CA1155830A - Porous crystalline synthetic material constituted by silicon and titanium oxides, a method for its preparation, and its uses - Google Patents

Porous crystalline synthetic material constituted by silicon and titanium oxides, a method for its preparation, and its uses

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Publication number
CA1155830A
CA1155830A CA000365222A CA365222A CA1155830A CA 1155830 A CA1155830 A CA 1155830A CA 000365222 A CA000365222 A CA 000365222A CA 365222 A CA365222 A CA 365222A CA 1155830 A CA1155830 A CA 1155830A
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Prior art keywords
titanium
sio2
silicon
silicon oxide
organic base
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CA000365222A
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French (fr)
Inventor
Marco Taramasso
Giovanni Perego
Bruno Notari
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SnamProgetti SpA
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SnamProgetti SpA
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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

Abstract

ABSTRACT OF THE DISCLOSURE:

This invention relates to a porous crystalline synthetic material constituted by silicon and titanium oxides, a method for synthesising said material, and the use thereof as a cata-lyst. The material corresponds to the following formula:
x Ti O2 ? (1-x) Si O2 where x lies between 0.0005 and 0.04, preferably between 0.01 and 0.025 . The material is prepared starting from a mixture constituted by a source of silicon oxide and a source of tita-nium oxide. The reaction takes place in the aqueous phase at a temperature of 130 to 200°C, and the solid product obtained is calcined in air at 550°C.

Description

1 15583~
CASl 1269 This inventi.o~l relates to a porous crystalline synthetic material contituted hy silicon and tit~nium oxides, a method for its preparation, and its uses.
Hereinafter in the descri.ption, said synthetic msterial will be known as titanium sil.i.calite, or more briefly TS-l.
U.S.A. patent 3,329,481 describes zeolites containing titanium, which are prepared from si].iceous materials and inorganic titanium compounds in the sbsence of organic bases.
IlSilicalitel~ a zeolite Lvruct~re constituted by pure crystalline Si 2~ h3s been described b~ Flanigen F,.M. and others (~sture 271, 512 (1978)).
A crystalline porous silica having a structure of silicalite type in which the titanium is mentioned, among many other metals, as modi.fier, i.s described in the Canadian Patent 15 Application N~330.300 filed on June 21, 1979.
The same patent application describes an embodiment in which the smount of titanium is about 29.5 mol 50 with respect to the silica.
'~lithin the composition range of 0.0001 - 1 Ti 2 . 1 Si 2 described in the aforesaid patent application, a composition rang~ has now been found which ensbles a titanium silicalite to be obtained having surprising catalytic properties in those reactions in which said catalysts are used.
The composition ran~e of the titanium silicalite accordinO to the present invention, exr:ressed in terms of molar reagent ratios, is as follows:

1 ~ 5583û -Molar reagent ratio Preferably Si O2/Ti 2 5-200 35-65 OH /Si 2 0.1-1.0 0.3-0.6 H2O/Si 2 20-200 60-100 Me/Si 2 0.0-0.5 0 RN /Si 2 0.1-2.0 0.4-1.0 RN indica,tes the nitrogenated organic cation deriving from the organic base used for preparing the titanium silicalite according to the invention.
Accordingly,the present invention in particular provides a method for preparing a silicon oxide and titanium oxide-based porous crys-talline synthetic material, possessing a silicalite-type struc-ture in which the titanium substitutes the silicon, and repre-sented by the formula x Ti 2 . (l-x) Si 2 where x lies between 0.0005 and 0.04, preferably between 0.01 and 0~025r wherein the starting reagents are constituted by a source of silicon and titanium oxides and, if desired, an alka-line oxide, a nitrogenated organic base and water in the follo-wing molar ratios:
SiO2/TiO2 from 5 to 200, preferably 35 to 65 OH /SiO2 from 0.1 to 1.0, preferably 0.03 to 0.6 H2O/SiO2 from 20 to 200, preferably 60 to 100 Me/SiO2 from 0.0 to 0.5, preferably zero RN /SiO2 from 0.1 to 2.0, preferably 0.4 to 1.0 where Me is an alkaline ion, preferably Na or K, and RN is the cation of the nitrogenated organic base, the mixture of the reagents with the water is subjected to hydrothermal treat-ment in an autoclave at a temperature of 130 to 200C under its own '30 pressure for a time of 6 to 30 days, the crystals obtained are then separated from the mother solution, washed with water and dried, a~d finally heated for 1 to 72 hours in air at 550C.

1 15583~
Me i5 an alkali~e ion, pxefe~ably Ma ~r K.
The final TS 1 has a compositio~ corresponding to the formula ~ Ti 2 (l-x) Si 2' where x lies between 0.0001 and 0.04, preferably between 0.~1 and 0.025. The TS-l is of the silicalite type, and all the titanium substitutes the silicon.
In the figures which illustrate embodiments of the present in~ention:
Figure la represents a typical silicate X-ray dif-fractian~spectrum Figure lb represents the X-ray diffraction spectrum of a product according to the present invention Figure 2 represents infrared absorption characte-ristics of ~arious products including products according to the present invention Figures 3a and 3b show respectively the variation of the ratio between intensities of the infrared absorption bands and the variation of the lattice volumes.
The synthetic material according to the invention has characteristics which are demonstrated by a X-ray and infrared examinatiOn.
The X-ray examination is carried out by means of a powder diffractometer provided with an electronic pulse counting system, using CuK~ radiation. The products according to the present invention are characterized by an X-ray diffraction spectrum as shown in Figure lb. This spectrum is similar overall to the typical silicalite spectrum (Figure la), however it com-prlses some clearly single reflections where evident double reflections are present in the pure silicalite spectrum. As the spectrum differences between TS-l and silicalite are relative-ly small, particular care is required in the spectral determina-tion. For this reason, TS-l and -'SJ~ ' - 2 a -1 ~SS83~

silic31ite were exalll.ined by t.he same apparatus usin~r ~ A1203 as the internal standard.
TDble 1 shows the most significant spectral data for a TS-l with x _ 0.017, and a pure silicalite.
~he elementary crystalline cell constants were determined by the method of minimum squares, on the basis of the inter-planar distances of 7-8 ~ingle reflections within the range of 10~40 for 2 ~ .
A ]arge proporti.on of the interpl3nar distances for the TS-l are, even though slight].y, tendenti.ally greater thsn the corresponding distances for the pure silicalite, in accordanca with the higher foreseeable value of the Ti-0 bond distance with respect to that of the Si 0 bond distance.
Yassage from a double reflection to a single reflcction is interpreted as a change from a monoclinic symmetry (pseudo orthorhombic) (silicallte~ to an effective orthoxhombic symmetry (titsnium silicalit~ (TS-l)). ~he arrows i.n Figs~la and lbindicate the more apparent of the afore~oinr spectral differences.
Passa~e from the monoclinic structure (silical.ite) to the orthorhombic structure takes place above a titanium concen-tration of the order of 1%.
However, both the element~ry cell volume and the intensity of a characteristic IR absorption band (see hereinafter) clearly demonstrate the continuity of the substitution phenomenon (see Figures 3a and 3b).
Infrared examination. '.~S-l shows 8 characteristic absorption band at about 9~0 cm (~ee Fig. 2, spectra B, C and ~) which 1 ~5583~

is not present in the pure silicalite spectrum (Fig. 2, spectrum l~), and is absen~ in tltanium oxides (rutile~
anatase) and in the alkaline titanates.
Spectrum B is that of the TS-l containing 5 mol %oof Ti 2 5pectrum C is that of the TS-l containing 8 mol %cof Ti 2~
Finally, spectrum D is that of the TS-l containing 2.3 mol %
of Ti 2-As can be seen from Fi~ure 2, the intensity of the b~nd at about 950 cm 1 increases with the quantity of titanium which substitutes the silicon i~ the silicalite structure.
~orphol~. In morphological terms, TS_l is in the form of parallelepipeds with rounded edges. A X_ray microprobe examination has deMonstrated that the titanium distribution within the crystal is perfectly uniform, thus confirming that the titgnium substitutes the silicon in the silicalite structure, and i6 not present in other forms.
Ad~orption. The adsorption isotherm deternined by the BET
method with 2 shows that l'S-l has the typical behaviour of 3 molecular sieve with a pore volume saturation capacity of 0.16-0.18 cn3 g 1.
This property makes TS_l suitable for use as an adsorbent with hydrophobic charscteristics.
The chemical and catalytic properties of TS-l can be modified by introducing other substituting elements such as B, Al, Fe etc. during the synthesis stage.
The present invention also relates to a method for preparing the synthetic mRterial conc~tituted by silicon and titanium oxides.

1 i5583~

In the aroros3id patonl ~ppliG-lti.~n i~ d~.s~ribe~ ~

method for preparing a silicon and titanium oxide-based material using~ a 3OCo hydro~cn peroxide .solution to ~].lo~
solubilisation of the ti-taniurn compolmds in a basic environ-ment, It has been found that the additi.on of the hydrogen peroxide solùtion is not neces6ary undcr certain conditions, and thus the preparation method for the material accordin~ to the invention is greatly sinp;.iied.

The method for preparin~ . comprises the preparation of a reactioll mixture consti.tu~ed by sources c,f silicon oxide and titanium oxide, and possibly an alkaline oxide, a nitrogenated organi.c base and water, hav.ng a reagent molar ratio composit-ion as heretofore defined.
The silicon oxide source can be a tetraalkyloxthosilicate, preferably tetraethylorthcsilicate~ or simply a silica in colloidsl form, or again a sili.cate of an alkaline metal, preferably Na or K.
The titanium oxide source is a hydrolysable tiianiurm compo~nd choscn prefcrably from Ti C14, Ti 0 C12, and Ti (alkoxy)4, preferably Ti (OC2 H5)4.
The organic base is a tetraalkylammonium hydroxide, in particular tetrapropylammcnium hydroxide.
~Ihe reagent mi.xture is sub~jected to hydrothermal treatmen~ in an autoclave at a temperature of between 130 and 200 C, under its own pressure, for a tire of 6-~o days until the crys als Gf the T~~] precursor are formed. These are separated from the mother solution~ careflllly washed with water and dried~

1~5.~&3~`

ln the anhydrous st~te they haYe the follo~ing composition:
~: Ti 2 ~ x) Si 0~ O.O'I(RN )2 The precursor crysta:l.s are heated fo.r 1 to 72 hours in air at 550C in order to comple-tely eliminate the ni.trogenated orp;anie base. The final TS-l has the composi.l~on: x Ti 2 . (].-x) Si 2 ~here x is as heretofore defined. Chemical-physical examinations are carried out on the products thus obtained.
The uses of the titanium silicalite accordi.r.~ to Ihe invention are in parti.cular the followin~:
1) alkylation of ben~ene ~ h ethylene or e-thanol, anci alkylntion of toluene with methanol
2) disproportioning of to].uene to produce paraxylol
3) eracking and hydrocr~c!cing
4~ isome.risation of n-par~ffins and naphthenes
5~ reforming
6) isomerisation of substi.tuted polyalkyl aromaties
7) disproportioning of aromatics
8) conversion of dimethylether and/or methanol or other low molecul.ar ~eight alcollois into hydrocarbons
9) polymerisation of compounds which contain olefine or acetylene bonds
10) conversion of aliphatic c~rbonyl compounds into at least partly aromatic hydrocarbons
11) separation of ethybenzellce from other ar~matic ~8 hyclro-carbons
12) hyclro,renation and dehyl1ro,-,enation of hydrocarbons
13) methanation i4) o~idation 11558~

15~ dehydration Or aliph~tlc compollnds containing oxy~en 16) conversion of olefines into ccmpounds of hiGh octane n~miber.
Some examples are g:iven hereirlafter in order to better illustrate the inventionS ~ut without limiting it in any way.
Example 1 This e~ample illustrates the preFaration of TS-l with a high degree of purity.
455 g of tetraethylortho~ilicate are placed in a pyrex ~lass vessel fitted with a stirrer and kept under a ~02-free atmos phere, and 15 g of tetraethyl~itanste are added follo ed gradually by 800 g of a 25,C'~ weight so]ution of tetrapropyl ammonium hydroxide (free from :inorganic alkali~. The mixture i6 kept stirred for about one hour~ then heating is commenced carefully in order to accelerate hydrolysis and evaporate the ethyl alcohol which is released.
After about 5 hours at 80_90 C, the alcohol has been completely eliminated. The volu~e is increased to 1.5 litres with distilled ~ater, and the opal3scent homogelleous solution -s transferred to a titanium autoclave fitted with a stirrer~
The mi~ture is heated to 175 C, and is kept stirred at this temperature under its own pressure for a time of ten days.
~Ihen the treatm~nt is finished, the autoclave is cooled, the contents are dischar~ed, and the mass of fine cry~tals Gbtained is recovered. Th:~ is careflllly washed on a filter with hot distilled water many times.
The product is then dried and finaliy Galcined at 550C for six hours.

1 15~30 The X-ray diffraction spe&tru~ for the calcinetl product corresponds to that of thc TS-l g~lven in Figure l ~ and Table l.
xample 2 This exomple illustrates tho preparation of TS-l using tetrapropylammonillm peroxytitanate as th~ titaniUn1 oxide source.
The pertitanates arc known 1:o be stable in a strongly basic solution.
150 g of t~traethyltitanate are h~Jdrolysed by filowly Aripping into 2.5 litres of distilled water under stirring. A whit~
~clatinous suspension is ob1n~ined. It is cooled to 5C and 1.8 litres of 30~ hydrogen peroxide, also cooled to 5 C, are added, then stirring occasionally over two hours while maintain-ing the temperature low. A clear oran~e-coloured solution ifi obtained. At this point, 2.4 litres of a 25~ aqueous tetrapropylammonium hydroxide solution pre-cooled to 5 C are sdded. After one hour, ~00 g of Ludox colloidal silica containing 40% of Si 2 are ~ddcd, mixing is carried out carefully, and the mixture left standing ovcrnight at ambient temperature. It is finally heated under stirring to 70_~0C
for 6_7 hours. Thc mixture thus obtained is transferrcd to Dn ~utoclavo, and the oporations describod in oxomple l ~re then carried out.
Tho fi~ l product whon undcr .Y-rDY cxan1il1otioll is found ~o bo proper~y crystallised pure TS_l Examples 3 - 7 Operatin6 under the cond:i~ions described in exa.~ple 2, five * Trade Mark prepar~tions were made in ~ ;.ch the molar ratios Or ths re~gents (expressed as Si 02/Ti 2) and the tetrapropyl_ am~nonillm qualltity (expressed ~s ~tN /Si 2) ~ere varied, The results of the chemical analysis, the variation in Iatticc volume and the IR absorbency rDtio for the bands at 950 cm 1 (Ti) and ~t 800 cm (Si~ ~re ~umm~rised in tzb].e 2.
Figures 3a and 3b show respec~ively the variation oE the ratio between the intensities of the Il~ absorption bands and the variation of the lattice ~olumes.
10 The abscissa in these f:ignres represents the content x of Ti 2 expressed in mol ~
The.point O on the absci.s,sa corresponds to tlle aforesaid values for pure silicalite. 1'he approximately linear variation of both the aforesaid q~antiti.es as the titanium concentration varies can be seen.
Example 8 This example illustratefi how the acid properties oï TS_1 are considerably influenced by the i.ntroduction of tracss of alllminium.
Operating exactly as in exaJnlJle 2, 4.27 g of NaA102 were previously added tu tne 500 g of Luuox*colloidal silica (molar reagellt ratio Si 02/A12 03 128). ~lthough the TS-l obt~ ed does not sho~ appreciable d;fferences under X-ray examination from that obtained in example 2, i.' sho}Js in the H form eonsiderably incre3sed ~ci.dity (pa~;sing from a concelltratio~
of 1.10 3 meq H+/g for the TS-l to a concentration of 0.5 meq ,H+/g for the sample doped ~ith aluminium).
Example 9 * Trade Mark 1 ;55830 ThiS ex~mple illustrgteg how the acidity Or 'l'S.1 is influ3nced by the introductioll of bc,ron.
Opersting exactly as in exarnple 2, llO g of boric acid dissolve in 35 ~ of KO}I were added to the Ludox* silica.
The acidity of the final product is 0.8~1 meq H+~g.
In this case, the simult~ncolls subst:ilution by the boron and titsnium is demonstrated by I~ examin~tior~. Be.sides the l'i band at 950 crn ~ the characteristic band of boron in tetra-hedral coordination is cle~rly visible at 920 cm - 10 Exa~le 10 5.8 g of allyl alcohol ~cre added to e solution Or tertiary butyl slcohol (80 cc) containin~ 64 g Or a 6.3,~' hy~ro~en peroxide solution in anhydrolls tcrtiary butyl ~lcohol. 2 of TS-l cat~lyst(2 mol S' Ti 2) ~ere added to this mixture, and the resultant mixture \18S stirred st ambient temperatllre.
After 12 hours the reaction mixture ~as filtered, and the solvent distilled off under vscuum.
The purified residue contained 8 g ol` glycerin ~ith a yield Of 86S~.

* Trade Mark B

1 1 ~ 5 & ~ ~

TS-l Silicalitc ( ) 2 Q Interplan3r Rel. 2 ~ Interplan~r 2el, (C ~ distance, Int.( ) tCuK~ dista~lce, Int.
d(A) d(A) ~ 7-94 11.14 væ 7-94 11.14 V8 : 8,85 9-99 s 8.85 9.99 æ
9.o8 9.74 m 9.o8 9.74 m 13.21 6.702 w 13.24 6.687 w 1013.92 6.362 ~w13.g5 6.348 mw
14.78 5.993 mw14.78 5.9g3 mw
15.55 5.698 w 15.55 5.698 w~
15.90 5.574 w 15.90 5.574 w 17.65 ~.025 w 17.65 5.025 w 1517.81 4.980 w ;7.83 ~'.975 w 20.37 L~.360 w 20.39 L;.355 w 20.85 4.260 mw20.87 4.256 mw 23.07 3-855 ~ 23.08 3.853 s 23.28 3.821 ms 2023.29 3~819 s 23.37 ~.806 ms 23.71 3.753 ms 23072 3.751 s 23.80 3.739 ms 25Z3.92 3.720 s 23.94 ~.717 s 24.35 3.655 mw 2J+.41 3.646 m 24.60 3o619 mw l~ssa30 2~.84 3.l~48 w 25.87 3~4~4 w 25.~7 3.431 w 26.87 3.31~ W4 2~.95 3.30S w 29.23 3.055 w 29.27 3.051 ~
29.L~5 3.033 w 29.90 2.988 mw 29.~0 2.98S mw 3.34 2.9~6 w 30.25 2.954 w 45.00 2.014 mw' 45.05 2.0-12 mw*
45.49 1.994 mw* 45.60 1.9&9 mw*
(3) prepared by the method o~ ~I.S. patent 4,061,724.
Product c~lcined ~t 550 C.
(b) vs: very strong; s: stIong; ms: medium strong;
m: medium; mw: medium weak; w: we~k; 4: multiplet 1 ;S583~

~, V ~, ~ o ~ ~ ,~ a~
1~ o ~ r ~ 0~ ~ r I .
I O O O O~
r~ ~ ) ~, I

.C ~U
a Vc ~ t ~
0~ ~I r~ N N~1 o~ O ~ ~
U
u~ o o o oa~
Nr I r~ IJ r-l ~) In rl C
~ ~ ~ ~ C U~
N ~D N ~ C 13 t~
N O
~J O ~ r c~ o o o o a~
C~ S ~
o O
p~ r-l ~ ~ ~ C ,L~ N
0~ r-l O ~~ rl ~ O
r l O r l N Or~ CO tlO 3 0 O O O OCl~ ~ O
~1 ~I r-lr~ U
~1 ~ tlD r ~
o-C
~d O
r I.Cr~
N ~ ~t~
<r~ r ~ ,C 0 r cO~ ur~ OQ~
r~ O O O O ~ ~ Oc0 4~
Nr-~ r~ C C
In t.~.~D .,, ~ U~

r-l ~q O ~r I
~.r ~
O ~ ~ U11 O ~J ~rlc~
^ ~ e ~ .,, o~ o~ o¢ o ~ ~ ~ a ~q ~q ,. ... .~ . O .r ' .r~
C V ~ C td ~ O15 P ~ r~ u~~
v ,r~ ~ S~ r~ r~l ~U nS 0 r~ C r~l r I
~ v r~ o~ o O ~ d Q) ~1 11 ~ ' o~ e ~ C c ~ s 4~ ~ ~
;~ N _ ~ r

Claims (20)

The embodiments of the invention in which an exclusive property or privilege is being claimed are defined as follows:
1. A method for preparing a silicon oxide and titanium oxide-based porous crystalline synthetic material, possessing a silicalite-type structure in which the titanium substitutes the silicon, and represented by the formula x Ti O2 ? (1-x) Si O2 where x lies between 0.0005 and 0.04, wherein the starting rea-gents are constituted by a source of silicon and titanium oxides and, if desired, an alkaline oxide, a nitrogenated organic base and water in the following molar ratios:
SiO2/Tio2 from 5 to 200, OH-/SiO2 from 0.1 to 1.0, H2O/SiO2 from 20 to 200, Me/SiO2 from 0.0 to 0.5, RN+/SiO2 from 0.1 to 2.0, where Me is an alkaline ion, and RN+ is the cation of the nitro-genated organic base, the mixture of the reagents with the water is subjected to hydrothermal treatment in an autoclave at a temperature of 130 to 200°C under its own pressure for a time of 6 to 30 days, the crystals obtained are then separated from the mother solu-tion, washed with water and dried, and finally heated for 1 to 72 hours in air at 550°C.
2. A method as claimed in claim 1 wherein the silicon oxide source is a tetraalkylorthosilicate.
3. A method as claimed in claim 1, wherein the silicon oxide source is a silica in colloidal form.
4. A method as claimed in claim 1 wherein the silicon oxide source is a silicate of an alkaline metal.
5. A method as claimed in claim 1, wherein the titanium oxide source is a hydrolysable titanium compound.
6. A method as claimed in claim 5, wherein the hydro-lysable titanium compound is chosen from TiC14, TiOC12 and Ti(alkoxy)4.
7. A method as claimed in claim 6 wherein Ti(alkoxy)4 is Ti(OC2H5)4.
8. A method as claimed in any one of claims 1, 2 and 3, wherein the nitrogenated organic base is tetraalkylammonium hydroxide.
9. A method as claimed in any one of claims 4, 5 and 6, wherein the nitrogenated organic base is tetraalkylammonium hydroxide.
10. A method as claimed in claim 7 wherein the nitroge-nated organic base is tetraalkylammonium hydroxide.
11. A method for preparing a silicon oxide and titanium oxide-based porous crystalline synthetic material, possessing a silicalite-type structure in which the titanium substitutes the silicon, and represented by the formula x Ti O2 ? (1-x) Si O2 where x lies between 0.0005 and 0.04, wherein the starting reagents are constituted by a source of silicon and titanium oxides, a nitrogenated organic base and water in the following molar ratios:
SiO2/TiO2 from 35 to 68, OH-/SiO2 from 0.3 to 0.6, H2O/SiO2 from 60 to 100, RN+/SiO2 from 0.4 to 1.0, and RN+is the cation of the nitrogenated organic base, the mixture of the reagents with the water is subjected to hydrothermal treatment in an autoclave at a temperature of 130 to 200°C under its own pressure for a time of 6 to 30 days, the crystals obtained are then separated from the mother solution, washed with water and dried, and finally heated for 1 to 72 hours in air at 550°C.
12. A method as claimed in claim 11, wherein the silicon oxide source is a tetraalkylorthosilicate.
13. A method as claimed in claim 11 wherein the silicon oxide source is a silica in colloidal form.
14. A method as claimed in claim 11, wherein the titanium oxide source is a hydrolysable titanium compound.
15. A method as claimed in claim 14, wherein the hydro-lysable titanium compound is chosen from TiC14, TiOC12 and Ti(alkoxy)4.
16. A method as claimed in claim 15, wherein Ti(alkoxy)4 is Ti(OC2H5)4.
17. A method as claimed in any one of claims 11, 12 and 13 , wherein the nitrogenated base is tetrapropylammonium hydro-xide.
18. A method as claimed in any one of claims 14, 15 and 16, wherein the nitrogenated base is tetrapropylammonium hydroxide.
19. A method as claimed in claim 1, wherein Me is Na or K.
20. A method as claimed in claim 1 wherein the silicon oxide source is a silicate of Na or K.
CA000365222A 1979-12-21 1980-11-21 Porous crystalline synthetic material constituted by silicon and titanium oxides, a method for its preparation, and its uses Expired CA1155830A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT28323A/79 1979-12-21
IT28323/79A IT1127311B (en) 1979-12-21 1979-12-21 SYNTHETIC, CRYSTALLINE, POROUS MATERIAL CONSTITUTED BY SILICON AND TITANIUM OXIDES, METHOD FOR ITS PREPARATION AND ITS USES

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CA1155830A true CA1155830A (en) 1983-10-25

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AR231610A1 (en) 1985-01-31
PT72248A (en) 1981-01-01
AU6451380A (en) 1981-07-02
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JPS5696720A (en) 1981-08-05
IT7928323A0 (en) 1979-12-21
US4410501A (en) 1983-10-18
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