CS267357B1 - Method of high-siliceous zeolite production - Google Patents
Method of high-siliceous zeolite production Download PDFInfo
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- CS267357B1 CS267357B1 CS879514A CS951487A CS267357B1 CS 267357 B1 CS267357 B1 CS 267357B1 CS 879514 A CS879514 A CS 879514A CS 951487 A CS951487 A CS 951487A CS 267357 B1 CS267357 B1 CS 267357B1
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- alcohols
- oxygenated organic
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- 239000010457 zeolite Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 aliphatic alcohols Chemical class 0.000 claims abstract description 14
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 8
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 150000002576 ketones Chemical class 0.000 claims abstract description 7
- 239000011734 sodium Substances 0.000 claims abstract description 7
- 150000001298 alcohols Chemical class 0.000 claims abstract description 6
- 150000002148 esters Chemical class 0.000 claims abstract description 5
- 150000002170 ethers Chemical class 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 239000012736 aqueous medium Substances 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 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 claims abstract description 3
- 150000001241 acetals Chemical class 0.000 claims abstract description 3
- 238000010899 nucleation Methods 0.000 claims abstract description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 28
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 10
- 238000002474 experimental method Methods 0.000 claims description 7
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 5
- 238000007127 saponification reaction Methods 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- PWVHLUKAENFZIA-UHFFFAOYSA-N cyclohexanol;cyclohexanone Chemical compound OC1CCCCC1.O=C1CCCCC1 PWVHLUKAENFZIA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 2
- 150000001983 dialkylethers Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 229910052681 coesite Inorganic materials 0.000 claims 2
- 229910052906 cristobalite Inorganic materials 0.000 claims 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 2
- 229910052682 stishovite Inorganic materials 0.000 claims 2
- 229910052905 tridymite Inorganic materials 0.000 claims 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Natural products O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000007859 condensation product Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 6
- 230000031018 biological processes and functions Effects 0.000 abstract 1
- 229910009112 xH2O Inorganic materials 0.000 abstract 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 12
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 8
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003708 ampul Substances 0.000 description 4
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 4
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241001432959 Chernes Species 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- IIFFFBSAXDNJHX-UHFFFAOYSA-N 2-methyl-n,n-bis(2-methylpropyl)propan-1-amine Chemical compound CC(C)CN(CC(C)C)CC(C)C IIFFFBSAXDNJHX-UHFFFAOYSA-N 0.000 description 1
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XUZDJUDKWXESQE-UHFFFAOYSA-N chromium copper zinc Chemical compound [Cr].[Zn].[Cu] XUZDJUDKWXESQE-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical class CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Spósob výroby vysokokremičitého zeolitu obecného vzorca NanAlnSi<)fJ._nOi92 · xH2O, kde n je váčšie než 27, x = 0 až 20 (zeolit ZSM-5) sa uskutočňuje hydrotermálnou syntézou z východiskových zmesi, obsahujúcich hlavně zdroj kremíka, hliníka a sodika, za přídavku očkovacieho vysokokremičitého zeolitu, prevážne vo vodnom prostředí za přídavku zmezi najmenej dvoch alifatických alkoholov Ci až C8 alebo ich zmesi s najmenej jednou ďalšou kyslíkatou organickou zlúčeninou o počte uhlíkov v molekule 1 až 8, resp. 2 až 10 (ketóny, aldehydy, étery, estery, acetály). Dajú sa tak využiť vedfajšie produkty chemických, zvlášť petrochemických, ale aj biologických procesov, obsahujúce zmesi alkoholov a dalších uvedených kyslíkatých organických komponentov. Spósob je vhodný na výrobu syntetických zeolitov a katalyzátorov v chemickom priemysle.A method for producing high silica zeolite of the formula NanAlnSi <) fJ_nOi92 · xH2O, where n is greater than 27, x = 0 to 20 (zeolite ZSM-5) is carried out by hydrothermal synthesis from starting mixtures containing mainly the source of silicon, aluminum and sodium, with the addition seeding high silica zeolite, predominantly in aqueous medium with addition at least two aliphatic alcohols C 1 to C 8 or mixtures thereof with at least one with another oxygenated organic compound with a number of carbons per molecule of 1 to 8, respectively. 2 to 10 (ketones, aldehydes, ethers, esters, acetals). They give to use the by-products of chemical, especially petrochemical but also biological processes containing mixtures of alcohols and others of said oxygenated organic components. The method is suitable for the production of synthetic zeolites and catalysts in the chemical industry.
Description
Vynález sa týká sposobu výroby vysokokremičitého zeolitu typu ZSM-5 očkováním východiskovej reakčnej zmesi cielenými zeolitmi za přítomnosti technicky Fahko dostupných látok.The invention relates to a process for the production of a high-silica zeolite of the ZSM-5 type by seeding the starting reaction mixture with targeted zeolites in the presence of technically readily available substances.
Stále rastiici význam vysokokrcmičilých zco litov samotných, ale aj ako aktívnych nosičov katalyzátorov a katalytických systémov vyvot, láva potřebu rastu výroby a zjednodušenie spósobov výroby takých zeolitov. Ich zloženie sa čo do obsahu kremíka a hliníka móže meniť, w pričom v hraničnom případe móže ísť až o zeolit bez hliníka, tzv. silikalit.The ever-growing importance of high-silica aluminates themselves, but also as active supports for catalysts and catalyst systems, is growing by the need to increase production and simplify methods of producing such zeolites. Their composition in terms of the content of silica and alumina can vary, w being in borderline cases can go to the zeolite without aluminum so. silicalite.
Póvodný postup firmy Mobil (USA pat. 3 702 886) používá na formovanie kryštálovej mriežky zeolitu ZSM-5 tetrapropylamóniové zlúčeniny, ktoré sú však technicky ťažšie dostupné a preto sa hl’adá ich vhodná náhrada. K takým patří použitie etylamínu a ďalších alifatických amínov (čs. autorské osvedčenie 234 814), diamínov, amoniaku, pyridinu a alkanolamínov (Mravec D., Ilavský J.: Ropa a uhlie 28, 197 /1986/; Seidl V.: tamtiež str. 202; USA pat. 3 702 886, 4 151 189, 4 046 859 a 4 139 600). Navýše sa zeolity tohto typu syntetizujú použitím očkovacích kryštálov právě zeolitov ZSM-5 ako kryštalizačných zárodkov a zo zmesi aceton —voda bez ďalších organických šablon (Narita E. a ini: Chern. Letters, 1984, s. 1 055; Narita E. a ini: Ind. Eng. Chern. Prod. Res. Dev. 24, 1985, s. 507). Dokonca sa hydrotermálna syntéza zeolitov typu ZSM-5 uskutočňuje vo vodnom prostředí za přídavku 0 až 30 % hmot, alifatického alkoholu Ci až C8 (čs. autorské osvedčenie 255 394). Avšak napriek uvedenému evidentnému pokroku týchto najnovších riešení, nevyčerpali sa všetky technické možnosti zdokonalenia výroby silikalitových zeolitov, zvlášť typu ZSM-5. Uvedené extraktné postupy je však možné ďalej modifikovat’ s využitím technicky Fahko dostupných organických medziproduktov, vrátane vedFajších produktov hlavně petrochemických procesov.The original process of Mobil (U.S. Pat. No. 3,702,886) uses tetrapropylammonium compounds to form the crystal lattice of zeolite ZSM-5, which are, however, more technically difficult to obtain and are therefore sought to be a suitable substitute. These include the use of ethylamine and other aliphatic amines (Czech author's certificate 234 814), diamines, ammonia, pyridine and alkanolamines (Mravec D., Ilavský J .: Petroleum and Coal 28, 197 (1986); Seidl V .: ibid. P. 202; U.S. Pat. Nos. 3,702,886, 4,151,189, 4,046,859 and 4,139,600). In addition, zeolites of this type are synthesized using seed crystals of ZSM-5 zeolites as crystallization nuclei and from an acetone-water mixture without further organic templates (Narita E. et al., Chern. Letters, 1984, p. 1,055; Narita E. et al. : Ind. Eng. Chern. Prod. Res. Dev. 24, 1985, p. 507). Even the hydrothermal synthesis of zeolites of the ZSM-5 is carried out in an aqueous medium with the addition of 0-30% by weight, of the aliphatic alcohol C 8 to C (MS. Author's certificate 255 394). However, despite the above-mentioned evident progress of these latest solutions, not all technical possibilities for improving the production of silicalite zeolites, especially of the ZSM-5 type, have been exhausted. However, said extraction processes can be further modified using technically readily available organic intermediates, including by-products of mainly petrochemical processes.
A tak podlá tohto vynálezu sa spósob výroby vysokokremičitého zeolitu obecného vzorca NatlAl„Si%_nO|92. xH2O, v ktorom n je váčšie než 27 a x = 0 až 20, hydrotermálnou syntézou pri teplote 130 až 250 °C, spravidla za tlaku pár sústavy pri použitej pracovnej teplote, z východiskovej zmesi obsahujúcej hlavně zdroj kremíka, hliníka a sodíka, za přídavku 0,01 až 10 % hmot, očkovacieho vysokokremičitého zeolitu s obsahom kryštalickej fázy 75 až 100 %, aspoň prevážne vo vodnom prostředí, za přídavku alifatického alkoholu Ct až C8 sa uskutočňuje tak, že prídavok v množstve 0,1 až 40 % hmot, tvoří zmes najmenej dvoch alifatických alkoholov C! až C8 a/alebo zmes pozostávajúca z 50 až 95 % hmot, najmenej dvoch alifatických alkoholov Ct až C8 a 5 až 50 % hmot, najmenej jednej ďalšej kyslíkatej organickej zlúčeniny vybranej z ketónov C3 až C8, aldehydov C( až C8, dialkyléterov C2 až Cio> esterov C3 až C7 a cyklohexanolu.Thus, the present invention is a method of making zeolites of the formula vysokokremičitého For thick Al "_% Si n H | 9 second xH 2 O, in which n is greater than 27 and x = 0 to 20, by hydrothermal synthesis at a temperature of 130 to 250 ° C, usually under vapor pressure at the operating temperature used, from a starting mixture containing mainly a source of silicon, aluminum and sodium, for adding 0.01 to 10% by weight, seed vysokokremičitého zeolite comprising a crystalline phase of 75 to 100%, at least predominantly in the aqueous medium, with the addition of an aliphatic alcohol C t to C 8 was accomplished by the addition in an amount of 0.1 to 40% mass, forms a mixture of at least two aliphatic alcohols C! to C 8, and / or a mixture comprising 50 to 95% by weight, of at least two aliphatic alcohols, C t to C 8, and 5 to 50% by weight, of at least one other oxygenated organic compound selected from ketones of C 3 to C 8, aldehyde C (to C 8 , C 2 to C 10 dialkyl ethers of C 3 to C 7 esters and cyclohexanol.
Výhodou sposobu výroby podlá tohto vynálezu je technická jednoduchost formulácie komponentov reakčného systému. Ďalej syner gický účinok zmesi najmenej dvoch alifatických alkoholov C, až C8, ako aj ich zmesí s ďalšími kyslíkatými organickými zlúčeninami, najmi ketóntní, étermi a aldehydmi na výrobu vysokokremičitých zeolitov s vysokou kryštalinitou (90 až 94 %) a nájdenie nových komponen tov modifikácie výroby uvedených zeolitov. Spósob umožňuje technicky využiť prevážne alkoholické aj vedlajšie produkty chemických a zvlášť petrochemických procesov, pre ktoré nezriedka chýbajú procesy vyššieho technickoekonomického zhodnotenia. Navýše, výhodou je aj nízká toxicita aplikovaných komponentov sposobu výroby podFa tohto vynálezu a jeho uskutočniteFnosť na bežnom výrobnom zariadení. Takto vyrobený vysokokremičitý zeolit možno zbaviť pri zvýšenej teplote kryštalickej i adsorbovanej vody.An advantage of the production method of the present invention is the technical simplicity of formulating the components of the reaction system. Furthermore, the synergistic effect of a mixture of at least two C 1 to C 8 aliphatic alcohols, as well as their mixtures with other oxygenated organic compounds, especially ketones, ethers and aldehydes, for the production of high silica zeolites with high crystallinity (90-94%) and finding new modification components production of those zeolites. The method makes it possible to technically use mainly alcoholic and by-products of chemical and especially petrochemical processes, for which processes of higher technical and economic recovery are often lacking. In addition, the low toxicity of the applied components of the process of the present invention and its feasibility on conventional manufacturing equipment is also advantageous. The high-silica zeolite thus produced can be freed of crystalline and adsorbed water at elevated temperatures.
Prídavok tvoří zmes najmenej dvoch alifatických alkoholov Ci až C8 a najmenej jednej ďalšej kyslíkatej organickej zlúčeniny, ako aldehydov, ketónov, éterov, acetálov a esterov. Tieto tvoria jednak záměrně syntetizované a vyrábané produkty, ako např. Fischerovou-Tropschovou syntézou zo syntézneho plynu na železnatých, resp. zinočnato-železnato-chromitých alebo zinočnato-meďnatých katalyzátoroch, zvlášť aktivovaných acetylénom, pričom vznikajú alifatické alkoholy Ct až C4 a dokonca až Ci2, jednak zmesi alifatických alkoholov vznikajúce ako vedFajší produkt chemických, najma však petrochemických procesov a biochemických procesov. K najvhodnejším patří predný alkoholický podiel z rektifikácie 2-etylhexanolu (2-EHLP), obvykle frakcia o t. v. 109 až 182,5 °C/101 kPa, z oxoprocesu, s obsahom n-butanolu, izobutanolu, 2-etylhexanolu, izoamylalkoholu, 3-heptanónu i 2-etylhexanolu ako hlavných komponentov, s prímesami ďalších kyslíkatých organických látok. Potom takisto z výroby butanolov a 2-etylhexanolu oxosyntézou (z propénu a syntézneho plynu s následnou aldolizáciou n-butyraldehydu dehydratáciou, hydrogenáciou až na 2-etylhexanolu, ako aj hydrogenáciou n-butyraldehydu a izobutyraldehydu na butanol a izobutanol), resp. oxoprocesom, z organického podielu vypieracích vod, tzv. stripol, obsahujúci 70 až 85 % zmesi n-butanolu s izobutanolom, 1 až 5 % hmot, n-butyraldehydu, 5 až 25 % hmot, vody, příměsí toluénu, esterov a ďalších bližšie neidentifikovaných příměsí.The additive consists of a mixture of at least two C 1 to C 8 aliphatic alcohols and at least one other oxygenated organic compound, such as aldehydes, ketones, ethers, acetals and esters. These consist of intentionally synthesized and manufactured products, such as Fischer-Tropsch synthesis from synthesis gas on ferrous, resp. iron, zinc or chromium, zinc-copper catalysts, particularly activated acetylene to form the aliphatic alcohols, C t to C 4 Cl 2, and even up to, first, a mixture of the aliphatic alcohol produced as a product of chemical-based side, especially the petrochemical processes and biochemical processes. The most suitable is the leading alcohol fraction from the rectification of 2-ethylhexanol (2-EHLP), usually a fraction of tv 109 to 182.5 ° C / 101 kPa, from oxoprocess, containing n-butanol, isobutanol, 2-ethylhexanol, isoamyl alcohol, 3 -heptanone and 2-ethylhexanol as main components, with admixtures of other oxygenated organic substances. Then also from the production of butanols and 2-ethylhexanol by oxosynthesis (from propene and synthesis gas followed by aldolization of n-butyraldehyde by dehydration, hydrogenation up to 2-ethylhexanol, as well as hydrogenation of n-butyraldehyde and isobutyraldehyde to butanol and isobutanol), respectively. oxoprocess, from the organic part of the washing water, the so-called stripol containing 70 to 85% of a mixture of n-butanol with isobutanol, 1 to 5% by weight, n-butyraldehyde, 5 to 25% by weight, water, toluene admixtures, esters and other unidentified additives.
Potom vedFajší produkt z výroby cyklohexanolu — cyklohexanónu katalytickou oxidáciou cyklohexánu, konkrétné predný alkoholický produkt, izolovaný z rektifikácie (z kolony FK.-102) prevážne cyklohexanol — cyklohexanónovej zmesi. Hustota tohoto bezfarebného vedFajšieho produktu pri 20 °C bývá v rozsahu 840 až 865 kg. m J a v rozsahu 92 až 142 °C/ 101 kPa vydestiluje 95 %; číslo kyslosti = 0,01 až 5mgKOH/g; číslo zmydelnenia = 10 až 60 mg KOH/g; bromové číslo = 8 až 38 mg KOH/g; hydroxylové skupiny = 8 až 22 % hmot.; karbonylové skupiny = 2 až 8 % hmot.; obsahuje obvykle 48 až 58 % hmot, amylalkoholu; 8 až 10% hmot, n-butanolu; 1 až 2 % hmot. sek. butylalkoholu; 3 až 5% hmot izoamylalkoholu; 4 až 20% hmot cyklohexanónu; 2 až 10% hmot, cyklopentanolu; 0,1 až 6% hmot, cyklopentanónu a 0,5 až 3 % hmot vody. Příměsi cvklohcxanónu, cyklohcxánii a cyklohcxanolu (vona 0,1 az 2% hmot.Then the by-product of the production of cyclohexanol-cyclohexanone by catalytic oxidation of cyclohexane, in particular the leading alcohol product, isolated from the rectification (from column FK.-102) of a predominantly cyclohexanol-cyclohexanone mixture. The density of this colorless by-product at 20 DEG C. is in the range from 840 to 865 kg. m J and distills 95% in the range 92 to 142 ° C / 101 kPa; acid number = 0.01 to 5 mgKOH / g; saponification number = 10 to 60 mg KOH / g; bromine number = 8 to 38 mg KOH / g; hydroxyl groups = 8 to 22% by weight; carbonyl groups = 2 to 8% by weight; usually contains 48 to 58% by weight of amyl alcohol; 8 to 10% by weight of n-butanol; 1 to 2 wt. check. butyl alcohol; 3 to 5% by weight of isoamyl alcohol; 4 to 20% by weight of cyclohexanone; 2 to 10% by weight of cyclopentanol; 0.1 to 6% by weight of cyclopentanone and 0.5 to 3% by weight of water. Admixtures of cyclohexanone, cyclohexane and cyclohexanol (from 0.1 to 2% by weight).
Dalej surový „syntetický“ metanol, produkty 1'ischerovej Tropschovej syntézy, resp. katalyzovanej hydrokondenzácie syntézneho plynu, najma iniciovanej alkínmi a zvlášť uskutečňovaných na katalyzátorech na báze železa, zinku, médi a chrómu.Furthermore, crude "synthetic" methanol, products of the 1'ischer Tropsch synthesis, resp. catalyzed hydrocondensation of synthesis gas, in particular initiated by alkynes and carried out in particular on catalysts based on iron, zinc, copper and chromium.
Možno využiť tiež zmesi alkoholov a připadne tiež zmesi alkoholov a acetonu vyrobeného fermentačnými procesami.It is also possible to use mixtures of alcohols and, if appropriate, also mixtures of alcohols and acetone produced by fermentation processes.
Ďalšie údaje o uskutočňovaní spósobu výroby podl’a tohto vynálezu, ako aj ďalšie výhody sú zřejmé z príkladov.Further details of carrying out the production method according to the invention, as well as further advantages, are apparent from the examples.
Příklad 1Example 1
Příprava vysokokremičitých zeolitov obecného vzorca Na„AI SiM(> „O)92.~ 16 H2O (typ ZSM-5) sa uskutočňuje v ocelových poteflónovaných ampuliach o objeme 130 cm’, umiestnených v ohrevnom bloku, opatrenom reguláciou teploty a běžným príslušenstvom. Do každej ampule sa nadávkuje po 25,2 g hydrosólu kyseliny kremičitej o koncentrácii 29,75% hmot oxidu křemičitého, ku ktorému sa po kvapkách přidává vodný roztok síranu hlinitého (0,83 g síranu hlinitého v 30 cm* vody) a potom vodný roztok hydroxidu sódneho (1,50 g hydroxidu sodného v 33 cm’ vody). Ďalej sa do zmesi každej ampule přidá očkovací zárodok zeolitu ZSM-5 o module 28,1 v množstve po 0,33 g a po 4,50 g zmesi na jmenej dvoch alifatických alkoholov s přísadou najmenej jednej ďalšej kyslíkatej organickej zlúčeniny.The preparation of high-silica zeolites of the general formula Na "Al Si M (> " O ) 92. ~ 16 H 2 O (type ZSM-5) is carried out in steel poteflonated ampoules with a volume of 130 cm 3, placed in a heating block equipped with temperature control and conventional accessories. 25.2 g of silica hydrosol with a concentration of 29.75% by weight of silica are metered into each ampoule, to which an aqueous solution of aluminum sulphate (0.83 g of aluminum sulphate in 30 cm * of water) is added dropwise, followed by an aqueous solution sodium hydroxide (1.50 g of sodium hydroxide in 33 cm 3 of water). Next, a seed seed of zeolite ZSM-5 with a modulus of 28.1 is added to the mixture of each ampoule in an amount of 0.33 g and 4.50 g of a mixture of two aliphatic alcohols with the addition of at least one other oxygenated organic compound.
Připravená zmes každej ampule sa počas 20 min zhomogenizuje pri teplote miestnosti (20 °C). Reakčná zmes má v každej ampuli takéto zloženie vyjádřené v molových pomeroch oxidov: SiO2/AI2O3 = 100; Na2O/SiO2 = 0,15; II2O/SiO2 = 35,90. Hydrotermálna syntéza sa uskutočňuje pri teplote 190 ± 3 °C počas 14 h. Po ochladení sa krystalický podiel odfiltruje, prornyje destilovanou vodou a potom vysuší vo vákuovej sušiarni počas 4 h pri teplote 110 °C. Získaný produkt sa váži a analyzuje. Okrem stanovenia komponentov sa pomocou róntgenovej difrakčnej analýzy vzoriek takto vyrobeného zeolitu typu ZSM-5 stanovuje ich kryštalinita (v %). Dosiahnuté výsledky sú zhrnuté v tabul’ke 1.The prepared mixture of each ampoule is homogenized at room temperature (20 ° C) for 20 minutes. The reaction mixture in each ampoule has the following composition expressed in molar ratios of oxides: SiO 2 / Al 2 O 3 = 100; Na 2 O / SiO 2 = 0.15; II 2 O / SiO 2 = 35.90. The hydrothermal synthesis is performed at 190 ± 3 ° C for 14 h. After cooling, the crystalline fraction is filtered off, washed with distilled water and then dried in a vacuum oven at 110 DEG C. for 4 hours. The product obtained is weighed and analyzed. In addition to the determination of the components, their crystallinity (in%) is determined by means of X-ray diffraction analysis of the samples of zeolite ZSM-5 thus produced. The results obtained are summarized in Table 1.
V každom pokuse sa používá přísada inej zmesi kyslíkatých organických zlúčenín. Tak v pokuse la je to predný alkoholický vedfajší produkt z procesu oxidácie cyklohexánu na cyklohexanol a cyklohexanón, izolovaný z rektifikácie (z kolony FK-102, ďalej označovaný ako FK-102 prevážne cyklohexanol-cyklohexanóIn each experiment, the addition of a different mixture of oxygenated organic compounds is used. Thus, in Experiment 1a, it is the leading alcoholic by-product of the process of oxidation of cyclohexane to cyclohexanol and cyclohexanone, isolated from rectification (from the FK-102 column, hereinafter referred to as FK-102 predominantly cyclohexanol-cyclohexanone).
CS 267 357 B1 novej zmesi. Charakteristika a zloženie produktu FK-102 (bezfarebná kvapalina) je takéto: hustota pri 20 °C = 855 kg. m ’; 95 % vydestiluje v rozsahu teplot varu 106 až 142 °C/ -/1()1 kPa; priemerná mól. hmotnosť =CS 267 357 B1 new mixture. The characteristics and composition of FK-102 (colorless liquid) are as follows: density at 20 ° C = 855 kg. m ’; 95% distills in the boiling range 106 to 142 ° C / - / 1 () 1 kPa; average mol. weight =
109,4 g. (iiól 1 kinetická viskozita pii 20°C = 3,86.10 nď.s ’; obsah vody = = 3,6 % hmot.; OH = 14,25 % hmot.; brómové číslo = 27,8 g Br/lOOg; CHO = 4,50% hmot.; číslo kyslosti = 0,95 mg KOH/g; číslo zmydelnenia = 21,0 mg KOH/g; n-amylalkohol = = 51,9 % hmot.; izoamylalkohol = 3,7 % hmot.; n-butanol = 9,5 % hmot.; sek. butylalkohol = = 1,1 % hmot.; izobutylalkohol = 5,6% hmot.; izopropylalkohol = 0,2 % hmot.; zmes cyklohexanónu so 4-metyl-l-pentanolom = 19,7% hmot, a 9 příměsí hlavně kyslíkatých organických zlúčenín bližšie neidentifikovaných.109.4 g. (iiol 1 kinetic viscosity at 20 ° C = 3.86.10 nd.s'; water content = = 3.6 wt%; OH = 14.25 wt%; bromine number = 27.8 g Br / 100 g; CHO = 4.50% by weight, acid number = 0.95 mg KOH / g, saponification number = 21.0 mg KOH / g, n-amyl alcohol = = 51.9% by weight, isoamyl alcohol = 3.7% by weight. n-butanol = 9.5% by weight, sec-butyl alcohol = = 1.1% by weight, isobutyl alcohol = 5.6% by weight, isopropyl alcohol = 0.2% by weight, a mixture of cyclohexanone and 4-methyl-1. -pentanol = 19.7% by weight, and 9 admixtures mainly of oxygenated organic compounds not yet identified.
Ďalej v pokuse 1b je to predný alkoholický podiel z rektifikácie 2-etylhexanolu (ďalej označovaný 2-EHLP) v procese oxosyntézy (hadroformylácia propylénu na zmes n-butyraldehydu, s izobutyraldehydom, aldolizácia n-butyroialdehydu spojená s dehydratáciou aldolu Cs a jeho hydrogenáciou na 2-etylhexanol, frakcia o t. v. 109 až 182,5 °C/101 kPa; hustota pri 20 °C = 812,2 kg. m1; 0^= 1,4088; OH = 19,4% hmot.; CHO = 0,24% hmot.; CHO viazané = 0,25 % hmot.; brómové číslo = 1,3 g Br/100g; číslo kyslosti = = 1,26 mg KOH/g; číslo zmydelnenia = = 2,50 mg KOH/g; obsah vody = 0,4 % hmot.; izobutanolu = 20,3 % hmot,; n-butanolu = = 50,7 % hmot.; izoamylalkoholu = 4,1 % hmot.; 3-heptanónu = 4,1 % hmot.; 2-etylhexanolu = 2,0% hmot.; 2-etylhexanolu = 15.3% hmot, a zvyšok tvoria najmenej 3 bližšie neidentifikované kyslíkaté organické zlúčeniny.Next, in experiment 1 b is a front alcoholic the proportion of the rectification of 2-ethylhexanol (hereinafter referred to 2-EHLP) in the process of oxo synthesis (hadroformylácia propylene to a mixture of n-butyraldehyde with isobutyraldehyde, aldolisation of n-butyroialdehydu associated with dehydration of the aldol C, and the hydrogenation of the 2-ethylhexanol, fraction of mp 109-182.5 ° C / 101 kPa, density at 20 ° C = 812.2 kg, m 1 , O 2 = 1.4088, OH = 19.4% by weight, CHO = 0.24% by weight, CHO bound = 0.25% by weight, bromine number = 1.3 g Br / 100 g, acid number = 1.26 mg KOH / g, saponification number = 2.50 mg KOH / g, water content = 0.4% by weight, isobutanol = 20.3% by weight, n-butanol = = 50.7% by weight, isoamyl alcohol = 4.1% by weight, 3-heptanone = 4.1% 2-ethylhexanol = 2.0% by weight, 2-ethylhexanol = 15.3% by weight, and the remainder consists of at least 3 unidentified oxygenated organic compounds.
V pokuse 1c je to zase ťažký podiel z rektifikácie 2-etylhexanolu v oxoprocese výroby butanolov a 2-etylhexanolu, ďalej označovaný ako 2-EHTP, o hustotě pri 20 °C = 896kg.m~3, so začiatkom destilácie 184 °C a koncom pri teplote 285°C/101 kPa (vydestiluje 86 %), s obsahom 36,3 % hmot. 2-etylhexanolu, zmesi dodekanolu s diolom Cl2 = 44,1 % hmot., butyraldehyddiizobutylacetátu = 0,7 % hmot., alkoholov C6 = 0,2 % hmot., éteralkoholov C8 = 0,4 % hmot., pričom zvyšok tvoří najmenej 7 ďalších zložiek, hlavně kyslíkatých organických zlúčenín.In Experiment 1c it is again a heavy fraction from the rectification of 2-ethylhexanol in the oxoprocess of the production of butanols and 2-ethylhexanol, hereinafter referred to as 2-EHTP, with a density at 20 ° C = 896 kg.m ~ 3, with the start of distillation 184 ° C and the end at a temperature of 285 ° C / 101 kPa (distills 86%), with a content of 36.3% by weight. 2-ethylhexanol, mixtures of dodecanol with diol C 12 = 44.1% by weight, butyraldehyde diisobutyl acetate = 0.7% by weight, alcohols C 6 = 0.2% by weight, ether alcohols C 8 = 0.4% by weight, the remainder consists of at least 7 other components, mainly oxygenated organic compounds.
V pokuse Id je to zmes organických látok vystripovaná z odpadných vod z výrobně butanolov a 2-etylhexanolu oxoprocesom, tzv. stripol, obsahujúci 11,5% hmot, vody, 4,1 % hmot, n-butyraldehydu, 32,7 % izobutanolu; 45,8 % hmot, n-butanolu; 1,1 % hmot, izobutyraldehydu; 0,1 % hmot, triizobutylamínu; 4,9 % hmot toluenu a ďalšie bližšie neidentifikované zložky; číslo kyslosti = 1,33 mg KOH/g; číslo zmydelnenia = 5,1 mg KOH; OH = 17,95 % hmot.; CHO = 0,89 % hmot.In experiment Id, it is a mixture of organic substances stripped from wastewater from the production of butanols and 2-ethylhexanol by an oxoprocess, so-called stripol, containing 11.5% by weight of water, 4.1% by weight of n-butyraldehyde, 32.7% of isobutanol; 45.8% by weight of n-butanol; 1.1% by weight, isobutyraldehyde; 0.1% by weight, triisobutylamine; 4.9% by weight of toluene and other components not further specified; acid number = 1.33 mg KOH / g; saponification number = 5.1 mg KOH; OH = 17.95% by weight; CHO = 0.89 wt.
CS 267 357 Bl 5 6 .CS 267 357 Bl 5 6 .
Tabulka 1Table 1
Příklad 2Example 2
Postupuje sa podobné ako v příklade 1, len ako zmes kyslíkatých organických zlúčenín sa aplikuje neutrálny podiel z produktu hydrokondenzácie oxidu uhol’natého vodíkom převážné na železnatých a zinočno-meďnato-chromitých katalyzátoroch.The procedure is the same as in Example 1, except that a neutral portion of the product of the hydrogen condensation of carbon monoxide with hydrogen, predominantly on ferrous and zinc-copper-chromium catalysts, is applied as a mixture of oxygenated organic compounds.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS879514A CS267357B1 (en) | 1987-12-21 | 1987-12-21 | Method of high-siliceous zeolite production |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS879514A CS267357B1 (en) | 1987-12-21 | 1987-12-21 | Method of high-siliceous zeolite production |
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| Publication Number | Publication Date |
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| CS951487A1 CS951487A1 (en) | 1989-07-12 |
| CS267357B1 true CS267357B1 (en) | 1990-02-12 |
Family
ID=5445132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS879514A CS267357B1 (en) | 1987-12-21 | 1987-12-21 | Method of high-siliceous zeolite production |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS267357B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ302373B6 (en) * | 1997-10-03 | 2011-04-20 | ENICHEM S. p. A. | Process for preparing zeolitic catalysts |
| CZ306416B6 (en) * | 2015-09-03 | 2017-01-11 | Unipetrol Výzkumně Vzdělávací Centrum, A. S. | A method of producing hollow spherical particles of zeolite ZSM-5 |
| CZ306852B6 (en) * | 2016-03-15 | 2017-08-09 | Unipetrol výzkumně vzdělávací centrum, a.s. | A method of production of the ZSM-5 zeolite with a high proportion of pairs of aluminium atoms |
-
1987
- 1987-12-21 CS CS879514A patent/CS267357B1/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ302373B6 (en) * | 1997-10-03 | 2011-04-20 | ENICHEM S. p. A. | Process for preparing zeolitic catalysts |
| CZ306416B6 (en) * | 2015-09-03 | 2017-01-11 | Unipetrol Výzkumně Vzdělávací Centrum, A. S. | A method of producing hollow spherical particles of zeolite ZSM-5 |
| CZ306852B6 (en) * | 2016-03-15 | 2017-08-09 | Unipetrol výzkumně vzdělávací centrum, a.s. | A method of production of the ZSM-5 zeolite with a high proportion of pairs of aluminium atoms |
Also Published As
| Publication number | Publication date |
|---|---|
| CS951487A1 (en) | 1989-07-12 |
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