DK157361B - Fremgangsmaade til fremstilling af titanmodificeret poroest, krystallinsk siliciumoxid og anvendelse af dette. - Google Patents

Fremgangsmaade til fremstilling af titanmodificeret poroest, krystallinsk siliciumoxid og anvendelse af dette. Download PDF

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DK157361B
DK157361B DK493980AA DK493980A DK157361B DK 157361 B DK157361 B DK 157361B DK 493980A A DK493980A A DK 493980AA DK 493980 A DK493980 A DK 493980A DK 157361 B DK157361 B DK 157361B
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titanium
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silica
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Marco Taramasso
Giovanni Perego
Bruno Notari
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Snam Progetti
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
    • 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
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/12—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the replacing atoms being at least boron atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S423/00—Chemistry of inorganic compounds
    • Y10S423/22—MFI, e.g. ZSM-5. silicalite, LZ-241

Description

DK 157361 B
Den foreliggende opfindelse angâr en fremgangsmâ-de til fremstilling af por0st, krystallinsk silicium-oxid, hvori silicium-gitterpladser er besat med titan, og som har den almene formel 5 x TiC^ · (1-x)S1O2 hvori x ligger mellem 0,0005 og 0,04, fortrinsvis mellem 0,01 og 0,025, ved hvilken der foretages hydrotermisk omsætning af kolloid silica eller tetraalkylorthosili-cat, tetraalkoxytitan eller tetrapropylammoniumperoxy-10 titanat, tetrapropylammoniumhydroxid og vand ved en temperatur pâ fra 130 til 200°C under autogent tryk i et tidsrum pâ fra 6 til 30 dage, og de opnâede krystaller derpâ adskilles fra moderoplasningen, vaskes med vand og terres og til sidst opvarmes i 1 til 72 timer i luft til 550°C.
15 I den efterfolgende beskrivelse vil det omhandle- de titanmodificerede siliciumoxid blive betegnet som titansilicalit, eller kortere TS-1. I USA-patentskrift nr. 3.329.481 er der beskrevet titanholdige zeolitter, som er fremstillet ud fra kiselholdige materialer og uor-20 ganiske titanforbindelser i fraværelse af organiske baser. "Silicalit", en zeolitstruktur bestâende af rent krystallinsk SiC^, er blevet beskrevet i Flanigen, E.M. et al. (Nature 271, 512 (1978)).
I beskrivelsen til dansk patentansagning nr.
25 2403/79 er der beskrevet fremstillingen af modificeret krystallinsk siliciumdioxid med stor specifik overflade og med den almene formel (0,0001-1)M 0 . Si0o n m 2 hvori de modificerende metaller (M) er chrom, béryllium, 30 titan, vanadium, mangan, jern, cobalt, zink, zirconium, rhodium, salv, tin og/eller antimon. Til denne fremstilling underkaster man i vandig, alkoholisk eller vandig-alkoholisk opl0sning silicageler og/eller tetraalkyl-orthosilicater og oxider, hydroxider, alkoxyderivater 35 og/eller salte af de modificerende metaller med 0,05 til 0,5 mol tertiære aminer, aminoalkoholer, aminosyrer, polyvalente alkoholer og/eller kvaternære ammoniumbaser pr. mol silica og en mineralisator i form af alkalime- 2
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tal- og/eller jordalkalimetalhydroxider og/eller -halo-genider krystallisation i fra nogle fâ timer til flere dage ved 100 til 220°C, frafiltrerer krystalmassen og opvarmer krystallisatet efter torring til 300 til 5 700°C i 2 til 24 timer.
If0lge eksempel 6 i ovennævnte patentans0gnïng indeholder den por0se krystallinske silica foruden 29,5 vægt% TiC>2 og 66,5 vægt% S1O2 endvidere 0,02 vægt% î^O. Molforholdet SiC^iTiC^ er 3.
10 Inden for dette særdeles brede omrâde med hensyn til modificeret silica har det overraskende vist sig, at bestemte titanmodificerede sâkaldte "titansilicalitter er særlig katalytisk virksomme ved bestemte reaktioner.
Formâlet med opfindelsen er at tilvejebringe en 15 fremgangsmâde til fremstilling af disse specielle titansilicalitter.
Dette formâl opnâs med fremgangsmâden ifolge opfindelsen, der er ejendommelig ved, at man i reaktions-blandingen overholder folgende molforhold: 20 Si02/TiC>2 fra 5 til 200, fortrinsvis fra 35 til 65, OH /S1O2 fra 0,1 til 1,0, fortrinsvis fra 0,03 til 0,6, H20/Si02 fra 20 til 200, fortrinsvis fra 60 til 100, RN+/SiO~ fra 0,1 til 2,0, fortrinsvis fra 0,4 til 1,0, hvor RN er kationen af tetrapropylammoniumhydroxid.
25 Da titanatomerne sidder pâ silicium-gitterplad- ser i titansilicalittet eller det titanmodificerede siliciumoxid ifolge opfindelsen, har dette helt speci-fikke rontgenstrâlediffraktions- og IR-spektre.
R0ntgenstrâleunders0gelsen udf0rtes ved hjælp af 30 et pulverdiffraktometer forsynet med et elektronisk im-pulstæ-llingssystem, under anvendelse af CuKa strâling. Produkterne if0lge den foreliggende opfindelse er karak-teriseret ved et r0ntgenstrâlediffraktionsspektrum som vist i fig. lb pâ tegningen. Dette spektrum ligner som 35 helhed det typiske silicalitspektrum (fig. la), men det omfatter visse tydelige "enkelf'-refleksioner, hvor der er tydelige dobbeltrefleksioner til stede i det rene silicalitspektrum. Da de spektrale forskelle mellem TS-1 3
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og silicalit er forholdsvis smâ, kræves der særlig oxnhu ved spektralbestexnmelsen. Af denne grund unders0gtes TS-1 og silicalit ved hjælp af det samme apparat under an-vendelse af cxA^Og som intern standard.
5 I nedenstâende tabel 1 er anfort de mest signifi- kante spektraldata for et ved fremgangsmâden ifolge op-findelsen fremstillet titanmodificeret siliciumoxid TS-1 med x = 0,017 samt for et rent silicalit.
Konstanterne for den elementære krystalcelle be-10 stemtes ved de mindste kvadraters metode pâ basis af de interplanare afstande for 7-8 enkeltrefleksioner inden for vinkelomrâdet 10-40° for 2 Θ.
En stor del af de interplanare afstande for TS-1 har, omend i ringe grad, tendens til at være st0rre end 15 tilsvarende afstande for det rene silicalit i overens-stemmelse med den forudseelige h0jere værdi af Ti-0 bin-dingsafstanden i forhold til Si-0 bindingsafstanden.
Overgang fra en dobbeltrefleksion til en enkeltref leksion fortolkes som en ændring fra en monoklin 20 symmetri (pseudo-orthorhombisk) for silicalit til en ef-fektiv orthorhombisk symmetri for titansilicalit (TS-1).
Pilene i fig. 1a og 1b angiver de tydeligste af de oven-nævnte spektrale forskelle.
Overgang fra den monokline struktur af silicalit 25 til den orthorhombiske struktur af titansilicalit finder sted over en titankoncentration af storrelsesordenen 1%.
Bade rumfanget af elementarcellen og intensiteten af et karakteristisk IR-absorptionsbând (se nedenfor) viser tydeligt kontinuiteten i substitutionen (med Ti 30 pâ Si-gitterpladser) (se fig. 3a og 3b).
•Infrar0d unders0gelse♦ TS-1 udviser et karakteristisk absorptionsbând ved ca. 950 cm 1 (se fig. 2, spek-trene B, C og D), der ikke er til stede i spektret for det rene silicalit (fig. 2, spektrum A), men kan iagt-35 tages i spektrene for titandioxider (rutil og anatas) samt for alkalititanater.
Spektrum B er spektret for TS-1 indeholdende 0,5 mol% τ^°2* Spektrum C er spektret for TS-1 indehol- 4
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dende 0,0 mol% Ti02. Endelig er spektrum D spektret for TS-1 indeholdende 2,3 mol% Ti02·
Som det ses af fig. 2, forages intensiteten af bândet ved ca. 950 cm ^ med mængden af titan, som erstat-5 ter siliciummet i silicalitstrukturen.
Morfologi. I morfologisk henseende er TS-1 i form af parallelepipeder med afrundede kanter. En r0ntgenstrâ-le-mikrosondeunders0gelse har vist, at titanfordelingen inden for krystallen er fuldstændig ensartet, hvilket 10 sâledes bekræfter, at titanet erstatter siliciummet i silicalitstrukturen og ikke er til stede i andre former.
Adsorption. Adsorptionsisotermen bestemt ved BET-metoden med 02 viser, at TS-1 typisk opf0rer sig som en molekylsigte med enporevolumenmætningskapacitet pâ 0,16-15 0,18 cm^ g ^.
Denne egenskab g0r TS-1 egnet til anvendelse som et adsorbens med hydrofobe egenskaber.
En hensigtsmæssig udferelsesform for fremgangs-mâden ifelge opfindelsen bestâr i, at man som substitue-20 rende grundstof yderligere indferer bor, aluminium eller jern.
Herved kan de kemiske og katalytiske egenskaber af TS-1 modificeres.
Ved fremgangsmâden ifelge opfindelsen til frem-25 stilling af TS-1 fremstilles en reaktionsblanding bestâ-ende af kilder for siliciumoxid og titanoxid, en nitro-genholdig organisk base og vand, hvor molforholdene sva-rer til de ovennævnte omrâder.
Siliciumoxidkilden er fortrinsvis tetraethyl-30 orthosilicat, og titanoxidkilden er fortrinsvis Ti(OC2H5)4.
Reaktionsblandingen underkastes hydrotermisk be-handling i en autoklav ved en temperatur pâ mellem 130 og 200°C, under autogent tryk, i et tidsrum pâ 6 til 30 35 dage, indtil der er dannet krystaller af TS-1-precurso-ren. Disse adskilles fra moderluden, vaskes omhyggeligt med vand og terres. I vandfri tilstand har de felgende sammensætning: x Ti02 . (1-x) Si02 . <^/0,04(RN+)20. Pre- 5
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cursor-krystallerne opvarmes i 1 til 72 timer i luft ved 550°C for fuldstændigt at fjerne den nitrogenholdige organiske base. Det som slutprodukt opnâede TS-1 har sammensætningen: x TiC>2 . (1-x) SiC>2, hvor x har den 5 ovennævnte betydning. Der udfores kemisk-fysiske under-sogelser pâ de sâledes opnâede produkter.
Opfindelsen angâr ogsâ anvendelse af det ved fremgangsmâden ifolge opfindelsen fremstillede silicium-oxid som katalysator og/eller adsorbens.
10 Titansilicalittet fremstillet ifolge den fore- liggende opfindelse anvendes navnlig til folgende reak-tioner: I) alkylering af benzen med ethylen eller éthanol, og alkylering af toluen med methanol, 15 2) disproportionering af toluen til dannelse af para-xy-len, 3) krakning og hydrokrakning, 4) isomerisering af n-paraffiner og naphthener, 5) reformering, 20 6) isomerisering af polyalkyl-substituerede aromatiske forbindelser, 7) disproportionering af aromatiske forbindelser, 8) omdannelse af dimethylether og/eller methanol eller andre lavmolekylære alkoholer til carbonhydrider, 25 9) polymérisation af forbindelser, der indeholder oie-fin- eller acetylenbindinger, 10) omdannèlse af alifatiske carbonylforbindelser til i det mindste delvis aromatiske carbonhydrider, II) aaskillelse af ethylbenzen fra andre aromatiske Cg-carbonhydrider, 30 12) hydrogenering og dehydrogenering af carbonhydrider, 13) methanisering, 14) oxidation, 15) dehydratation af oxygenholdige alifatiske forbindelser, 35 16) omdannelse af olefiner til forbindelser med h0jt ok-tantal.
6
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Fremgangsmâden if0lge opfindelsen belyses nærmere ved hjælp af de efterfolgende eksempler.
Eksempel 1 5 Dette eksempel belyser fremstillingen af TS-1 med h0j renhedsgrad.
455 g tetraethylorthosilicat anbringes i en pyrex-glaskolbe/ forsynet med en omr0rer og holdt under en COg· fri atmosfære, og der tilsættes 15 g tetraethyltitanat 10 efterfulgt af gradvis tilsætning af 800 g af en 25 vægt% opl0sning af tetrapropylammoniumhydroxid (fri for uorga-nisk alkali). Blandingen holdes under omr0ring i ca. 1 time, hvorefter man forsigtigt begynder at opvarme til fremskyndelse af hydrolysen og afdampning af den fri-15 gjorte ethylalkohol.
Efter ca. 5 timer ved 80-90°C er alkoholen fuld-stændig fjernet. Rumfanget for0ges til 1,5 liter med destilleret vand, og den opalescerende homogène opl0s-ning overf0res til en titanautoklav forsynet med en om-20 r0rer. Blandingen opvarmes til 175°C og holdes under om-r0ring ved denne temperatur under autogent tryk i et tidsrum pâ 10 dage. Nâr behandlingen er afsluttet, af-k0les autoklaven, indholdet udt0mmes, og den opnâede masse af fine krystaller udvindes. Denne masse vaskes 25 omhyggeligt mange gange pâ et filter med varmt destilleret vand.
Produktet t0rres derpâ og calcineres til sidst ved 550°C i 6 timer.
R0ntgenstrâlediffraktxonsspektret for det calci-30 nerede produkt svarer til det for TS-1 i fig. lb og ta-bel 1 angivne.
Eksempel 2
Dette eksempel belyser fremstillingen af TS-1 un-35 der anvendelse af tetrapropylammoniumperoxytitanat som titanoxidkilde.
Pertitanater vides at være stabile i stærkt ba-sisk opl0sning.
7
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150 g tetraethyltitanat hydrolyseres ved langsom tildrypning til 2,5 liter destilleret vand under omr0-ring. Der opnâs en hvid gelatin0s suspension. Den afk0-les til 5°C, og der tilsættes 1,8 liter 30% hydrogen-5 peroxid, der ligeledes er a£k01et til 5°C, hvorefter man af og til omr0rer over et tidsrum pâ 2 timer, medens temperaturen holdes lav. Der opnâs en klar orangefarvet opl0sning. Pâ dette punkt tilsættes der 2,4 liter af en 25% vandig tetrapropylammoniumhydroxidopl0sning, der er 10 for-k0let til 5°C. Efter 1 times forl0b tilsættes der 500 g"Ludox"kolloid silica indeholdende 40% SiC>2, og der blandes omhyggeligt, og blandingen henstilles natten over ved stuetemperatur. Den opvarmes derpâ under omr0-ring til 70-80°C i 6 til 7 timer. Den sâledes opnâede 15 blanding overf0res til en autoklav, og de i eksempel 1 beskrevne operationer udf0res derpâ.
Slutproduktet viser sig ved r0ntgenstrâleunder-s0gelse at være pâ rette mâde krystalliseret rent TS-1.
20 Eksempel 3-7
Idet man arbejdede under de i eksempel 2 beskrevne betingelser, blev der fremstillet fera præparationer, hvori man varierede de molære forhold mellem reaktanter-ne (udtrykt som SiC^/TiC^) og tetrapropylammoniummængden 25 (udtrykt som RN+/Si02)· Resultaterne af den kemiske analyse, ændringen i gitterrumfanget og IR-absorptionsfor- -i holdet for bândene ved 950 cm (Ti) og ved 800 cm (Si) er anf0rt i nedenstâende tabel 2.
Fig. 3a og 3b viser henholdsvis ændringen i for-30 holdet mellem intensitéterne af IR-absorptionsbândene og ændringen af gitterrumfanget.
Abscissen i disse figurer repræsenterer indholdet x af Ti02 udtrykt i mol%.
Punktet 0 pâ abscissen svarer til de ovennævnte 35 værdier for rent silicalit. Man kan se den tilnærmelses-vis lineære ændring af begge de ovennævnte st0rrelser, efterhânden som titankoncentrationen ændres.
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Eksempel 8
Dette eksempel belyser, hvorledes de sure egen-skaber af TS-1 pâvirkes i betydelig grad ved indf0ring af spor af aluminium.
5 Idet man arbejdede pâ n0jagtig samme mâde som i eksempel 2, sattes der pâ forhând 4,27 g NaAlC^ til de 500 g’ïiudox" kolloid silica (molært reaktantforhold SiC^/ A^O^ = 128). Selv om det opnâede TS-1 ved r0ntgenstrâ- leunders0geïse ikke viser kendelige forskelle fra det i 10 eksempel 2 opnâede, viser det i H -formen en betydeligt —3 for0get aciditet (gâende fra en koncentration pâ 1.10 mækv. H /g for TS-1 til en koncentration pâ 0,5 mækv.
H+/g for den med aluminium doterede pr0ve).
15 Eksempel 9
Dette eksempel belyser, hvorledes aciditeten af TS-1 pâvirkes ved indf0ring af bor.
Idet man arbejder n0jagtigt som i eksempel 2, tilsættes der 40 g borsyre opl0st i 35 g KOH til"Ludox" 20 silicaen.
Aciditeten af slutproduktet er 0,8-1 mækv. H /g.
I dette tilfælde pâvises den samtidige substitution med bor og titan ved IR-unders0gelse. Foruden Ti-bândet ved 950 cm ^ er det karakteristiske bând for bor 25 i tetraedrisk koordination klart synligt ved 920 cm
Anvendelseseksempel 5,8 g allylalkohol sattes til en opl0sning af 3 tert-butylalkohol (80 cm ) indeholdende 64 g af en 6,3%'s 30 hydrogenperoxidopl0sning i vandfri tert-butylalkohol.
Til denne blanding sattes 2 g TS-l-katalysator (2 mol%
TiC^), og den opnâede blanding omr0rtes ved stuetempe-ratur. Efter 12 timers forl0b filtreredes reaktionsblan-dingen, og opl0sningsmidlet afdestilleredes under vakuum.
55 Den rensede remanens indeholdt 8 g glycerol i et udbytte pâ 86%.
9
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Tabel 1 TS-1 Silicalit ^ 2 Θ Interplanar Belativ 2 Θ Interplanar Relativ (CuKa) af stand intensitet^^ (CuKÔc) af stand intensi- 5 d(Â) d{Â) tet(b) 7,94 11,14 vs 7,94 11,14 vs 8,85 9,99 s 8,85 9,99 s 9,08 9,74 m 9,08 9,74 m 13,21 6,702 w 13,24 6,687 w 10 13,92 6,362 mw 13,95 6,348 mw 14.78 5,993 mw 14,78 5,993 mw 15,55 5,698 w 15,55 5,698 w* 15.90 5,574 w 15,90 5,574 w 17,65 5,025 w 17,65 5,025 w 15 17,81 4,980 w 17,83 4,975 w 20,37 4,360 w 20,39 4,355 w 20,85 4,260 mw 20,87 4,256 mw 23,07 3,855 s 23,08 3,853 s 23,28 3,821 ms 20 23,29 3,819 s 23,37 3,806 ms 23,71 3,753 ms 23,72 3,751 s 23,80 3,739 ms 25 23,92 3,720 s 23,94 3,717 s 24,35 3,655 mw 24,41 3,646 m 24,60 3,619 mw 25,84 3,448 w 30 25,87 3,444 w 25,97 3,431 w 26,87 3,318 w* 26,95 3,308 w* 29,23 3,055 w 29,27 3,051 mw 35 29,45 3,033 w 29.90 2,988 mw 29,90 2,988 mw 30,34 2,946 w 30,25 2,954 w 45,00 2,014 mw!]! 45,05 2,012 mw* 45,49 1,994 mw 45,60 1,989 mw
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10 (a) Fremstillet ved fremgangsmâden if01ge USA-patent-skrift nr. 4.061.724. Produkt calcineret ved 550°C.
(b) vs: meget stærk; s: stærk; ms: middelstærk; m: mid-del; mw: middelsvag; w: svag; : multiplet.
11
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Claims (3)

1. Fremgangsmâde til fremstilling af porost, kry-stallinsk siliciumoxid, hvori silicium-gitterpladser er besat med titan, og som har den almene formel
5. Ti02 . (l-x)Si02 hvori x ligger mellem 0,0005 og 0,04, fortrinsvis mellem 0,01 og 0,025, ved hvilken der foretages hydrotermisk omsætning af kolloid silica eller tetraalkylorthosilicat, tetraalkoxytitan eller tetrapropylammoniumperoxytitanat, 10 tetrapropylammoniumhydroxid og vand ved en temperatur pâ fra 130 til 200°C under autogent tryk i et tidsrum pâ fra 6 til 30 dage,og de opnâede krystaller derpâ adskil-les fra moderopl0sningen, vaskes med vand og terres og til sidst opvarmes i 1 til 72 timer i luft til 550°C, 15kendetegnet ved, at man i reaktionsblandingen overholder folgende molforhold: Si02/Ti02 fra 5 til 200, fortrinsvis fra 35 til 65, OH /Si02 fra 0,1 til 1,0, fortrinsvis fra 0,03 til 0,6, H20/Si02 fra 20 til 200, fortrinsvis fra 60 til 100, og 20 RN+/SiO^ fra 0,1 til 2,0, fortrinsvis fra 0,4 til 1,0, hvor RN er kationen af tetrapropylammoniumhydroxid.
2. Fremgangsmâde ifolge krav 1, kendeteg-n e t ved, at man som substituerende grundstof yderlige-re indforer bor, aluminium eller jern.
3. Anvendelse af det ifolge krav 1 eller 2 frem- stillede siliciumoxid som katalysator og/eller adsorbens.
DK493980A 1979-12-21 1980-11-19 Fremgangsmaade til fremstilling af titanmodificeret poroest, krystallinsk siliciumoxid og anvendelse af dette. DK157361C (da)

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