures of two or more thereof, more preferably from the group consisting of water, C1 -C3 alcohols, C1 -C3 carboxylic acids, and mixtures of two or more thereof, more preferably from the group consisting of water, methanol, ethanol, propanol, formic acid, acetic acid, and mixtures of two or more thereof, more preferably from the group consisting of water, ethanol, acetic acid, and mixtures of two or more thereof, wherein more preferably the solvent system comprises water and/or ethanol, and wherein more preferably the solvent system comprises water, wherein even more preferably the solvent system consists of water.
The process of embodiment 1 or 2, wherein the zeolitic material in the suspension obtained in step (II) displays a particle size D90 ranging from 0.05 to 20 μηη, preferably from 0.1 to 10 μηη, more preferably from 0.5 to 5 μηη, more preferably from 0.8 to 4 μηη, more preferably from 1 to 3.5 μηη, more preferably from 1.3 to 2.9 μηη, and more preferably from 1 .5 to 2.5 μηι.
The process of any of embodiments 1 to 3, wherein mixing in step (III) is conducted under heating, wherein preferably the mixing is performed at a temperature ranging from 30 to 150°C, preferably from 35 to 130°C, more preferably from 40 to 1 10°C, more preferably from 45 to 90°C, more preferably from 50 to 70°C.
The process of any of embodiments 1 to 4, wherein the one or more binders in step (III) are selected from the group consisting of inorganic binders and derivatives thereof,
- 4 - wherein the one or more binders preferably comprise one or more sources of a metal oxide and/or of a metalloid oxide, more preferably one or more sources of a metal oxide and/or of a metalloid oxide selected from the group consisting of silica, alumina, titania, zirconia, lanthana, magnesia, and mixtures and/or mixed oxides of two or more thereof, more preferably from the group consisting of silica, alumina, titania, zirconia, magnesia, silica-alumina mixed oxides, silica-titania mixed oxides, silica-zirconia mixed oxides, silica- lanthana mixed oxides, silica-zirconia-lanthana mixed oxides, alumina-titania mixed oxides, alumina-zirconia mixed oxides alumina-lanthana mixed oxides, alumina-zirconia- lanthana mixed oxides, titania-zirconia mixed oxides, and mixtures and/or mixed oxides of two or more thereof, more preferably from the group consisting of silica, alumina, silica- alumina mixed oxides and mixtures of two or more thereof, wherein more preferably the one or more binders comprise one or more sources of silica, wherein more preferably the binder consists of one or more sources of silica, wherein the one or more sources of silica preferably comprise one or more compounds selected from the group consisting of fumed silica, colloidal silica, silica-alumina, colloidal silica-alumina, and mixtures of two or more thereof, more preferably one or more compounds selected from the group consisting of fumed silica, colloidal silica, and mixtures thereof, wherein more preferably the one or more binders consists of fumed silica and/or colloidal silica, and more preferably colloidal silica.
The process of embodiment 5, wherein the one or more binders further comprise one or more hydrolysable derivatives of one or more metal oxide and/or metalloid oxide, preferably one or more hydrolysable resins based on the one or more metal oxide and/or metalloid oxide, more preferably one or more hydrolysable resins based on one or more metalloid oxides, more preferably one or more hydrolysable resins based on silica, more preferably one or more hydrolysable silicone resins, more preferably one or more silicone resins containing one or more hydrolysable functional groups, more preferably one or more alkoxy functionalized silicone resins, more preferably one or more C1 -C5 alkoxy function- alized silicone resins, more preferably one or more C1 -C3 alkoxy functionalized silicone resins, more preferably one or more ethoxy and/or methoxy functionalized silicone resins, more preferably one or more methoxy functionalized silicone resins, wherein the functionalized silicone resin is preferably a functionalized alkyl oligo- and/or polysiloxane, more preferably a functionalized C1 -C5 alkyl oligo- and/or polysiloxane, more preferably a functionalized C1 -C3 alkyl oligo- and/or polysiloxane, more preferably a functionalized ethyl and/or methyl oligo- and/or polysiloxane, more preferably a functionalized methyl oligo- and/or polysiloxane, and more preferably a functionalized methyl polysiloxane.
The process of embodiment 6, wherein the weight ratio of the one or more hydrolysable derivatives of one or more metal oxide and/or metalloid oxide further comprised in the inorganic binder to the one or more sources of a metal oxide and/or of a metalloid oxide (hydrolysable derivatives : metal oxide and/or of a metalloid oxide) comprised in the binder ranges from (0.1 - 10) : 1 , preferably from (0.2 - 5) : 1 , more preferably from (0.5 - 3) :
- 5 -
1 , more preferably from (1 - 2.5) : 1 , more preferably from (1 .3 - 2.2) : 1 , more preferably from (1 .5 - 2) : 1 , and more preferably from (1 .6 - 1 .8) : 1 . The process of any of embodiments 1 to 7, wherein in step (III) the weight ratio of the zeo- litic material to the one or more binders to (zeolitic material : binder) ranges from (1 - 20) : 1 , preferably from (2 - 10) : 1 , more preferably from (3 - 8) : 1 , more preferably from (3.5 -
6) : 1 , more preferably from (4 - 5.5) : 1 , more preferably from (4.3 - 5.2) : 1 , more preferably from (4.5 - 5) : 1 , more preferably from (4.7 - 4.9) : 1 . The process of any of embodiments 1 to 8, wherein the solid content of the suspension obtained in step (II) in wt.-% of the total weight of the suspension ranges from 5 to 80%, preferably from 10 to 60%, more preferably from 15 to 50%, more preferably from 20 to
40%, more preferably from 25 to 35%, and more preferably from 28 to 32%. The process of any of embodiments 1 to 9, wherein the calcining of the dried powder or granulate obtained in step (IV) is performed at a temperature ranging from 350 to 850°C, preferably from 400 to 700°C, more preferably from 450 to 650°C, more preferably from 475 to 600°C, and more preferably from 500 to 550°C. The process of any of embodiments 1 to 10, wherein the suspension obtained in step (III) is spray-dried or spray-granulated, and is preferably spray-dried. The process of any of embodiments 1 to 1 1 , wherein the process further comprises
(VI) supporting one or more metals onto the calcined material obtained in step (V) as non-framework elements;
(VII) optionally drying the material obtained in step (VI); and
(VIII) optionally calcining the material obtained in step (VI) or (VII). The process of embodiment 12, wherein the one or more metals comprise one or more selected from the group consisting of Mg, Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Sr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Cr, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, wherein more preferably the one or more metals comprise Mo and/or Ni, preferably Mo and Ni, wherein even more preferably Mo and Ni are supported onto the calcined material obtained in step (V) as non-framework elements. The process of embodiment 13, wherein the amount of the one or more metals supported onto the calcined material ranges from 0.1 to 25 wt.-% calculated as the one or more elements and based on 100 wt.-% of the material obtained in step (VI), preferably based on
- -
100 wt.-% of the material obtained in step (VII), and more preferably based on 100 wt.-% of the material obtained in step (VIII), wherein preferably the amount of the one or more metals supported onto the calcined material ranges from 0.5 to 20 wt.-%, more preferably from 1 to 15 wt.-%, more preferably from 3 to 12 wt.-%, more preferably from 4 to 10 wt- %, more preferably from 5 to 9 wt.-%, more preferably from 6 to 8 wt.-%, and more preferably from 6.5 to 7.5 wt.-%.
15. The process of any of embodiments 1 to 14, wherein the 29Si MAS NMR of the zeolitic material comprises:
a first peak (P1 ) in the range of from -1 10.4 to -1 14.0, preferably of from - 1 10.8 to -1 13.4 ppm, and even more preferably of from -1 1 1 .2 to -1 12.8 ppm; and
a second peak (P2) in the range of from -101 .4 to -106.8 ppm, preferably of from -101 .6 to -106.5 ppm, and even more preferably of from -101 .8 to -106.2 ppm.
16. The process of any of embodiments 1 to 15, wherein the deconvoluted 29Si MAS NMR spectrum comprises one additional peak comprised in the range of from -1 13.2 to -1 15.2 ppm, more preferably of from -1 13.5 to -1 14.9 ppm, and even more preferably of from -
1 13.8 to -1 14.7 ppm.
17. The process of any of embodiments 1 to 16, wherein the YO2 : X2O3 molar ratio ranges from 1 to 500, preferably from 5 to 200, more preferably from 10 to 150, more preferably from 20 to 100, more preferably from 40 to 70, more preferably from 45 to 60, and even more preferably from 50 to 55.
18. The process of any of embodiments 1 to 17, wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof, Y preferably being Si.
19. The process of any of embodiments 1 to 18, wherein X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof, X preferably being Al and/or B, and more preferably being Al.
20. The process of any of embodiments 1 to 19, wherein the zeolitic material provided in step (I) comprises ZSM-5, wherein preferably the zeolitic material provided in step (I) consists of ZSM-5.
21 . A powder or granulate, obtainable by a process according to any of embodiments 1 to 20. 22. A powder or granulate, preferably obtainable and/or obtained by a process according to any of embodiments 1 to 20, wherein said powder or granulate comprises a zeolitic material having an MFI-type framework structure comprising YO2 and optionally comprising
- 7 -
wherein Y is a tetravalent element, and X is a trivalent element,
said material having an X-ray diffraction pattern comprising at least the following reflections:
wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern, and
wherein the powder or granulate further comprises one or more binders.
The powder or granulate of embodiment 22, wherein the 29Si MAS NMR of the zeolitic material comprises:
a first peak (P1 ) in the range of from -1 10.4 to -1 14.0, preferably of from - 1 10.8 to -1 13.4 ppm, and even more preferably of from -1 1 1 .2 to -1 12.8 ppm; and
a second peak (P2) in the range of from -101 .4 to -106.8 ppm, preferably of from -101 .6 to -106.5 ppm, and even more preferably of from -101 .8 to -106.2 ppm.
The powder or granulate of embodiment 22 or 23, wherein the deconvoluted 29Si MAS NMR spectrum comprises one additional peak comprised in the range of from -1 13.2 to - 1 15.2 ppm, more preferably of from -1 13.5 to -1 14.9 ppm, and even more preferably of from -1 13.8 to -1 14.7 ppm.
The powder or granulate of any of embodiments 22 to 24, wherein the YO2 : X2O3 molar ratio of the zeolitic material having an MFI-type framework structure ranges from 1 to 500, preferably from 5 to 200, more preferably from 10 to 150, more preferably from 20 to 100, more preferably from 40 to 70, more preferably from 45 to 60, and even more preferably from 50 to 55.
The powder or granulate of any of embodiments 22 to 25, wherein the MFI-type framework structure of the zeolitic material does not contain X2O3.
- - The powder or granulate of any of embodiments 22 to 26, wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof, Y preferably being Si. The powder or granulate of any of embodiments 22 to 27, wherein X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof, X preferably being
Al and/or B, and more preferably being Al.
The powder or granulate of any of embodiments 22 to 28, wherein the zeolitic material comprises one or more cations and/or cationic elements as ionic non-framework elements, said one or more cations and/or cationic elements preferably comprising one or more selected from the group consisting of H+, NH4 +, Mg, Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof, more preferably from the group consisting of H+, NH4 +, Mg, Sr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably from the group consisting of H+, NH4 +, Mg, Cr, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Mo, Fe, Ni, Cu, Zn, Ag, and mixtures of two or more thereof, wherein even more preferably the zeolitic material comprises Mo and/or Ni as ionic non- framework elements, preferably Mo and Ni.
The powder or granulate of embodiment 29, wherein the amount of the one or more cations and/or cationic elements ranges from 0.5 to 20 wt.-% calculated as the one or more elements and based on 100 wt.-% of the calcined powder or granulate, wherein more preferably the amount of the one or more cations and/or cationic elements ranges from 1 to 15 wt.-%, more preferably from 3 to 12 wt.-%, more preferably from 4 to 10 wt.-%, more preferably from 5 to 9 wt.-%, more preferably from 6 to 8 wt.-%, and more preferably from 6.5 to 7.5 wt.-%.
The powder or granulate of any of embodiments 22 to 30, wherein the one or more binders are selected from the group consisting of inorganic binders, wherein the one or more binders preferably comprise one or more sources of a metal oxide and/or of a metalloid oxide, more preferably one or more sources of a metal oxide and/or of a metalloid oxide selected from the group consisting of silica, alumina, titania, zirconia, lanthana, magnesia, and mixtures and/or mixed oxides of two or more thereof, more preferably from the group consisting of silica, alumina, titania, zirconia, magnesia, silica-alumina mixed oxides, sili- ca-titania mixed oxides, silica-zirconia mixed oxides, silica-lanthana mixed oxides, silica- zirconia-lanthana mixed oxides, alumina-titania mixed oxides, alumina-zirconia mixed oxides alumina-lanthana mixed oxides, alumina-zirconia-lanthana mixed oxides, titania- zirconia mixed oxides, and mixtures and/or mixed oxides of two or more thereof, more preferably from the group consisting of silica, alumina, silica-alumina mixed oxides and mixtures of two or more thereof, wherein more preferably the one or more binders com-
- - prise one or more sources of silica, wherein more preferably the binder consists of one or more sources of silica, wherein the one or more sources of silica preferably comprise one or more compounds selected from the group consisting of fumed silica, colloidal silica, silica-alumina, colloidal silica-alumina, calcined silicone resin, and mixtures of two or more thereof, more preferably one or more compounds selected from the group consisting of fumed silica, colloidal silica, calcined silicone resin, and mixtures thereof, wherein more preferably the one or more binders consists of colloidal silica and/or calcined silicone resin, and more preferably of colloidal silica and calcined silicone resin.
32. The powder or granulate of any of embodiments 22 to 31 , wherein the specific surface area of the powder or granulate determined according to DIN 66131 ranges from 50 to 700 m2/g, preferably from 100 to 500 m2/g, more preferably from 150 to 475 m2/g, more preferably from 200 to 450 m2/g, more preferably from 250 to 425 m2/g, more preferably from 300 to 400 m2/g, and more preferably from 325 to 375 m2/g.
33. The powder or granulate of any of embodiments 22 to 32, wherein the powder or granulate is obtained from spray-drying or from spray-granulation, preferably from spray-drying.
34. Use of a powder or granulate according to any of embodiments 21 to 33 as a catalyst, catalyst support, adsorbent, or for ion exchange, wherein preferably the powder or granulate is used as a catalyst and/or catalyst support, more preferably as a catalyst and/or catalyst support in a reaction involving C-C bond formation and/or conversion, and preferably as a catalyst and/or catalyst support in an isomerization reaction, in an ammoxidation reaction, in a hydrocracking reaction, in an alkylation reaction, in an acylation reaction, in a reaction for the conversion of alkanes to olefins and/or aromatics, or in a reaction for the conversion of one or more oxygenates to olefins and/or aromatics, wherein more preferably the powder or granulate is used in a process for the conversion of alkanes to aromatics, preferably in a methane to benzene process.
DESCRIPTION OF THE FIGURES
Figure 1 displays the X-ray diffraction pattern (measured using Cu K alpha-1 radiation) of the crystalline material obtained according to Reference Example 1. In the figure, the angle 2 theta in ° is shown along the abscissa and the intensities are plotted along the ordinate.
Figure 2 displays the scanning electron microscope (SEM) image obtained from the sample of the crystalline product obtained according to Reference Example 1 .
- -
Figure 3 shows the 29Si MAS NMR obtained from the sample obtained according to Reference Example 1 . In the figure, the values in ppm are plotted along the abscissa, wherein the exact ppm values are indicated above the respective peaks and shoulders, including the integration of the peaks in % indicated below the re- spective peaks. The values plotted along the ordinate indicate the intensity of the NMR signal for given values of the chemical shift in ppm.
Figure 4 shows the deconvoluted 29Si MAS NMR obtained from the sample obtained according to Reference Example 1 . In the figure, the values in ppm are plotted along the abscissa, wherein the relative intensities in % of the peaks identified by deconvolution is indicated next to the respective deconvoluted peak.
Figure 5 displays the results from catalytic testing in the conversion of methane to benzene (MTB). In the figure, the duration of the catalytic testing (cycles) in hours is plotted along the abscissa. The ordinate to the left indicates the selectivity of the reaction in % towards a particular product as indicated in the graph, whereas the right ordinate displays the conversion rate of methane in the MTB-reaction in %.
EXPERIMENTAL SECTION
Reference Example 1 : Synthesis of ZSM-5 with allyltripropylammonium hydroxide (ATPAOH) using aluminum triisoproylate 12.2 kg allyltripropylammonium hydroxide (20.2 wt-% in H2O) were mixed together with 0.125 kg NaOH (solid). Afterwards 0.448 kg aluminum triisopropylate was added under stirring to the reaction mixture until the solid was completely dissolved. Finally, 8.253 kg Ludox® AS 40 (40 wt-% colloidal S1O2 in H20) is added to the reaction mixture. The dispersion was then filled in an autoclave which was then heated under stirring within 7h to 170°C and then held at that temperature for 72h. After cooling down to room temperature, 37.77 kg nitric acid (10wt-% in H2O) was given into the slurry to precipitate the ZSM-5 crystals. The precipitated solid was then separated by filtration from the solvents and washed with 70kg of deionized H2O. Finally, the solid was dried at 120°C for 24h under N2 stream. The product was characterized by X-ray powder diffraction (see Fig. 1 ) and scanning electron microscopy (see Fig. 2). The crystallization degree of the ZSM-5 based on the XRD pattern was calculated to 99%.
To remove the organic residues from the ZSM-5 powder, the solid was then heated to 500°C for 5h. With the obtained sample, 29Si MAS NMR measurements were performed, the results of which are indicated in Figures 3 and 4, respectively. For the removal of residual Na ions, 5.0 kg of the solid is stirred together with 5.0 kg NH4NO3 dissolved in 44.8L H20 for 1 h at 80°C. Afterwards the solid is separated from the solvent by filtration and is washed with 100 kg Dl H2O.
- -
The product was characterized by elemental analysis to afford Si: 38.0 wt-%, Al: 1 .4 wt-%, Na: <0.01 wt-% and C< 0.5wt-%. Example 1: Preparation of a spray-dried powder
A suspension of 18.4 kg of the ZSM-5 powder obtained from Reference Example 1 in water (30 wt.-% solids content) was wet milled to a D90 value of < 3 μηη in a bead mill (Buhler DCP 30 SF 12). 2.4 kg of polymethoxysiloxane (Silres® MSE 100, Wacker Silicon) and 1 .4 kg of colloidal silica (Nalco® DVSZN006, Nalco Company) were then slowly mixed into the aqueous zeolite suspension. The resulting suspension was then further mixed and heated to 50-70°C for 1 h.
The suspension was then spray dried using a spray-dryer from Niro with a single-substance nozzle (0.6 mm diameter) employing nitrogen gas as the sprayer gas. The temperature used in the drying procedure ranged from 120 to 130°C. The resulting spray-dried powder was then dried over night at 120°C and subsequently calcined in air for 4h at 500 to 550°C.
1 kg of the resulting powder was impregnated by incipient wetness with a solution of ammonium heptamolybdate in water (1 18.75 g in 1.1 liters H2O) to obtain a loading of 6 wt.-% Mo calculat- ed as the element based on 100 wt.-% of the resulting catalyst powder. The powder was mixed for 1 h to obtain a homogenous distribution, after which the catalyst powder was dried over night at 120°C and subsequently calcined in air for 4 h at 500 °C.
1 kg of the powder loaded with Mo was then impregnated by incipient wetness which an aque- ous solution of Ni(ll) nitrate (53.33 g in 1 .1 liters of H2O) to obtain a loading of 1 wt.-% of Ni calculated as the element based on 100 wt.-% of the resulting catalyst powder. The powder was then again mixed for 1 h to obtain a homogenous distribution, after which the catalyst powder was dried over night at 120°C and subsequently calcined in air for 4 h at 500 °C. The powder loaded with Mo and Ni was characterized by elemental analysis to afford Mo:
5.95 wt-%, Ni: 0.97 wt-%. The BET surface area of the final powder was determined to 355 m2/g via N2 sorption according to DIN 66131 .
Example 2: Catalytic testing in conversion of methane to benzene (MTB)
MTB tests with 100 g samples of the catalyst powder obtained according to Example 1 were performed in a fluidized-bed reactor. Prior to catalytic testing, methane was conducted at a rate of 100 Nl/h (normliters per hour) through the reactor, until the reaction temperature was reached. The flow rate was calculated for standard pressure and temperature. The reaction was then initiated at a temperature of 700°C and 2.5 bar and was conducted using a mixture of methane and helium with a CH4 : He ratio of (90 : 10) at a flow rate of 20 Nl/h. During testing, the catalyst samples were regenerated at regular intervals by conducting hydrogen gas into the
- - reactor for 5 h at 4 bar and a temperature of 750°C. Each reaction cycle was conducted for a period of 10 h.
The results from catalytic testing according to Example 2 are displayed in Figure 5. Thus as may be taken from the figure, the inventive catalyst powders display a high selectivity towards the conversion of methane to benzene and an accordingly low selectivity towards the generation of ethene and coke as by-products. Accordingly, the inventive catalyst powder displays a high selectivity towards benzene when employed in the MTB reaction.
Claims
1 . A process for the production of a powder or granulate, comprising
(I) providing a zeolitic material;
(II) suspending the zeolitic material provided in step (I) in a solvent system;
(III) mixing the suspension obtained in step (II) with one or more binders;
(IV) drying the suspension obtained in step (III); and
(V) calcining of the dried material obtained in step (IV);
wherein the zeolitic material provided in step (I) has an MFI-type framework structure comprising YO2 and optionally comprising X2O3,
wherein Y is a tetravalent element, and X is a trivalent element,
said material having an X-ray diffraction pattern comprising at least the following reflections:
wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern.
2. The process of claim 1 , wherein the solvent system comprises one or more solvents.
3. The process of claim 1 or 2, wherein the zeolitic material in the suspension obtained in step (II) displays a particle size D90 ranging from 0.05 to 20 μηη.
4. The process of any of claims 1 to 3, wherein mixing in step (III) is conducted under heating.
5. The process of any of claims 1 to 4, wherein the one or more binders in step (III) are selected from the group consisting of inorganic binders and derivatives thereof.
6. The process of claim 5, wherein the one or more binders further comprise one or more hydrolysable derivatives of one or more metal oxide and/or metalloid oxide.
7. The process of claim 6, wherein the weight ratio of the one or more hydrolysable derivatives of one or more metal oxide and/or metalloid oxide further comprised in the inorganic binder to the one or more sources of a metal oxide and/or of a metalloid oxide (hydrolysable derivatives : metal oxide and/or of a metalloid oxide) comprised in the binder ranges from (0.1 - 10) : 1 .
8. The process of any of claims 1 to 7, wherein in step (III) the weight ratio of the zeolitic material to the one or more binders to (zeolitic material : binder) ranges from (1 - 20) : 1 .
9. The process of any of claims 1 to 8, wherein the solid content of the suspension obtained in step (II) in wt.-% of the total weight of the suspension ranges from 5 to 80%.
10. The process of any of claims 1 to 9, wherein the calcining of the dried powder or granulate obtained in step (IV) is performed at a temperature ranging from 350 to 850°C.
1 1 . The process of any of claims 1 to 10, wherein the suspension obtained in step (III) is
spray-dried or spray-granulated.
12. The process of any of claims 1 to 1 1 , wherein the process further comprises
(VI) supporting one or more metals onto the calcined material obtained in step (V) as non-framework elements;
(VII) optionally drying the material obtained in step (VI); and
(VIII) optionally calcining the material obtained in step (VI) or (VII).
13. The process of claim 12, wherein the one or more metals comprise one or more selected from the group consisting of Mg, Sr, Zr, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more thereof.
14. The process of claim 13, wherein the amount of the one or more metals supported onto the calcined material ranges from 0.1 to 25 wt.-% calculated as the one or more elements and based on 100 wt.-% of the material obtained in step (VI).
15. The process of any of claims 1 to 14, wherein the 29Si MAS NMR of the zeolitic material comprises:
a first peak (P1 ) in the range of from -1 10.4 to -1 14.0; and
a second peak (P2) in the range of from -101 .4 to -106.8 ppm.
16. The process of any of claims 1 to 15, wherein the deconvoluted 29Si MAS NMR spectrum comprises one additional peak comprised in the range of from -1 13.2 to -1 15.2 ppm.
17. The process of any of claims 1 to 16, wherein the YO2 : X2O3 molar ratio ranges from 1 to 500.
The process of any of claims 1 to 17, wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof.
The process of any of claims 1 to 18, wherein X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof.
20. The process of any of claims 1 to 19, wherein the zeolitic material provided in step (I) comprises ZSM-5.
21 . A powder or granulate, obtainable by a process according to any of claims 1 to 20.
A powder or granulate, wherein said powder or granulate comprises a zeolitic material having an MFI-type framework structure comprising YO2 and optionally comprising X2O3 wherein Y is a tetravalent element, and X is a trivalent element,
said material having an X-ray diffraction pattern comprising at least the following reflections:
wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern, and
wherein the powder or granulate further comprises one or more binders.
The powder or granulate of claim 22, wherein the 29Si MAS NMR of the zeolitic material comprises:
a first peak (P1 ) in the range of from -1 10.4 to -1 14.0; and
a second peak (P2) in the range of from -101 .4 to -106.8 ppm.
24. The powder or granulate of claim 22 or 23, wherein the deconvoluted 29Si MAS NMR spectrum comprises one additional peak comprised in the range of from -1 13.2 to -1 15.2 ppm.
25. The powder or granulate of any of claims 22 to 24, wherein the YO2 : X2O3 molar ratio of the zeolitic material having an MFI-type framework structure ranges from 1 to 500.
26. The powder or granulate of any of claims 22 to 25, wherein the MFI-type framework structure of the zeolitic material does not contain X2O3.
27. The powder or granulate of any of claims 22 to 26, wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof.
28. The powder or granulate of any of claims 22 to 27, wherein X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof.
29. The powder or granulate of any of claims 22 to 28, wherein the zeolitic material comprises one or more cations and/or cationic elements as ionic non-framework elements.
30. The powder or granulate of claim 29, wherein the amount of the one or more cations and/or cationic elements ranges from 0.5 to 20 wt.-% calculated as the one or more elements and based on 100 wt.-% of the calcined powder or granulate.
31 . The powder or granulate of any of claims 22 to 30, wherein the one or more binders are selected from the group consisting of inorganic binders.
32. The powder or granulate of any of claims 22 to 31 , wherein the specific surface area of the powder or granulate determined according to DIN 66131 ranges from 50 to 700 m2/g.
33. The powder or granulate of any of claims 22 to 32, wherein the powder or granulate is obtained from spray-drying or from spray-granulation.
34. Use of a powder or granulate according to any of claims 21 to 33 as a catalyst, catalyst support, adsorbent, or for ion exchange.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP13189906 | 2013-10-23 | ||
| EP13189906.4 | 2013-10-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2015059175A1 true WO2015059175A1 (en) | 2015-04-30 |
Family
ID=49486348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2014/072614 WO2015059175A1 (en) | 2013-10-23 | 2014-10-22 | Powder or granulate for a zeolitic material and process for its production |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2015059175A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10202324B2 (en) | 2015-05-04 | 2019-02-12 | Basf Se | Process for the preparation of melonal |
| US10202323B2 (en) | 2015-07-15 | 2019-02-12 | Basf Se | Process for preparing an arylpropene |
| US10556801B2 (en) | 2015-02-12 | 2020-02-11 | Basf Se | Process for the preparation of a dealuminated zeolitic material having the BEA framework structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011042451A1 (en) * | 2009-10-08 | 2011-04-14 | Basf Se | Method for producing an si-bound fluidized-bed catalyst |
| WO2012123557A1 (en) * | 2011-03-15 | 2012-09-20 | Süd-Chemie AG | Modified catalyst for conversion of oxygenates to olefins |
| EP2548644A1 (en) * | 2011-07-21 | 2013-01-23 | Reliance Industries Limited | FCC catalyst additive and a method for its preparation |
-
2014
- 2014-10-22 WO PCT/EP2014/072614 patent/WO2015059175A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011042451A1 (en) * | 2009-10-08 | 2011-04-14 | Basf Se | Method for producing an si-bound fluidized-bed catalyst |
| WO2012123557A1 (en) * | 2011-03-15 | 2012-09-20 | Süd-Chemie AG | Modified catalyst for conversion of oxygenates to olefins |
| EP2548644A1 (en) * | 2011-07-21 | 2013-01-23 | Reliance Industries Limited | FCC catalyst additive and a method for its preparation |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10556801B2 (en) | 2015-02-12 | 2020-02-11 | Basf Se | Process for the preparation of a dealuminated zeolitic material having the BEA framework structure |
| US10202324B2 (en) | 2015-05-04 | 2019-02-12 | Basf Se | Process for the preparation of melonal |
| US10202323B2 (en) | 2015-07-15 | 2019-02-12 | Basf Se | Process for preparing an arylpropene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Su et al. | Synthesis of microscale and nanoscale ZSM-5 zeolites: effect of particle size and acidity of Zn modified ZSM-5 zeolites on aromatization performance | |
| EP3152162B1 (en) | Cha type zeolitic materials and methods for their preparation using combinations of cyclohexyl- and tetramethylammonium compounds | |
| CA2778370C (en) | Method of preparing zsm-5 zeolite using nanocrystalline zsm-5 seeds | |
| Pan et al. | A fast route for synthesizing nano-sized ZSM-5 aggregates | |
| US9790143B2 (en) | Delaminated zeolite catalyzed aromatic alkylation | |
| CA2983038A1 (en) | Process for preparing a molecular sieve | |
| US10266417B2 (en) | Zeolitic materials and methods for their preparation using alkenyltrialkylammonium compounds | |
| WO2007094949A1 (en) | Process for manufacturing molecular sieve of mfs framework type and its use | |
| EP3993902A1 (en) | Methods for producing mesoporous zeolite multifunctional catalysts for upgrading pyrolysis oil | |
| EP3257813B1 (en) | Method for producing beta zeolite | |
| CN106582805B (en) | A method of SAPO-11/MOR composite molecular screen is prepared with preset MOR crystal seed | |
| KR20210113654A (en) | Sinter-resistant metal species in zeolites | |
| CN111250152B (en) | Packaging method of Ni @ ZSM-5 bifunctional catalyst | |
| EP2841383B1 (en) | Zeolitic materials and methods for their preparation using alkenyltrialkylammonium compounds | |
| WO2015059175A1 (en) | Powder or granulate for a zeolitic material and process for its production | |
| KR102413855B1 (en) | Synthesis of molecular sieve SSZ-41 | |
| JP2023549267A (en) | Silica-alumina composition containing 1 to 30% by weight of crystalline ammonium aluminum hydroxide carbonate and method for producing the same | |
| JP2021533075A (en) | Method for manufacturing a zeolite material having a skeletal type FER | |
| CN115231587B (en) | Nano ZSM-5 molecular sieve and preparation method and application thereof | |
| WO2012141833A1 (en) | Process for producing molecular sieve materials | |
| CN115518678A (en) | Light hydrocarbon catalytic cracking catalyst, preparation method and application thereof | |
| WO2020227888A1 (en) | Zsm-57 zeolite and preparation method therefor | |
| JP2019034879A (en) | Mfi zeolite | |
| Cheng et al. | Microwave hydrothermal synthesis and acidity of nanosize gallosilicate mesoporous molecular sieves | |
| CN107572549B (en) | Preparation method of SAPO-34 molecular sieve and application of SAPO-34 molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14786929 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 14786929 Country of ref document: EP Kind code of ref document: A1 |