CS255394B1 - Method of zsm-5 type crystalline zeolite production - Google Patents
Method of zsm-5 type crystalline zeolite production Download PDFInfo
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- CS255394B1 CS255394B1 CS865555A CS555586A CS255394B1 CS 255394 B1 CS255394 B1 CS 255394B1 CS 865555 A CS865555 A CS 865555A CS 555586 A CS555586 A CS 555586A CS 255394 B1 CS255394 B1 CS 255394B1
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- 239000010457 zeolite Substances 0.000 title claims description 33
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 23
- 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 23
- 238000000034 method Methods 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 239000011541 reaction mixture Substances 0.000 description 12
- 229910052681 coesite Inorganic materials 0.000 description 10
- 229910052906 cristobalite Inorganic materials 0.000 description 10
- 229910052682 stishovite Inorganic materials 0.000 description 10
- 229910052905 tridymite Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000010899 nucleation Methods 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- -1 aliphatic amines Chemical class 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- NMGSERJNPJZFFC-UHFFFAOYSA-N carbonic acid;sulfuric acid Chemical compound OC(O)=O.OS(O)(=O)=O NMGSERJNPJZFFC-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012297 crystallization seed Substances 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical class CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910021489 α-quartz Inorganic materials 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
Vynález' sa týká sposobu výroby krystalických zeolitov typu ZSM-5 očkováním východiskovej reakčnej zmesi zeolitom ZSM-5.The present invention relates to a process for the production of crystalline ZSM-5 type zeolites by seeding the initial reaction mixture with ZSM-5 zeolite.
Význam zeolitov typu ZSM-5 neustále rastie. Je to dané ich strukturou, z'ožením, vel'kosťou a tvarom kanálov, čo ovplyvňuje ich tvarovo — selektivně a katalytické posobenie pri katalyzovaní niektorých významných priemyselných procesov, najmii z oblasti spracovania ropy a petrochémie. Tieto zeolity sú termicky stále asi do 1 000 ?C, čo umožňuje ich dobrú reaktiváciu, ked sa používajú ako katalyzátory. Zloženia týchto zeolitov, čo do obsahu kremíka a hliníka može byť značné variabilně, pričom sa može jednat v medznom případe až o zeolit bez hliníka, tzv. silikalit.The importance of ZSM-5 type zeolites is steadily increasing. This is due to their structure, loading, size and shape of the channels, which affects their shape - selectively and catalytic position in the catalysis of some important industrial processes, particularly in the field of oil processing and petrochemistry. These zeolites are still thermally up to about 1000 ? C, allowing their good reactivation when used as catalysts. The composition of these zeolites, in terms of silicon and aluminum content, can be varied considerably; silicalite.
Původný postup firmy Mobil Oi' podlá US pat. 3 702 886 používá na formovanie kryštálovej mriežky zeolit ZSM-5 tetrapropyla móniové zlúčeniny, ktoré sú však obecne ťažko dostupné, preto sa hladá ich vhodná’ náhrada. Novšie práce dokazuji!, že pre vytvorenie kryštálovej mriežky tohto zeolitu nie sú kvartérne amóniové zlúčeniny potřebné. Je možné ich připravil' za přítomnosti alifatických amínov, diamíuov, alkanolamínov, alifatických alkoholov spolu s amoniakom, glycerolu, dodecylbenzénsulfonanu a celého radu dalších látok, alebo aj bez použitia šablon.The original procedure of Mobil Oi 'according to US Pat. No. 3,702,886 uses zeolite ZSM-5 tetrapropyla mono-compounds to form a crystal lattice, but these are generally difficult to obtain and therefore a suitable substitute is sought. More recent work has shown that quaternary ammonium compounds are not required to form the crystal lattice of this zeolite. They can be prepared in the presence of aliphatic amines, diamines, alkanolamines, aliphatic alcohols together with ammonia, glycerol, dodecylbenzenesulfonate and a variety of other substances, or even without the use of templates.
V najnovších prácach sa tieto zeolity pripravujú očkováním pomocou přídavku dobré vykrystalizovaného zeolitu do východiskovej zmesi.In recent works, these zeolites are prepared by seeding by adding good crystallized zeolite to the starting mixture.
Podta Narita E., Sáto K., Okabe T.: Chem. Letters, 1984, s. 1 055 a Narita E., Sáto K., Yatabe N., Okabe T.: Ind. Eng. Chem. Prod. Ros. Dev. 24, 1985, s. 507 sa zeolity typu ZSM-5 syntetizujú použitím ZSM-5 očkovacích kryštálov ako kryštalizačných zárodkov zo zmesi aceton—voda bez dalších organických šablon. Malé množstvo acetonu v reakčnej zmesi inhibuje tvorbu alfa kremeňa a značné urýchluje kryštalizáciu ZSM-5 na očkovacích kryštáloch pri teplote 170 až 190 °C. Okrem acetonu sú účinné aj dalšie tóny ako metyietylketón a cyklohexanon. Nevýhodou ketónov je, že pečas reakcie možu z nich vznikat kondenzačně produkty. Nevýhody predchádzajúcich sposobov sú odstránené sposobom výroby krystalického zeolitu typu ZSM-5 hydrotermálnou syntézou pri teplote 170 až 200 °C za přítomnosti očkovacieho zeolitu ZSM-5 o obsahu kryštalickej fázy 75 až 100 % hmot. vo vodnom prostředí z východiskovej zmesi s obsahom 1,8 až 6,5 % hmot. kremíka, 0,01 až 0,15 % hmot. hliníka a 0,4 až 3,6 °/o hmot. sodíka vo formě oxidov, pričom % hmot. sú vztiahnuté na hmotnost východiskovej zmesi. Podstatou riešenia podlá vynálezu je, že reakcia prebieha za přítomnosti alifatického alkoholu s počtom uhlíkov v reťazci 1 až 8 v množstve do 30 % hmot., kde % hmot. sú vztiahnuté na hmotnost východiskovej zmesi počas 8 až 18 hod. za tlaku, ktorý zodpovedá tlaku pár sústavy pri po užitej pracovnej teplote. Reakčná zmes sa po kryštalizácii spracuje tak, že sa kryštalický podiel odfiltruje, dokonale premyje destilovanou vodou a vysuší. Dokladné vysušená vzorka zeolitu sa vyhodnotí kvalitativně a kvantitativné pomocou rontgenovej difrakčnej analýzy. Takto připravené zeolity sa po kalcinácii, iónovej výměně a aktivácii možu použit ako kyslé katalyzátory s tvarovo-selektívnym účinkom.Podta Narita E., Sato K., Okabe T .: Chem. Letters, 1984, p. And Narita E., Sato K., Yatabe N., Okabe T, Ind. Eng. Chem. Prod. Ros. Dev. 24, 1985, p. 507, ZSM-5 type zeolites are synthesized using ZSM-5 seed crystals as crystallization seeds from an acetone-water mixture without additional organic templates. A small amount of acetone in the reaction mixture inhibits alpha quartz formation and greatly accelerates crystallization of ZSM-5 on seeding crystals at 170-190 ° C. In addition to acetone, other tones such as methyl ethyl ketone and cyclohexanone are also effective. A disadvantage of ketones is that the reaction passage can result in condensation products. The disadvantages of the foregoing processes are eliminated by a process for producing crystalline ZSM-5 type zeolite by hydrothermal synthesis at 170-200 ° C in the presence of ZSM-5 seeding zeolite having a crystalline phase content of 75-100% by weight. in an aqueous medium from a starting mixture containing 1.8 to 6.5 wt. % silicon, 0.01 to 0.15 wt. % aluminum and 0.4 to 3.6% w / w; % sodium in the form of oxides; are based on the weight of the starting mixture. According to the invention, the reaction is carried out in the presence of an aliphatic alcohol with a number of carbons in the chain of 1 to 8 in an amount of up to 30 wt. are based on the weight of the starting mixture for 8 to 18 hours. at a pressure corresponding to the vapor pressure of the system at the operating temperature used. After crystallization, the reaction mixture is worked up by filtering off the crystalline fraction, thoroughly washing with distilled water and drying. The documented dried zeolite sample is evaluated qualitatively and quantitatively by X-ray diffraction analysis. The zeolites thus prepared can be used as acid catalysts with a shape-selective effect after calcination, ion exchange and activation.
Výhodou postupu podlá vynálezu je to, že sa pre přípravu zeolitov typu ZSM-5 nevyžadujú drahé a ťažko dostupné tetrapropylamóniové zlúčeniny, alebo iné organické šablóny a že sa takto pripravia zeolity o vysokej kryštalinite za kratší reakčný čas oproti predchádzajúcim postupom, ktoré vyžadujú reakčné časy až niekolko dní. Ďalšou výhodou spůsobu výroby kryštalického zeolitu podlá vynálezu je, že v alkoholickou! prostředí pri reakcii nevznikajú žiadne následné kondenzačně produkty, čo pri ketónoch sa nedá vylúčiť. Zanedbatelný tu nie je ani rozdiel v cene alifatický alkoholov a ketónov.An advantage of the process according to the invention is that expensive and hardly available tetrapropylammonium compounds or other organic templates are not required for the preparation of ZSM-5 type zeolites and that high crystallinity zeolites are thus prepared in a shorter reaction time compared to previous processes requiring reaction times up to several days. Another advantage of the process for producing the crystalline zeolite according to the invention is that it is alcoholic. No subsequent condensation products are formed during the reaction, which cannot be excluded with ketones. Negligible here is not even the difference in price of aliphatic alcohols and ketones.
Postup přípravy zeolitov typu ZSM-5 je v ďalšom opísaný v niekolkých príkladoch prevedenia, na ktoré sa však neobmedzuje. Příklad 1The process for preparing zeolites of the ZSM-5 type is described in the following examples, but is not limited thereto. Example 1
Do poteflónovanej tlakovej ampule o objeme 120 cm3, ktorá bola temperovaná v ohrevnom bloku opatrenom reguláciou teploty sa nadávkovala reakčná zmes, ktorá sa připravila tak, že sa k 25,2 g hydrosólu kyseliny kremičitej o koncentrácii 29,7 °/o hmot. oxidu křemičitého, po kvapkách za miešania přidal roztok síranu hlinitého 0,83 gramu síranu v 30 cm3 vody a potom roztok hydroxidu sodného 1,5 g v 33 cm3 vody. K zmesi sa přidal očkovací zeolit 0,33 g ZSM-5 o module 28,1 a kryštalinite 90 % hmot. a 4,5 g etanolu. Připravená zmes sa počas 20 minút pri laboratórnej teplote homogenizovala a preliaia do ampule. Reakčná zmes mala následovně zloženie vyjádřené v molových pomeroch oxidov:The reaction mixture was charged into a 120 cm 3 teflon-filled pressure ampoule which was tempered in a heating block equipped with a temperature control solution and was prepared by adding to 25.2 g of a 29.7% by weight silica hydrosol. A solution of aluminum sulfate 0.83 grams of sulfate in 30 cm 3 of water was added dropwise with stirring, followed by a solution of sodium hydroxide 1.5 g in 33 cm 3 of water. To the mixture was added a seeding zeolite of 0.33 g ZSM-5 of module 28.1 and a crystallinity of 90% by weight. and 4.5 g of ethanol. The prepared mixture was homogenized for 20 minutes at room temperature and poured into an ampoule. The reaction mixture had the following composition expressed in molar ratios of oxides:
SÍO2/AI2O3 100SiO2 / Al2O3 100
Na2O/SiO2 = 0,15Na2O / SiO2 = 0.15
H2O/S1O2 = 36H2O / S1O2 = 36
Hydrotermálna syntéza sa uskutečňovala pri 190 °C po dobu 14 hodin. Po ochladeni sa krystalický podiel odfiltroval, premyl destilovanou vodou a vysušil 4 h vo vákuovej sušiarni pri 110 °C. Získalo sa 6 g produktu. Pomocou rontgenovej difrakčnej analýzy sa zistilo, že sa jedná o zeolit ZSM-5 o obsahu kryštalickej fázy 85 % hmot. Příklad 2The hydrothermal synthesis was carried out at 190 ° C for 14 hours. After cooling, the crystalline fraction was filtered off, washed with distilled water and dried in a vacuum oven at 110 ° C for 4 h. 6 g of product were obtained. X-ray diffraction analysis revealed ZSM-5 zeolite with a crystalline phase content of 85% by weight. Example 2
Použilo sa zariadenie, pracovný postup a východisková zmes o zložení ako v přiklade 1, no s tým rozdielom, že sa pracovalo za přídavku 4,5 g propanolu. Za rovnakých reakčných podmienok ako v příklade 1 sa získalo 6 g zeolitu ZSM-5 o obsahu kryštalickej fázy 98 % hmot.The apparatus, process and starting mixture of composition as in Example 1 were used, except that 4.5 g of propanol were added. Under the same reaction conditions as in Example 1, 6 g of ZSM-5 zeolite having a crystalline phase content of 98% by weight were obtained.
Příklad 3Example 3
Do reaktora z příkladu 1 sa nadávkovala reakčná zmes pozostávajúca z 25,2 g bydrosólu kyseliny kremičitej o obsahu 29,7 % hmot. SiO2, ďalej 8,83 g síranu hhnitého, 1,5 gramu hydroxidu sodného, 63 g vody, 0,33 gramu očkovacieho zeolitu ZSM-5 o module 28,1, ktorý obsahoval 92 % hmot. kryštalickej fázy a 4,5 g n-butanolu. Reakčná zmes mala následovně zloženie dané molovými pomermi oxidov:The reactor of Example 1 was charged with a reaction mixture consisting of 25.2 g of silicic acid bydrosol of 29.7 wt%. SiO 2 , 8.83 g of carbonate sulphate, 1.5 g of sodium hydroxide, 63 g of water, 0.33 g of seeding zeolite ZSM-5 of module 28.1, which contained 92 wt. crystalline phase and 4.5 g of n-butanol. The reaction mixture had the following composition given by molar ratios of oxides:
SÍO2/AI2O3 = 100SiO2 / Al2O3 = 100
NazO/SiO2 — 0,15Na 2 / SiO 2 - 0.15
H2O/SÍO2 == 36H2O / SiO2 == 36
Pracovalo sa pri teplote 180 °C po dobu 15 h. Získalo sa 6,1 g zeolitu ZSM-5 o zložsní danom mólovým zastúpením oxidov:The reaction was carried out at 180 ° C for 15 h. 6.1 g of zeolite ZSM-5 were obtained with a composition given by the molar content of oxides:
S1O2 : AI2O3 : Na2O = 66,1 : 1 : 0,85 o kryštalinite 97 °/o.S1O2: AI2O3: Na 2 O = 66.1: 1: 0.85 a crystallinity of 97 ° / o.
Příklad 4Example 4
Do reaktora sa nadávkovala reakčná zmes připravená rovnako ako v příklade 1 s tým rozdielom, že sa použil očkovací zeolit ZSM-5 o module 50, ktorý obsahoval 93 % hmot. kryštalickej fázy v množstve 0,33 g na hmotnost reakčnej zmesi a ako rozpúšťadlo sa použila voda za přídavku n amylalkoholu v množstve 4,5 g. Zloženie východiskovej zmesi bolo následovně:The reaction mixture prepared as in Example 1 was metered into the reactor, except that a seeding zeolite ZSM-5 of module 50 containing 93% by weight was used. of the crystalline phase in an amount of 0.33 g per weight of the reaction mixture and water was used as solvent with the addition of n amyl alcohol in an amount of 4.5 g. The composition of the starting mixture was as follows:
SÍO:/Al2O3 — 100SiO: / Al2O3 - 100
Na2O/SiO2 = 0,15Na 2 O / SiO 2 = 0.15
H2O/SÍO2 = 36H2O / SiO2 = 36
Syntéza zeolitu sa uskutočňovala pri teplote 195 CC po dobu 13 h. Izo’áciou z reakčnej zmesi sa získalo 6,2 g zeolitu ZSM-5 o mólovom zložení:Zeolite synthesis was carried out at 195 ° C for 13 h. Isolation from the reaction mixture yielded 6.2 g of zeolite ZSM-5 having a molar composition:
SiO2 : AI2O3 : NasO = 66,5 : 1 : 0,77SiO 2 : Al 2 O 3: NasO = 66.5: 1: 0.77
Kryštalinita zeolitu bola 100 % hmot.The crystallinity of the zeolite was 100 wt.
P r i k 1 a d 5Example 1 and d 5
Do reaktora sa nadávkovala východisková zmes tak ako je to uvedené v příklade 1, s tým rozdielom, že sa pracovalo za přídavku 5 g heptylalkoholu a ako očkovací zeolit sa použil zeo it ZSM-5 o module 35 o obsahu kryštalickej fázy 90 % hmot. v množsive 0,5 g na celá hmotnost východiskovej zmesi.The starting mixture as in Example 1 was metered into the reactor except that 5 g of heptyl alcohol was added and the seeding zeolite was ZSM-5 of module 35 having a crystalline phase content of 90% by weight. in an amount of 0.5 g for the total weight of the starting mixture.
Reakčná zmes mala následovně zloženie v molových pomeroch oxidov:The reaction mixture had the following composition in molar ratios of oxides:
S1O2/AI2O3 = 100S1O2 / Al2O3 = 100
Na20/SiO2 == 0,15Na 2 O / SiO 2 == 0.15
HjO/SíOž = 36H2O / SiO2 = 36
Hydrotermálna syntéza sa uskutočňovala pri j90°C po dobu 14 h. Izoláciou z reakčnej zmesi sa získalo 6.5 g zeolitu ZSM-5 o mólovom zložení:The hydrothermal synthesis was performed at 90 ° C for 14 h. Isolation from the reaction mixture yielded 6.5 g of zeolite ZSM-5 having a molar composition:
S1O2 : AI2O3 : Na2O 80 : 1 : 0,7S1O2: AI2O3: Na 2 O 80: 1: 0.7
Kryštalinita zeolitu stanovená rtg. difrakčnou dialýzou boia 95 % hmot.Zeolite crystallinity determined by X-ray. by diffractive dialysis boia 95 wt.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS865555A CS255394B1 (en) | 1986-07-22 | 1986-07-22 | Method of zsm-5 type crystalline zeolite production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS865555A CS255394B1 (en) | 1986-07-22 | 1986-07-22 | Method of zsm-5 type crystalline zeolite production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS555586A1 CS555586A1 (en) | 1987-06-11 |
| CS255394B1 true CS255394B1 (en) | 1988-03-15 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS865555A CS255394B1 (en) | 1986-07-22 | 1986-07-22 | Method of zsm-5 type crystalline zeolite production |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS255394B1 (en) |
-
1986
- 1986-07-22 CS CS865555A patent/CS255394B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS555586A1 (en) | 1987-06-11 |
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