NO753623L - - Google Patents
Info
- Publication number
- NO753623L NO753623L NO753623A NO753623A NO753623L NO 753623 L NO753623 L NO 753623L NO 753623 A NO753623 A NO 753623A NO 753623 A NO753623 A NO 753623A NO 753623 L NO753623 L NO 753623L
- Authority
- NO
- Norway
- Prior art keywords
- zeolite
- zeta
- compound
- quaternary
- zeolite zeta
- Prior art date
Links
- 239000010457 zeolite Substances 0.000 claims description 33
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 30
- 229910021536 Zeolite Inorganic materials 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- -1 aluminum compound Chemical class 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 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 description 6
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- 150000003377 silicon compounds Chemical class 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 230000001089 mineralizing effect Effects 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002441 X-ray diffraction Methods 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 125000005270 trialkylamine group Chemical group 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 claims 2
- 239000010970 precious metal Substances 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical group 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 claims 1
- TXPMUPUOSOZCCS-UHFFFAOYSA-N hexadecyl(trimethyl)phosphanium Chemical compound CCCCCCCCCCCCCCCC[P+](C)(C)C TXPMUPUOSOZCCS-UHFFFAOYSA-N 0.000 claims 1
- XOGCTUKDUDAZKA-UHFFFAOYSA-N tetrapropylphosphanium Chemical compound CCC[P+](CCC)(CCC)CCC XOGCTUKDUDAZKA-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- PWOXNBGGNATVJE-UHFFFAOYSA-N 1-bromo-16,16-dimethylheptadecane Chemical group CC(CCCCCCCCCCCCCCCBr)(C)C PWOXNBGGNATVJE-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 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
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 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
-
- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Den foreliggende oppfinnelse angår en ny fremgangsmåte til fremstilling av syntetiske krystallinske zeolitter, særlig en ny zeolitt som i det foreliggende betegnes Zeta 3. Krystallinske zeolitter som i almindelighet kalles molekylsikter, er velkjente og erkarakterisert veden meget høy-gradig krystallinsk struktur med et skjelett av SiO^- og Al04~tetraedre som, er forbundet ved at de deler O-atomer^ slik at forholdet O/Al + Si er 2. Skjelettets negative ladning balanseres av kationer, vanligvis The present invention relates to a new process for the production of synthetic crystalline zeolites, in particular a new zeolite which is herein designated Zeta 3. Crystalline zeolites, which are generally called molecular sieves, are well known and are characterized by a very high-grade crystalline structure with a skeleton of SiO ^- and AlO4~ tetrahedra which are connected by sharing O atoms^ so that the ratio O/Al + Si is 2. The skeleton's negative charge is balanced by cations, usually
Na eller K. - -:;, Na or K. - -:;,
Oppfinnelsen angår også en ny zeolitt, Zeta 3, som i likhet med zeolitt Zeta 1 er i slekt med zeolitt ZSM5 (se britisk patent-søknad 46970/74 og britisk patent nr. 1.161.974). The invention also relates to a new zeolite, Zeta 3, which, like zeolite Zeta 1, is related to zeolite ZSM5 (see British patent application 46970/74 and British patent no. 1,161,974).
Det ble nå funnet at dette nye medlem av ZSM5-familien av zeolitter kan syntetiseres ved bruk av mineraliserende midler It has now been found that this new member of the ZSM5 family of zeolites can be synthesized using mineralizing agents
sammen med kvaternære nitrogen- eller fosfor-forbindeIser og meget små mengder natriumhydroksyd. Zeolitt Zeta 3 kan skillés fra zeolitt Zeta 1 ved pulver-røntgen-uridersøkelser og ved forskjeller together with quaternary nitrogen or phosphorus compounds and very small amounts of sodium hydroxide. Zeolite Zeta 3 can be distinguished from Zeolite Zeta 1 by powder X-ray uride examinations and by differences
i sorpsjonsegenskaper. Typiske pulver-røntgendata erholdt ved anvendelse av kobber-Ka-strållng.er gitt i tabell 1» disse data gjelder produktet ifølge eksempel 1 nedenfor, hvilket hadde følgende sammensetning etter tørring ved 120°C» in sorption properties. Typical powder X-ray data obtained using copper Ka radiation are given in table 1" these data apply to the product according to example 1 below, which had the following composition after drying at 120°C"
0,6Q20.0,25 Na2O.Al203.60 Si02;12 H20, hvor Q tetrapropylammonium. 0.6Q20.0.25 Na2O.Al203.60 Si02;12 H20, where Q is tetrapropylammonium.
(Prøve A). (Try to).
Dette, produkt ble kalsinert i luft ved 550°C i 24 timer og deretter utvekslet med 10% NH4Cl-løsning ved 25°C i 1 time ( to ganger den mengde som teoretisk er påkrevet for å erstatte alle Na-ioner). Denne utveksling ble gjentatt fire ganger ialt, og produktet ble vasket og tørret og hadde den følgende sammensetning: This product was calcined in air at 550°C for 24 hours and then exchanged with 10% NH4Cl solution at 25°C for 1 hour (twice the amount theoretically required to replace all Na ions). This exchange was repeated four times in total, and the product was washed and dried and had the following composition:
0,01 Na2O.Al203.65 Si02.12 HjO og en krystallitt-størrelse på 0.01 Na2O.Al203.65 Si02.12 HjO and a crystallite size of
ca. 4 »m. (Prøve B). about. 4 » m. (Sample B).
I tabell 2 er typiske sorpsjonsdata gitt for Prøver A og B. Prøve A ble aktivert i vakuum ved kalsinering ved 320°C i 2 timer (bare en ubetydelig mengde av tetrapropylammoniumet ble fjernet ved denne aktiveringsteknikk). Prøve B ble også aktivert i vakuum ved 320°C i 2 timer. Prøve C ble fremstilt ved fullstendig utveksling av Prøve B med 10% NaCl og hadde den følgende sammensetning etter tørring ved 120°Cx In Table 2, typical sorption data are given for Samples A and B. Sample A was activated in vacuo by calcination at 320°C for 2 hours (only a negligible amount of the tetrapropylammonium was removed by this activation technique). Sample B was also activated in vacuum at 320°C for 2 hours. Sample C was prepared by complete exchange of Sample B with 10% NaCl and had the following composition after drying at 120°Cx
0,9 Na2O.Al203.63Si02.ll,5 HgO 0.9 Na2O.Al2O3.63Si02.11.5 HgO
Disse data antyder at zeolitt Zeta 3 med lavt natrium-innhold har åpninger som meget nær har samme størrelse som m-xylen, dvs. litt større enn 6,2Å, mens Zeta 1 har åpninger på omtrent 6,0Å. Med bare 25% av sine kationer tilstede som These data suggest that zeolite Zeta 3 with a low sodium content has openings that are very close to the size of m-xylene, i.e. slightly larger than 6.2Å, while Zeta 1 has openings of approximately 6.0Å. With only 25% of its cations present as
natrium er zeolitt Zeta 3 et marginalt cykloheksan-absorpsjons-middel, hvilket antyder at natriumioner har en tendens til å tilstoppe åpningene ved denne størrelse ned til, nær eller mindre enn 6,0Å. Disse data antyder at åpningene i zeolitt Zeta 3 er meget ømfintlige overfor innholdet av enverdige kationer og kan varieres mellom ca. 5,9Å og 6,2Å ved at kationinnholdet varieres. sodium, zeolite Zeta 3 is a marginal cyclohexane absorbent, suggesting that sodium ions tend to plug the openings at this size down to, near, or less than 6.0Å. These data suggest that the openings in zeolite Zeta 3 are very sensitive to the content of monovalent cations and can be varied between approx. 5.9Å and 6.2Å by varying the cation content.
Zeolitt Zeta 3 har eksepsjonelle egenskaper for Zeolite Zeta 3 has exceptional properties for
separasjon av aromatiske stoffer og cykloparaffiner og er i almindelighet anvendbar for separasjon, på basis av statisk størrelse, av molekyler med kinetisk diameter mindre enn ca. 6,0Å fra molekyler med diameter større enn 6,0Å. separation of aromatic substances and cycloparaffins and is generally applicable for the separation, on the basis of static size, of molecules with a kinetic diameter smaller than approx. 6.0Å from molecules with diameter greater than 6.0Å.
o Det er karakteristisk for zeolitt Zeta 3 at den, som et medlem av ZSM5-familien har bemerkelsesverdige egenskaper ved dehydratisering av alkoholer og ved dannelse av olefiner og aromater fra alifatiske forbindelser, og ved isomerisering av xylen. o It is characteristic of zeolite Zeta 3 that, as a member of the ZSM5 family, it has remarkable properties in the dehydration of alcohols and in the formation of olefins and aromatics from aliphatic compounds, and in the isomerization of xylene.
Eksempel 1 Example 1
Det følgende eksempel illustrerer fremstillingen av zeolitt Zeta 3. - 1,83 g fast aluminat (1,25 Na20.Al203) og 1,32 g! natriumhydroksyd-pellets ble oppløst i 330 ml vann, fulgt av 23,6 g tetrapropylammoniumklorid. Deretter ble 50 g fast silika (Hoechst'8"KS300") dispergert i blandingen i 15 minutter, hvoretter 91 g natriumklorid ble innrørt. Blandingen fikk reagere ved 95°C i 8 dager under moderat omrøring (50 onidr. pr. min.) Produktet ble filtrert og vasket med 2 liter varmt vann og tørret ved 120°C. Det hadde følgende sammensetning: 0,6Q20.0,25 Na2O.Al203.60 Si02.12 Hj<O,>The following example illustrates the preparation of zeolite Zeta 3. - 1.83 g of solid aluminate (1.25 Na20.Al203) and 1.32 g! sodium hydroxide pellets were dissolved in 330 ml of water, followed by 23.6 g of tetrapropylammonium chloride. Then 50 g of solid silica (Hoechst'8"KS300") was dispersed in the mixture for 15 minutes, after which 91 g of sodium chloride was stirred in. The mixture was allowed to react at 95°C for 8 days with moderate stirring (50 onidr. per min.) The product was filtered and washed with 2 liters of hot water and dried at 120°C. It had the following composition: 0.6Q20.0.25 Na2O.Al203.60 Si02.12 Hj<O,>
hvor Q «* tetrapropylammonium (Prøve A). Dette produkt ble ;kalsinert i luft ved 550°C i 24 timer og deretter utvekslet med 10% NH4C1-løsning ved 25°C i 1 time (to ganger den mengde som teoretisk er påkrevet for å erstatte alle Na-ioner). Denne utveksling ble gjentatt fire ganger ialt,"og produktet blev vasket og tørret og hadde den følgende sammensetnings . 0,01 Na2b.Al203.65 SiQ2.12 H20 og en krystallittstørrelse på ;ca. 4 ym (Prøve B). ;Dén foreliggende oppfinnelse tilveiebringer en ny zeolitt, Zeta 3, som har sammensetningen!0,2 - 1, 3 R20.A1203. (25 - 100) Si02. (20 -v 48) H20, hvor R er Na eller Ba i en mengde som ikke overstiger 0,7 mol, ;H, eller^et kvaternært nitrogen- eller f os f or radikal, eller hvilken som helst .kombinasjon deray, og som har et røntgen-diffraksjonsmønster hovedsakelig som vist i tabell 1. ;Oppfinnelsen tilveiebringer videre en fremgangsmåte til fremstilling av zeolitt Zeta 3,karakterisert vedat man omsetter minst én silisiumforbindelse, minst én aluminiumforbindelse, minst én forbindelse inneholdende kvaternært nitrogen eller kvaternært fosfor, og et mineraliseringsmiddel omfattende natriumsulfat ;eller kloridet, bromideteller iodidet av natrium eller barium. Sllisiumforbindelsen kan eksempelvis være et reaktivt ;fast silika eller en silikaløsning eller et vannglass eller hvilken som helst kombinasjon derav. ;Aluminiumforbindelsen kan eksempelvis være natriumaluminat eller et aluminiumsalt, f.eks. aluminiumsulfat. ;De foretrukne kvatemære forbindelser er tetraalkyl- og tetraalkylaryl-ammonium- og fosfonium-forbindelser, hvbr minst ;tre av gruppene er alkyl og ikke mér enn tre av gruppene er metyl, ;f.eks. tetrapropylammoniumklorid eller -hydroksyd. Kationiske ;nedbygningsprodukter av de kvatemære forbindelser kan også brukes, samt blandinger av forbindelser som gir de kvatemære forbindelser in situ under reaksjonen, f.eks. blandinger av trialkylaminer og alkoholer eller alkylhalogenider. ;Zeolitt Zeta 3 fremstilles av reaksjonsblahdinger med ;de følgende sammensetninger:Si02/Ai203•'- 25 til 100;Na20/Al2<03><=>ul < 6 ;H20/Na20 + 2QY1Øh = 25 til 500V H20/Na20 » 300 til 5000 ;OHVsiOj « * 0,07 where Q «* tetrapropylammonium (Sample A). This product was calcined in air at 550°C for 24 hours and then exchanged with 10% NH 4 Cl solution at 25°C for 1 hour (twice the amount theoretically required to replace all Na ions). This exchange was repeated four times in total, and the product was washed and dried and had the following composition: 0.01 Na 2 b . invention provides a new zeolite, Zeta 3, which has the composition!0.2 - 1.3 R20.Al203.(25 - 100) SiO2.(20 -v 48)H20, where R is Na or Ba in an amount not exceeds 0.7 mol, ;H, or^a quaternary nitrogen or f os f or radical, or any .combination deray, and having an X-ray diffraction pattern substantially as shown in Table 1. ;The invention further provides a method for the production of zeolite Zeta 3, characterized by reacting at least one silicon compound, at least one aluminum compound, at least one compound containing quaternary nitrogen or quaternary phosphorus, and a mineralizing agent comprising sodium sulfate; or the chloride, bromide or iodide of sodium or barium. The silicon compound can be for example being a reactive solid silica or a silica solution or a glass of water or any combination thereof. The aluminum compound can, for example, be sodium aluminate or an aluminum salt, e.g. aluminum sulfate. The preferred quaternary compounds are tetraalkyl and tetraalkylaryl ammonium and phosphonium compounds, where at least three of the groups are alkyl and no more than three of the groups are methyl, e.g. tetrapropylammonium chloride or hydroxide. Cationic degradation products of the quaternary compounds can also be used, as well as mixtures of compounds which give the quaternary compounds in situ during the reaction, e.g. mixtures of trialkylamines and alcohols or alkyl halides. ;Zeolite Zeta 3 is produced from reaction sheets with ;the following compositions:Si02/Al203•'- 25 to 100;Na20/Al2<03><=>ul < 6;H20/Na20 + 2QY1Øh = 25 to 500V H20/Na20 » 300 to 5000 ;OHVsiOj « * 0.07
M<1>/aX/Al203«12 til 300 M<1>/aX/Al2O3«12 to 300
QbY/S1026,01 til 20 QbY/S1026,01 to 20
hvor M er natrium eller barium med valensen å (dvs. henholdsvis 1 eller 2), X er sulfat, klorid, bromid eller jodld, Q er den ovenfor nevnte kvatemære eller fos for forbindelse, og Y er 0H, halogen eller et syreradikal med valensen b. where M is sodium or barium with a valence of 0 (i.e., 1 or 2, respectively), X is sulfate, chloride, bromide, or iodide, Q is the aforementioned quaternary or phos for compound, and Y is OH, halogen, or an acid radical of the valence b.
Eksempel 2 Example 2
0,5 kg fast silika ble suspendert i 2,16 kg av en 10% vandig løsning av tetrapropylammohiumhydroksyd. Deretter ble 18,3 g 0.5 kg of solid silica was suspended in 2.16 kg of a 10% aqueous solution of tetrapropylammonium hydroxide. Subsequently, 18.3 g
fast natriumaluminat og 12,2 g natriumhydroksyd oppløst i 1,26 liter vann. Denne natriumaluminat-væske ble dispergert i silikasuspensjonen (10 min.), og deretter ble 0,9 kg fast natriumklorid innrørt (10 min.). Blandingen ble så omsatt i en "Pyrex"-beholder under kraftig omrøring i 8 dager ved 95°C under tilbakeløp. solid sodium aluminate and 12.2 g of sodium hydroxide dissolved in 1.26 liters of water. This sodium aluminate liquid was dispersed in the silica suspension (10 min.), and then 0.9 kg of solid sodium chloride was stirred in (10 min.). The mixture was then reacted in a "Pyrex" container under vigorous stirring for 8 days at 95°C under reflux.
Produktet ble vasket med 10 liter varmt vann og filtrert og deretter tørret ved 700°C. The product was washed with 10 liters of hot water and filtered and then dried at 700°C.
Produktet hadde én midlere krystallittstørrelse på The product had one average crystallite size
0,005 ym og den følgende sammensetning: 0.005 ym and the following composition:
0,1 Na20.0,8 Q2Q.A1203.68 Si02.24 H20, hvor Q tetrapropylammonium. 0.1 Na2O.0.8 Q2Q.A1203.68 Si02.24 H20, where Q tetrapropylammonium.
Eksempel 3 Example 3
1 kg silika (KS300) ble suspendert i 10 liter vann. Deretter ble 36,6 g natriumaluminat og 26,4 g natriumhydroksyd oppløst i 4,6 liter vann fulgt av 472 g trimetylcetylammonium-bromld. Denne løsning ble rørt inn i silikasuspensjonen (10 min.), og deretter ble 2,4 kg vannfritt natriumsulfat rørt inn (10 min.). Blandingen fikk så reagere under moderat omrøring (50 omdr./min.) i en "Pyrex"-foret beholder i 20 dager ved 95°C. Produktet ble vasket med 20 liter varmt vann.og filtrert og tørret ved 120°C. Den midlere krystallittstørrelse var 0,3 ym, og sammensetningen var som følger: 0,25 Na20.0,8 Q2O.Al203.74 Si<0>2.20 H20, hvor Q ■ trimetylcetylammonium. 1 kg of silica (KS300) was suspended in 10 liters of water. Then 36.6 g sodium aluminate and 26.4 g sodium hydroxide dissolved in 4.6 liters of water followed by 472 g of trimethylcetylammonium bromide. This solution was stirred into the silica suspension (10 min.), and then 2.4 kg of anhydrous sodium sulfate was stirred in (10 min.). The mixture was then allowed to react under moderate agitation (50 rpm) in a "Pyrex" lined container for 20 days at 95°C. The product was washed with 20 liters of hot water and filtered and dried at 120°C. The average crystallite size was 0.3 µm, and the composition was as follows: 0.25 Na 2 O.0.8 Q 2 O.Al 2 O 3 .74 Si<0>2.20 H 2 O, where Q ■ trimethylcetylammonium.
Eksempel 4 Example 4
Eksempel 2 ble gjentatt i en 10 liters "Pyrex<n->foret autoklav» reaksjonen var rolig i 24,timer ved 180°C. Produktet hadde en krystallittstørrelse på 1 ym og sammensetningen: 0,3 Na20.0,6 Q20.A1203.59 Si02.20 H20, hvor Q « trimetylcetylammonium. Example 2 was repeated in a 10 liter "Pyrex<n-> lined autoclave" the reaction was calm for 24 hours at 180°C. The product had a crystallite size of 1 ym and the composition: 0.3 Na2O.0.6 Q20.A1203 .59 Si02.20 H20, where Q « trimethylcetylammonium.
Eksempel 5 Example 5
Eksempel 3 ble gjentatt, men trimetylcetylbromidet ble erstattet med 287 g tetrapropylammoniumklorid, og natrium-sulfatet ble erstattet med 2.kg natriumklorid. Produktets midlere krystallittstørrelse var 0,3 ym, og sammensetningen var som følgert Example 3 was repeated, but the trimethyl cetyl bromide was replaced with 287 g of tetrapropylammonium chloride, and the sodium sulfate was replaced with 2 kg of sodium chloride. The average crystallite size of the product was 0.3 µm, and the composition was as follows
0,2Na20.0,65 Q2O.Al203.64,5 Si02.24 HjO, hvor Q » tetrapropylammonium. 0.2Na20.0.65 Q2O.Al203.64.5 Si02.24 HjO, where Q » tetrapropylammonium.
Eksempel 6 Example 6
Produktet i eksempel 5 ble kalsinert i 17 timer ved 550°C i luft og deretter utvekslet med ammoniumklorid som i eksempel 1. The product in example 5 was calcined for 17 hours at 550°C in air and then exchanged with ammonium chloride as in example 1.
Produktet inneholdt mindre enn 0,01 vekt% Na20. Etter aktivering ved brenning ved 550°C i 17 timer i luft viste produktet seg å være en eksepsjonell katalysator for væskefaseisomerisering av blandede xylener, samtidig som det viste meget lav nedbrytnings-hastighet og ga praktisk talt fullstendig omdannelse av etylbenzen til dietylbenzen (hvilket gjør en påfølgende separasjon fra The product contained less than 0.01% by weight of Na 2 O. After activation by firing at 550°C for 17 hours in air, the product proved to be an exceptional catalyst for the liquid phase isomerization of mixed xylenes, while exhibiting a very low degradation rate and giving virtually complete conversion of ethylbenzene to diethylbenzene (which makes a subsequent separation from
xylener meget enkel), samt meget lave xylen-tap. Ytterligere detaljer vedrørende dette materialets katalytiske aktivitet er gitt i britisk patentsøknad rir. 17699/75., xylenes very simple), as well as very low xylene losses. Further details regarding the catalytic activity of this material are given in British patent application no. 17699/75.,
I almindelighet kan kationet eller kationene i zeolitt Zeta 3 erstattes med hvilke eller hvilket som helst kation av metaller i gruppe IA, IB, III (innbefattende sjeldne jordarter), gruppe VIIA (innbefattende mangan), gruppe VIII (innbefattende edelmetaller) og med bly og vismut.Utvekslingen utføres fortrinnsvis ved enkel kontakt i vandig løsning. Syre- eller hydrogen-formen kan erholdes ved at alkaliformen omsettes med en lang rekke sure forbindelser (nemlig hvilken som helst kilde for hydrogenioner), eller ved at man først fremstiller en ammonium-eller alkyl- eller arylammonium-zeolitt ved loneveksling fulgt av spaltning, fortrinnsvis i luft, ved oppvarming, hvorved hydrogen-zeolitten av Zeta 3 dannes. Om det ønskes kan katalysatorer fremstilt ut fra zeolitt Zeta 3 inkorporeres i en uorganisk grunn-masse, sammen med andre materialer som enten kan være inerte eller katalytisk aktive. Grunnmassen kan ganske enkelt være tilstede som et bindemiddel som holder de små zeolittpartikler sammen, eller den kan tilsettes som et fortynningsmiddel til å regulere mengden eller graden av omdannelse i en prosess som, ved anvendelse av zeolitter basert på Zeta 3, ellers kan gå altfor fort, hvilket fører til passivering ay katalysatoren på grunn av for sterk koksdannelse. Typiske uorganiske fortynningsmidler innbefatter kaolinleirer, bentonitter, montmorillonitter, sepiolitt, attapulgitt, Fuller-jord, syntetiske porøse materialer så som Si02-Al203, Si02-Sr<0>2, Si02-Th02, Si02-BeO, Si02~Ti02, eller In general, the cation or cations in zeolite Zeta 3 can be replaced by any or any cation of metals in group IA, IB, III (including rare earths), group VIIA (including manganese), group VIII (including noble metals) and with lead and bismuth. The exchange is preferably carried out by simple contact in aqueous solution. The acid or hydrogen form can be obtained by reacting the alkali form with a wide range of acidic compounds (namely any source of hydrogen ions), or by first preparing an ammonium or alkyl or arylammonium zeolite by ion exchange followed by cleavage, preferably in air, upon heating, whereby the hydrogen zeolite of Zeta 3 is formed. If desired, catalysts produced from zeolite Zeta 3 can be incorporated into an inorganic base mass, together with other materials that can be either inert or catalytically active. The matrix may simply be present as a binder to hold the small zeolite particles together, or it may be added as a diluent to control the amount or degree of conversion in a process which, using Zeta 3 based zeolites, may otherwise proceed too quickly , which leads to passivation of the catalyst due to excessive coke formation. Typical inorganic diluents include kaolin clays, bentonites, montmorillonites, sepiolite, attapulgite, Fuller's earth, synthetic porous materials such as SiO2-Al2O3, SiO2-Sr<0>2, SiO2-Th02, SiO2-BeO, SiO2~Ti02, or
kombinasjoner av disse oksyder. En effektiv måte til å blande zeolitt Zeta 3 med slike fortynningsmidler er å blande passende vandige oppslemninger i en blahdedyse og deretter forstøvnlngs-tørre oppslemningen. Andre blandemetoder kan anvendes. combinations of these oxides. An efficient way to mix Zeolite Zeta 3 with such diluents is to mix suitable aqueous slurries in a blower nozzle and then spray-dry the slurry. Other mixing methods can be used.
Jordalkali-former, sjeldne-jordarter-former og sure former av zeolitt Zeta 3 kan videre utveksles eller impregneres med hydrogenerings/dehydrogenerings-komponenter,, så som Ni, Co, Pt, Alkaline earth forms, rare earth forms and acidic forms of zeolite Zeta 3 can further be exchanged or impregnated with hydrogenation/dehydrogenation components, such as Ni, Co, Pt,
Pd, Re, Rh. Gode hydrokrakking- og omformingskatalysatorer kan fremstilles på denne måte ut fra zeolitt Zeta 3 forutsatt at dennes K20- og/eller Na20-innhold reduseres til mindre enn 3 vekt%. Pd, Re, Rh. Good hydrocracking and reforming catalysts can be prepared in this way from zeolite Zeta 3, provided that its K20 and/or Na20 content is reduced to less than 3% by weight.
Claims (19)
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BE (1) | BE834959A (en) |
DE (1) | DE2548695A1 (en) |
DK (1) | DK489375A (en) |
FR (1) | FR2289445A1 (en) |
NL (1) | NL7512645A (en) |
NO (1) | NO753623L (en) |
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EP0018089B1 (en) * | 1979-03-21 | 1982-10-27 | Mobil Oil Corporation | Method for preparing zeolite zsm12 and zeolite prepared by this method |
NZ195358A (en) * | 1979-11-05 | 1983-05-31 | Mobil Oil Corp | Preparation of zeolites trialkylmethylammonium ion present in reaction mixture |
EP0030444B1 (en) * | 1979-12-03 | 1985-01-30 | Kitasato Kenkyusho | A process for preparing substances having interferon inducing activity |
IT1140784B (en) * | 1980-03-13 | 1986-10-10 | Anic Spa | METHOD FOR THE PRODUCTION OF ZEOLITHIC STRUCTURE ALUMINUM SILICATES |
CA1157450A (en) * | 1980-03-18 | 1983-11-22 | Martin F.M. Post | Process for the preparation of crystalline aluminium silicates, crystalline aluminium silicates so prepared and process for the production of an aromatic hydrocarbon mixture |
DE3165950D1 (en) * | 1980-05-13 | 1984-10-18 | Ici Plc | ZEOLITE NU-3 |
EP0051318B2 (en) * | 1980-11-04 | 1990-03-21 | Teijin Petrochemical Industries Ltd. | A catalyst composition containing as catalytically active components alumina and a cristalline aluminosilicate zeolite, a process for isomerizing xylenes and ethylbenzene, and use of this catalyst composition |
JPS58204817A (en) * | 1982-05-19 | 1983-11-29 | Teijin Yuka Kk | Production of crystalline aluminosilicate zeolite |
US4554146A (en) * | 1983-11-10 | 1985-11-19 | Exxon Research And Engineering Co. | Process for preparing a zeolite of the L type using organic templates |
US5013536A (en) * | 1988-08-22 | 1991-05-07 | Exxon Research And Engineering Company | ECR-18, method of its preparation, and uses for sorption and separation |
KR101369345B1 (en) | 2011-12-22 | 2014-03-06 | 인하대학교 산학협력단 | Method for selective dealkylation of alkyl-substituted C9+ aromatic compound at low temperature using bimodal porous catalyst for dealkylation |
CN114538461B (en) * | 2020-11-26 | 2023-08-08 | 中国科学院大连化学物理研究所 | SSZ-13 silicon-aluminum molecular sieve and preparation method and application thereof |
CN113428870B (en) * | 2021-06-24 | 2022-05-31 | 华中科技大学 | Polymer bentonite composite impermeable material and pyrogen-free synthesis method thereof |
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- 1975-10-28 BE BE161329A patent/BE834959A/en unknown
- 1975-10-29 FR FR7533035A patent/FR2289445A1/en not_active Withdrawn
- 1975-10-29 NL NL7512645A patent/NL7512645A/en unknown
- 1975-10-29 SE SE7512089A patent/SE7512089L/en not_active Application Discontinuation
- 1975-10-30 DK DK489375A patent/DK489375A/en unknown
- 1975-10-30 DE DE19752548695 patent/DE2548695A1/en active Pending
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ZA756745B (en) | 1976-10-27 |
DK489375A (en) | 1976-05-01 |
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