EP0625125A1 - Verfahren zur synthese von zeolithen vom typ zsm-48 - Google Patents
Verfahren zur synthese von zeolithen vom typ zsm-48Info
- Publication number
- EP0625125A1 EP0625125A1 EP94901992A EP94901992A EP0625125A1 EP 0625125 A1 EP0625125 A1 EP 0625125A1 EP 94901992 A EP94901992 A EP 94901992A EP 94901992 A EP94901992 A EP 94901992A EP 0625125 A1 EP0625125 A1 EP 0625125A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zeolite
- aluminum
- reaction mixture
- zsm
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000010457 zeolite Substances 0.000 title claims abstract description 52
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 40
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 39
- 238000001308 synthesis method Methods 0.000 title 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 25
- 229910001868 water Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- -1 hydroxide ions Chemical class 0.000 claims abstract description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 239000003463 adsorbent Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 53
- 239000000377 silicon dioxide Substances 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- 239000011541 reaction mixture Substances 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000012690 zeolite precursor Substances 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 238000002441 X-ray diffraction Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000004645 aluminates Chemical class 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000000017 hydrogel Substances 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 229910052605 nesosilicate Inorganic materials 0.000 claims description 2
- 229910052700 potassium Chemical group 0.000 claims description 2
- 239000011591 potassium Chemical group 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 239000004115 Sodium Silicate Substances 0.000 claims 1
- 238000010586 diagram Methods 0.000 claims 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims 1
- 229910052911 sodium silicate Inorganic materials 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 25
- 239000013078 crystal Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000000499 gel Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000009331 sowing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000012297 crystallization seed Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000004762 orthosilicates Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 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
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/703—MRE-type, e.g. ZSM-48
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
Definitions
- This invention relates to a process for the synthesis of zeolites of the ZSM-48 type and their use as a selective organophilic catalyst and adsorbent.
- the zeolites whose structure corresponds to the topology of type ZSM-48, known to date, are EU-2, EU-ll and ZBM-30 (P. Jacobs and J. Martens, Synthesis of high silica aluminosilicate zeolites , Stud. Surf. Sci. Catal., 33, 275, 1987). They are solids of interest for the catalytic transformation of hydrocarbons and organic compounds and for adsorption.
- the synthesis of zeolites of the ZSM-48 type is described in several patents and publications in the scientific literature, the main ones of which are summarized in Table 1.
- the zeolites of the ZSM-48 type are prepared by hydrothermal crystallization of reactive alkaline gels of aluminosilicates or silicates. The syntheses are carried out in the presence of one or more nitrogenous organic agents such as alkylamines, diamines, tertiary, quaternary and bis-quaternary alkyl ammoniums or pyrrolidine.
- nitrogenous organic agents such as alkylamines, diamines, tertiary, quaternary and bis-quaternary alkyl ammoniums or pyrrolidine.
- microporous zeolite is carried out by an oxidative calcination at a temperature generally above 500 ° C.
- This calcination stage has a certain number of drawbacks because, in addition to its energy cost, it can cause degradation of the crystal structure and it is accompanied by the release of nitrogen oxides which it is imperative to treat for environmental reasons.
- the cost of syntheses is increased because the organic agent is generally the most expensive component of the preparation.
- zeolite precursor can be transformed into zeolite without calcination, by a simple moderate heat treatment. This treatment does not lead to degradation of the crystal structure.
- the zeolite obtained has remarkable thermal and chemical stability.
- This mixture is maintained at a temperature above 80 ° C. and under a pressure at least equal to the vapor pressure of the solution for a time sufficient to effect the crystallization of the reaction mixture into a zeolite precursor, then the enzéolite precursor is transformed by removing the glycol and the water retained in the porosity .
- the reaction mixture may optionally contain a source of trivalent aluminum.
- the hydroxide ions are derived from compounds of formula M (OH) n where M is a cation of valence n, n being generally 1 or
- M is generally an alkali metal from group IA of the periodic table, an alkaline earth metal or an organic compound, such as a quaternary ammonium.
- tetravalent silicon which can be used in the preparation of the reaction mixture
- finely divided solid silicas in the form of hydrogels, aerogels or colloidal suspensions, water-soluble silicates such as alkali silicates, hydrolyzable silicic esters such as that orthosilicates, tetraalkyl formula Si (OR) 4 wherein R is alkyl to C 4 such as methyl and ethyl.
- the silicon source is used in the form of a true aqueous solution, in the case of water-soluble silicates, or else of an aqueous suspension which may be colloidal, in the case of finely divided silicates.
- the traces of aluminum present in the silicon source do not interfere with crystallization.
- Aluminum can also be deliberately incorporated into the synthesis in the form of aluminum salts such as sulphate, nitrate, chloride, fluoride, acetate, aluminum oxides and hydroxides, aluminates and in particular alkali alu inates, aluminum esters such as the aluminum trialkoxides of formula Al (OR) 3 in which R denotes a C1 to C4 alkyl radical such as methyl, ethyl, propyl or butyl.
- the mixing of the ingredients constituting the reaction mixture can be carried out in any order.
- an alkaline solution is first prepared by dissolving the strong base in water.
- the strong base is generally potash or soda in pellets.
- To this alkaline solution is added the glycol and then the source of silicon. These two operations are generally carried out at room temperature.
- the whole is transferred to an autoclave.
- the mixture is heated under autogenous pressure until the zeolite has completely crystallized.
- the reaction time is generally between 10 and 150 hours.
- the temperature varies between 80 and 200 ° C.
- the duration of the synthesis can be shortened by adding to the reaction medium crystallization seeds.
- the germs are obtained by grinding a zeolite of the ZSM-48 type.
- the crystals obtained are the precursor of the zeolite consisting of the zeolite trapping in its pores and cavities the water of hydration, cations and glycol. These crystals are separated from the reaction medium by filtration, washed with distilled or deionized water, until washing waters are obtained at neutral pH. The washed crystals can then be dried at a temperature between room temperature and 90 ° C, preferably around 70 ° C.
- the stoichiometric composition of the zeolite precursor expressed in moles of oxides is as follows: a M g. b AI 2 O 3 . Si ⁇ 2 . cH 2 ⁇ .dG n where - M is a cation with valence n, in general an alkali metal from group IA of the Periodic Table of the Elements, an alkaline earth metal or a quaternary ammonium. M is preferably potassium or sodium. G is a glycol molecule.
- the X-ray diffractogram was obtained by a conventional method using K alpha copper radiation and an amplifying detector.
- the signal intensities are recorded as a function of their position expressed in two theta, where theta is the Bragg angle.
- d (nm) the reticular distances
- the values may differ slightly depending on the size of the crystals and their hydration state, but in general the X-ray diffractogram is a characteristic of the structure concerned.
- the zeolite is obtained from the precursor by liberation from its cavities and channels.
- the cavities and channels contain nitrogenous organic bases.
- the porosity can only be released by calcination, by thermally degrading the structuring molecules.
- the porosity of the ZSM-48 zeolite prepared according to the invention is released by treatments at moderate temperature, sufficient to cause the departure of the water and glycol molecules. A simple air drying is sufficient.
- ethylene glycol is particularly advantageous because it can be removed by drying at a temperature below 200 ° C.
- the zeolite thus obtained has an X-ray diffraction spectrum substantially equal to that of the precursor, except for some variations in intensity of the peaks at small angles.
- the crystallinity and the adsorption capacities of the zeolite are retained after heat treatment and hydrothermal prolonged or after treatment with acid or basic solutions.
- the zeolite Before use, the zeolite can be subjected to a treatment aimed at eliminating traces of cations, generally alkaline cations which may be present.
- the zeolites obtained according to the invention are suitable as organophilic adsorbents, allowing the separation of "organic molecules from water.
- EXAMPLE 1 This example describes a general method for preparing a zeolite of the ZSM-48 type according to the invention and its use as an adsorbent.
- the solid presents an X-ray diffractogram corresponding to that of Table 3.
- This zeolite adsorbs 0.1% by weight of water (5 torr, 25 ° C), and 4.7% by weight of methanol (15 torr, 25 ° C).
- the zeolite After calcination under air flow at 850 ° C for ten hours, the zeolite retained its crystallinity, evaluated by X-ray diffraction, and its specific surface at
- the solid has an X-ray diffractogram corresponding to that of Table 3.
- the weight of solid, dried at 70 ° C, obtained in this synthesis, is 7.6 grams which corresponds to a yield relative to the silica used for 72%.
- This example illustrates a synthesis of zeolite according to the invention in which the content of ethylene glycol in the starting gel and the crystallization temperature have been reduced.
- the solid presents an X-ray diffractogram corresponding to that of Table 3.
- the weight of solid, dried at 70 ° C., collected in this synthesis is 27.4 grams, which corresponds to a yield relative to the committed silica of 89%.
- This example illustrates a synthesis of zeolite according to the invention from a medium richer in aluminate.
- KOH potassium hydroxide
- Al (OH) 3, Merck aluminum hydroxide
- a 200 ml stainless steel autoclave containing 41 ml of deionized water.
- 66 g of ethylene glycol Labosi for analyzes
- 9.2 g of silica Si ⁇ 2, Aerosil Serva
- the composition of the crystallization gel obtained is as follows 0.16 K2O, 0.005 AI2O3, SiO2, 15 H2O, 7 C2H4 (0H) 2
- the solid has an X-ray diffractogram corresponding to that of Table 3.
- EXAMPLE 5 This example illustrates a synthesis of zeolite according to the invention from a medium in which the ethylene glycol has been replaced by diethylene glycol and in the absence of stirring during crystallization.
- the solid has an X-ray diffractogram corresponding to that of Table 3.
- EXAMPLE 6 This example illustrates a synthesis of zeolite according to the intervention from a medium in which the ethylene glycol has been replaced by triethylene glycol.
- the solid has an X-ray difractogram corresponding to that of Table 3.
- the weight of solid, dried at 70 ° C., collected in this synthesis is 2.68 grams, which corresponds to a yield relative to the committed silica of
- catalytic activity of zeolites according to the invention was evaluated as a fresh additive of an industrial FCC catalyst, called in short ECAT (for Equilibrium
- Example 3 The additive obtained in Example 3 is mechanically mixed in an amount of 5 and 10% by weight with the ECAT catalyst.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9214776 | 1992-12-08 | ||
FR9214776A FR2698863B1 (fr) | 1992-12-08 | 1992-12-08 | Procédé de synthèse de zolithes du type ZSM-48, produits obtenus et leur application en adsorption et catalyse. |
PCT/FR1993/001200 WO1994013583A1 (fr) | 1992-12-08 | 1993-12-07 | Procede de synthese de zeolithes du type zsm-48 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0625125A1 true EP0625125A1 (de) | 1994-11-23 |
Family
ID=9436346
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94901992A Withdrawn EP0625125A1 (de) | 1992-12-08 | 1993-12-07 | Verfahren zur synthese von zeolithen vom typ zsm-48 |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0625125A1 (de) |
JP (1) | JPH07503699A (de) |
CA (1) | CA2129662A1 (de) |
FR (1) | FR2698863B1 (de) |
WO (1) | WO1994013583A1 (de) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2818285B1 (fr) * | 2000-12-15 | 2004-12-17 | Inst Francais Du Petrole | Procede flexible ameliore de production de bases huiles et de distillats par une conversion-hydroisomerisation sur un catalyseur faiblement disperse suivie d'un deparaffinage catalytique |
FR2818284B1 (fr) * | 2000-12-15 | 2006-08-04 | Inst Francais Du Petrole | Procede flexible ameliore de production de bases huiles et distillats moyens avec une conversion-hydroisomerisation suivie d'un deparaffinage catalytique |
TWI450762B (zh) | 2005-12-13 | 2014-09-01 | Exxonmobil Res & Eng Co | 具有高活性之zsm-48及用以去蠟之方法 |
US7482300B2 (en) | 2005-12-13 | 2009-01-27 | Exxonmobil Research And Engineering Company | High activity ZSM-48 and methods for dewaxing |
-
1992
- 1992-12-08 FR FR9214776A patent/FR2698863B1/fr not_active Expired - Fee Related
-
1993
- 1993-12-07 JP JP6513858A patent/JPH07503699A/ja active Pending
- 1993-12-07 WO PCT/FR1993/001200 patent/WO1994013583A1/fr not_active Application Discontinuation
- 1993-12-07 EP EP94901992A patent/EP0625125A1/de not_active Withdrawn
- 1993-12-07 CA CA 2129662 patent/CA2129662A1/fr not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO9413583A1 * |
Also Published As
Publication number | Publication date |
---|---|
FR2698863B1 (fr) | 1995-01-13 |
FR2698863A1 (fr) | 1994-06-10 |
WO1994013583A1 (fr) | 1994-06-23 |
CA2129662A1 (fr) | 1994-06-23 |
JPH07503699A (ja) | 1995-04-20 |
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