CA1184739A - Crystalline silicate compounds and process for preparing hydrocarbons or unsaturated alcohols by using said silicate compounds as catalyst - Google Patents

Abstract

Abstract of the Disclosure Photocurable compositions are provided which can be cured with ultraviolet light at a wave length greater than 300 nm. The photocurable compositions are based on the use of cationically polymerizable organic materials, for example, an epoxy resin and a photoinitia-tor in the form of a dialkylphenacyl sulfonium salt or hydroxyaryldialkyl sulfonium salt which have been sensi-tized with a particular dye sensitizer.

Description

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1 This invention relates to crystalline silicate compounds and a process for preparing hydrocarbons or unsaturated alcohols by using said crystalline sillcate compounds as catalysts.
Zeolites are crystalline aluminosilicates and have a three-dimensional network structure constituted by tetrahedrons consisting of SiO~ and A104. The tetra-hedrons which have silicon or aluminum at the center are bonded to one another by sharing the oxygen atoms, and the valency of the aluminum is well balanced by coor-dinating cations of alkali or alkaline-earth metals around the crystals, thereby maintaining electrical neutrality of the whole structure~ These cations are exchanged with other kinds of cations by conventional ion-exchanging techniques.
Zeolites originally occur in nature, and owing to their specific catalytic activities, adsorbability, molecular sieve effect and other properties, they are very useful industrially. Many studies have been made on said substances, and consequently, the new types of zeolites have been synthesized which have not been found in nature, and a great number of synthetic zeolites have been reported by now. Many of these zeolites are crystalline aluminosilicates. However, attempts are 73~
1 also being made to synthesize novel compounds having a zeolitic stereo-structure in which both aluminum and silicon constituting the network structure of zeolite have been replaced by other elements, and there are already available compounds having a zeolitic stereo-structure in which aluminum has been replaced by gallium, phosphorus, beryllium or arsenic, and compounds having a zeolitic stereo-structure in which silicon has been replaced by germanium.
The present inventors have conducted extensive research on the synthesis of a novel compound with a high industrial utility, and as a result, have succeeded in synthesizing novel crystalline silicate compounds.
According to the present invention, there is provided a crystalline silicate compound represented by the composition formula (1):

(M2O) (SiO2)x (Y 1 Ol)y .~...... ..... (1) n m xn n wherein M is at least one element selected from ~the group consisting of antimony, bismuth and lanthanide series rare earth elements, n is the valency of the ele ment M, O is oxygen, x is a number of 1 to 5,000, Y is one or more kinds of coordinating cations, m is the valency of the cation Y, and y is a number of 0.1 to 1.
The present invention also provides a process for preparing a hydrocarbon compound characterized by 3~

contacting a catalyst comprising as the main component a crystalline silicate compound having the above composition for~ula (1) with methanol ancl/or dimethyl ether, wherein the xeaction is carried out at a temperature of 200 to 800C and under a pressure of 0.1 to 100 kg~cm .
There is further provided according to this invention a process for preparing an unsaturated alcohol represented by the following formula (4), char-acterized by con-tacting a catalyst comprising as the main componen-t a crystalline silicate compound having the above composition formula ~1) with an ~-olefin rep-resented by the following formula (2) and an aldehyde compound represented by the following formula (3~:

R \ R13

2 / 2 ~ ~ (2) R -CHO ................................... (3) R \ R13 IR4 / C=C-CH2-CH .................................... (4) R OH
wherein R , R , R and R , which may be the same or different, represent hydrogen atoms or alkyl groups having 1 to 8 carbon atoms or alkenyl groups having 2 to 8 carbon atoms, wherein the reaction is carried out at a temperature of 20 to 200C
and the molar ratio of the ~-olefin to the aldehyde is 0.25-20.

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1 Symbol M in the composition formula (1) stands for at least one metal selected from the group con-sisting of the lanthanide series rare earth elements, antimony and bismuth, but in view of the advantages in the industrial applications, it is preferred to use lanthanum, cerium, praseodymium, neodymium, antimony or bismuth, more preferably lanthanum, cerium or antimony.
Symbol x in the formula (1) represents a number of 1 to 5,000, preferably 5 to 1,000. If x is less than 1, there is not provided a compound having the same stereo-structure as possessed by the crystalline silicate com-pounds of the present invention. Also, if x exceeds 5,000, the resulting compound proves to be poor in industrial utility because of, for example, very low catalytic actiVity.
It is considered that the crystalline silicate compounds of this invention have a crystal structure in which the atoms of a lanthanide series rare earth ele-ment, antimony or bismuth are in a negatively charged state due to the biased electric charges. It is also considered that the negative charges are coordinated with cations to keep the whole electroneutral. Thus, said coordinating cations are involved in the crystalline silicate compounds of this invention as shown by the composition formula (1). Said coordinating cations are either inorganic cations such as hydrogen cations or metallic cations, or organic cations such as ammonium ~L~8~ 3~i 1 ions or alkylammonium ions. These coordinating cations are exchangeable with one another, and can be easily replaced by other cations by the conventional ion-exchanging techniques. The symbol y is a number that is variable depending on the degree of crystallization men-tioned hereinafter. For exampler y is 1 when the degree of crystallization is 100% and 0.1 when the degree of crystallization is 10% In view of the activity of the crystalline silicate compounds of this invention when used as said catalyst, y is preferably 0.4 to 1, more preferably 0.7 to 1.
The crystalline silicate compounds of this invention have X ray diffraction patterns as shown in the Examples given hereinafter~
The crystalline silicate compounds of this invention can be produced by reacting a mixed solution or suspension in water of a SiO~ source, an M source, and an inorganic alkali and/or a nitrogen containing compound (said mixed solution or suspension being hereinafter referred to as the solution for reaction), thereby crystallizing the solution.
As the SiO2 sources usable in this invention, there may be mentioned silicic acid, silicates of alkali metals or alkaline-earth metals, water glass, silica hydrogel, silica gel, organic silicates and the like, among which alkali metal silicates, water glass and organic silicates are preferred. Sodium silicate and ' ,.

1 potassium silicate may be mentioned as examples of the alkali metal silicates usable in this invention, and tetraethyl orthosilicate may be men~ioned as an example of the organic silicates. These SiO2 sources may be S used either alone or in combination of two or more.
Said SiO2 source is used usually in an amount o~ 1/10 to 1/200 mole, preferably 1/15 to 1/60 mole, per mole of water which is the medium for the solution for reaction.
As the M source, there may be used any salts which are soluble in water or in aqueous solutions of acids or bases, and as examples of said salts, there may be mentioned chlorides, bromides, acetates, nitra-tes, sulfatesr oxalates, etc. of lanthanide series rare earth elements, antimony and bismuth. More specifically, there may be used lanthanum chloride, lanthanum sulfate, lanthanum nitrate, cerium chloride, cerium bromide, antimony trichloride, antimony triacetate, bismuth chloride, praseodymium chloride, neodymium trichloride, lanthanum oxalate and the like. It is~ of course t possible to use these M sources either alone or in com-bination of two or more. The amount of said M source may be properly decided on the basis of the SiO2 source so that the objective synthetic proc~uct can be obtained.
As the inorganic alkali, there may be used hydroxides of alkali metals or alkaline-earth metals, and they may be used either alone or in combination.
Preferred examples of the alkali metal hydroxides are .

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1 sodium hydroxide and potassium hydroxide, and sodium hydroxide is particularly pre~erred~ Calcium hydroxide is preferred as the alkaline-earth metal hydroxides.
As the nitrogen-containing compounds usable in this invention, there may be mentioned organic compounds such as alkylammoniums and amines. Quaternary ammonium compounds having an alkyl group with 2 to 5 carbon atoms are preferably used as the alkylammonium. Examples of quaternary ammonium compounds include tetraethylam-monium, tetrapropylammonium, te-trabutylammonium, tetra-pentylammonium and the like. Among them, tetrapropylam-monium and tetrabutylammonium are particularly preferred.
The alkylammonium may be supplied in the form of a hydroxide such as tetrapropylammonium hydroxide, tetra-butylammonium hydroxide, etc., or in the form of anappropriate salt such as tetrapropylammonium bromide, tetrapropylammonium chloride, or the like. As the ami-nes~ there may be appropriately used water-soluble ami-nes such as et:hylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethy-lenediamine and the like. It is also possible to use even water-insoluble alkylamines having an alkyl group with 2 to 5 carbon atoms if they are used with a suitable solvent such as acetone, methyl ethyl ketone or the like.
Said inorganic alkali and/or nitrogen-containing compound are pre~erably used in the ~ 7 73~

1 stoichiometrical amount or less based on the SiO2 source, more preferably in an amount of O.OS to 0.5 mole per mole of the SiO2 source~ In the synthesis of the crystalline silicate compounds of this inventlon, joint use of an inorganic alkali and a nitrogen~containing compound is recommended as it proMotes the crystalliza-tion of the reaction product. Although the pH range of the solution for reaction is not critical, the reaction is usually conducted in an alkaline state of a pH of 8 or more, preferably 9.5 to 14. If necessary, a promoter for the crystallization such as an inorganic salt of an alkali metal or an alkaline-earth metal, for example, sodium chloride, sodium bromide, potassium chloride, calcium chloride or the like may be added to lS the solution for reaction.
For accomplishing the desired crystallization, the said solution for reaction is heated to usually 100 to 250C, preferably 120 to 200C and maintained at this temperature for usually 0.5 to 30 days, preferably 1 to 10 days.
It is preferred to stir the solution for reac-tion in the course of the crystallization, whereby the crystallization can be allowed to proceed smoothly.
After completion of this crystallization, the resulting reaction product solution is filtered to obtain the crystalline silicate compound of this invention.
The crystallinity of the crystalline silicate ; compounds of this invention may be varied depending on L73~
1 the crystallization rate and the reaction time. Both SiO2 and M20n which remain uncrystallized at the time of comple~ion of the reaction are contained in the product in the form of non-crystalline SiO2 and non-crystalline M~On when the product compound is separated from the reaction product solution, whereby the crystallinity of the crystalline silicate compound of this invention becomes low. The crystalline silicate compounds of this invention are usually obtained with a crystallinity in the range of 10 to 100%, but in view of the activity in their practical use as catalyst, it is preferable that the crystallinity of the compound is within the range of 40 to 100%, particularly 70 to 100%.
A crystalline silicate compound can be obtained by the above-described operations, but when it is intended to use said compound as a catalyst, it is washed with distilled water, dried, thereafter calcined at a temperature of usually 300 to 1,000C, preferably 400 to 850C, for a period of usually 1 to 30 hours, preferably 3 to 20 hours, and then if necessary, sub-jected to a conventional ion-exchanging technique to replace a part or the whole of the alkali cations con-tained in the crystal by protons or other metallic cations such as mentioned below.
The conversion into a proton type by ion exchange can be accomplished, for example, by contacting the compound with an aqueous solution oE an acid capable of supplying H , such as HCl, HNO3 or H2SO4, or by first _ g _ 3~

1 treating~the compound with a salt capable of supplying NH4 , such as N~4Cl, NH4NO3 or NH400CCH3, and then calcining it at a temperature of 100 to l,000C~ It is, of course, possible to effect said ion exchange with other cations than protons, and there can be easily obtained crystalline silicate compounds containing various types of metallic cations Any cations may be used for effecting the ion exchange in this invention as mentioned above, but from the aspect of the industrial applications, it is advan-tageous to employ hydrogen, alkali metals, alkaline-earth metals, metals of group VIII of the Periodic Table, copper, silver, zinc, cadminum, manganese, rhe-nium, chromium, molybdenum, tungsten and rare earth ele-ments as the cations to be contained in the crystallinesilicate compounds of this invention, and it is desirable to perform the ion exchange with the cations of these elements. As a typical example of the ion-exchanging techniques employable in this invention, there may be mentioned a method in ~hich a compound capable of releasing said elements in the form of cations is formed into an aqueous solution and the crystalline silicate compound oE this invention is immersed therein. The cations contained in the crystalline silicate compound as a result of said ion e~change may not necessarily be of a single type but may, of course, be of two or more different types.
The crystalline silicate compounds of this 73~

1 invention demonstrate an acidity corresponding to the lanthanide series rare earth element, antimony or bismuth contained therein and have an ion~
exchangeability. They also show an extremely high cata lytic activity and a high thermal stability and can be used as a catalyst very effective for the conversion reactions of various types of organic compounds.
Particularly, the compounds of this invention show a prominently high activity with a long service life when used as a catalyst for a reaction for producing a hydro-carbon compound from methanol and/or dimethyl ether or a reaction for producing an unsaturated alcohol of the general formula (4) from an ~-olefin of the general for-mula ~2) and an aldehyde compound of the general formula (3).
Described below is a process for preparing a hydrocarbon by contacting a crystalline silicate com-pound of this invention, used as a catalyst, with metha-nol and/or dimethyl ether.
The methanol and dimethyl ether used as the starting materials in the process may be those which are generally employed in industry, and both substances may be used either alone or in admixture. The reaction is usually carried out in the gaseous phase, and in this case, the reaction system may be diluted with a suitable inert gas such as nitrogen or the like. It may also be diluted with water vapor, hydrogen or a lower hydrocar-, ~1~34739 1 bon such as methane, ethane, propane, ethylene, propy-lene or the like. The starting materials may, of course, contain water. The starting materials may also contain an alcohol having more carbon atoms such as ethanol, propanol or the like.
The reaction temperature is usually 200 to 800C, preferably 250 to 600C. The pressure to be applied during the reaction is usually 0.1 to 100 kg/cm2, preferably 0.5 to 50 kg/cm~, more preferably 0.8 to 20 kg/cm2.
Most of the reaction products obtained are aliphatic or aromatic hydrocarbons having 1 to 10 carbon atomsl and those having more than 10 carbon atoms are very little. Particularly, most of the aliphatic hydro-carbons are straight-chain or branched chain saturted or unsaturated hydrocarbons having 3 to 10 carbon atoms.
Most of the aromatic hydrocarbons produced are benzene, and alkylbenzenes such as toluene, xylene, ethylbenzene and the like.
In the case of using only methanol as the starting material, dimethyl ether is also produced as a by-product. This dimethyl ether is considered as a precursor for the formation of a hydrocarbon, and in the case where the reaction is conducted by using only dimethyl ether as the starting material, there is obtained quite the same reaction product as in the case o using only methanol as the starting material.

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1 ~his reaction produces a hydrocarbon having 1 to about 10 carbon atoms from methanol or dimethyl ether in a single step, and further, said hydrocarbon is close to that which i5 commonly used as the gasoline fraction. The crystalline silicate compound of this invention, when used as a catalyst, has the advan~age that the catalyst life is significantly longer than that of the conventional catalysts because the present compound is extremely high in thermal stability and also in resistance to catalyst poisons. Also, the compound of this invention, when used as a catalyst~
can easily be regenerated by calcining the used com-pound at a temperature of 500 to 700C.
Moreover, an explanation is made below of a process for preparing an unsaturated alcohol of the general formula (4) by contacting an -olefin of the general formula (2) and an aldehyde of the general formula (3) w:ith the crystalline silicate compound of this invention used as a catalyst.
As the ~-olefin of the general formula (2) used as one of the starting materials, the following may be mentioned: propylene, isobutene, 2-methyl-butene-l, 2-methyl-pentene-1, 2-methyl hexene-l, 2~methyl-heptene-1, 2-methyl-octene-1, 2,3-dimethyl-butene-l and the likeO Among them, pre~erred are -olefins represented by the general formula (5):

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l3 CH3-C=CH2 ....... ~.... (5) wherein R3 is as defined above, and isobutene is par-ticularly important for the industrial uses. In use of these ~-alefins, the concentration thereof is not critical and they may be suitably diluted with other solvents. Also, they may be used in the form of a mixture with other types of olefins. In the case of, for example, isobutene, it may be used in admixture with other olefins such as butene, butane, or the like.
Examples of the aldehyde represented by the general formula (3) include formaldehyde, acetaldehyde, propion-aldehyde, butyraldehyde and the like. Formaldehyde isparticularly preferred in view of reactivity. As the formaldehyde, there may be used paraformaldehyde;
formaldehyde polymers having a higher degree oE poly-merization such as -polyoxymethylene, or the like;
aqueous solutions of formaldehyde; formal; etc.
Although the ratio of the a-oleEin to the al-dehyde used as the starting materials is not critical, it is preferred that the ~-oleEin/aldehyde molar ratio is within the range of 0.25 to 20, particularly prefer-ably 0.4 to 10. Use of the aldehyde in excess of theabove-defined range promotes formation, as by-product, of other compounds than the objective unsaturated alco-31L~l34~73~9 1 hol, whereby it is made impossible to obtain the desired unsaturated alcohol industrially advantageously. Also, in the case of using the a-olefin in excess of the said range, there is necessitated a large amount o~ energy for the separation o-f the objective product 7 unsaturated alcohol, from the unreacted ~-olefin, and hence it is disadvantageous in energy.
As the solvent, there may be used any organic solvent inert to the reaction such as a saturated aliphatic hydrocarbon, an aromatic hydrocarbon, an alcohol, an ester, an ether, a heterocyclic compound and the like, and the typical examples of such organic solvents are pentane, hexane, benzene, ethanol, acetone~
dioxane, N-~ethyl-2-pyrrolidone, sulfolane and the like.
It is, however, possible to carry out the reaction without using the solvent.
The reaction temperature may be varied depend-ing on the kind of starting material used, but it is usually within the ragne of 20 to 200C, more pre-ferably 50 to 150C. If the reaction temperatureexceeds 200C, side reactions tend to occur such as decomposition or polymerization of unsaturated com-pounds such as ~-olefins and unsaturated alcohols, resulting in a reduced yield oE the objective unsat-urated alcohol. At a temperature as low as below 20C,the reaction rate is so low that the process is un~
suitable to carry out industrially. The pressure 73~

1 during the reaction is not critical, and usually the reaction may be performed under the own pressure of the reaction system or under a pressure of an inert gas or the like.
According to the process of this invention, it is possible to obtain the objective unsaturated alcohol with a high selectivity un~er relatively mild conditions without requiring a high temperature and a high pressure such as required in the conventional methods for the production of unsaturated alcohols, and because the crystalline silicate compound of this inven-tion is used in the solid form as a catalyst, the separation of the catalyst after the reaction is very easy.
This invention is described in further detail below referring to Examples, which are merely by way of illustration and not by way of limitation.

Example 1 In 32 g of distilled water was dissolved 41 g of water glass (containing 36.6% by wei~ht of 5iO2).
There was also prepared a solution of 1.36 g of lantha num sulfate, 6.4 g of tetrapropylammonium bromide and 5 ml of concentrated sulfuric acid in 43 g of distilled water. Both the solutions were added dropwise to 80 ml of a 20 wt~ aqueous NaCl solutLon with stirring. The resulting solution was fed into a 300-ml autoclave pro-3~

1 vided with a Teflon-sealed electromagnetic stirrer, heated to 160~C over 2 hours with stirring and then subjected to reaction at 160C for 48 hours. The stirring rate was maintained at 600 r.pOm. during this reaction~ The reaction product thus prepared was fil-tered to obtain about 12 g of a white powdery crystal-line lanthanum silicate. This product was well washed with distilled water, dried overnight at 80C under reduced pressure and then calcined at 550C for 6 hours.
As a result of an elemental analysis of the resulting product, it was ascertained that the product had a com-position represented by the formula:

(La203)- (sio2)ll2- (Na2)O.91-The thus obtained crystalline lanthanum sili-cate was subjected to the following ion-exchanging technique to remove Na+ and convert it into an H+ type.
The ion exchange was carried out by immersing said crystalline lanthanum silicate in 200 ml of a 5 wt%
aqueous NH~Cl solution for 6 hours, then removing the supernatant fluid and adding 200 ml of a 5 wt% aqueous NH4Cl solution again, after which this operation was repeated five times. The resultant proton type crystal-line lanthanum silicate was dried overnight at ao oc under reduced pressure and then calcined at 550C for 6 hours. Na was not detected as the result of elemental analysis of this product.

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~ he X-ray diffraction pattern of the specimen obtained is shown in Table 1.

Table 1 . . . _ _ ~
Lattice spacing ~ (A) Relative intensity (I/Imax) (~) _ _ - - , _ 11~ 0~2) 100~0 10~0 (+0~2) 65~1 6~69 (~0~05) 7~7 6~33 (+0~05) 11~0 5~98 (+0~05) 16~6 5069 (+0~0~) 9~0 ~
5~56 (+0~05) 9~8 5~02 (+0~05) 2~2

4~97 (+0O05) 2~6 4~60 (+0~02) 2~4 4~35 (+0~02) 5~9 4~23 (+0~02) 8~0 3~84 (+0~02) 57~0 3~71 (+0~02) 31~2 3~65 (+0~01) 7~4 3~44 (+0~01) 6~4 3~30 (+0~01) 7~4 3~06 (+0~01) 3~1 2~99 (~0~01) 3~0 2~96 (+0~01) ~
:

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1 In Table 1, the relative intensity refers to the peak ratio (%) to the maximum peak. The relative intensity of each peak may vary depending upon treat-ments involved such as ion exhcange with various types of cations or calcination at a high temperature. In the case of the specimen of the instant Example, the cations contained in the crystals are H~, and hence~ the peak corresponding to the lattice spacing of 11.13 A
is the maximum peak. In some cases, the lattice spacing may also vary slightly depending upon treatments. The amount of the solid acid in the crystalline silicate compound in the present Example was 0.268 meq/g, and the maximum value of the solid acid strength was at least -8.2 in terms of Hammett's acidity function.
This crystalline lanthanum silicate was press-molded under a pressure of 160 kg/cm2 to form particles having a size of 10 to 30 meshes. A tubular flow-reactor was filled with 1.5 g of these particles, and methanol was supplied thereto at a rate of 3.94 g/hr at a temperature of 350C under normal pressure, to obtain the results shown in Table 2.

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Table 2 Methanol conversion (~) 86O3 _. . _ . C~ ._ Aliphatic ~3 17.5 Selec-hydrocarbons C4 14.2 t v ty C5 9.1 C6 or more 13.1 . . ,.. _ . _ ... ~_.
Aromatic hydrocarbon 7.0 ¦ Dimethyl ether 26.1 Note: The table gives the data obtained after 2 hours from the start of the reaction.
Cn signifies a hydrocarbon having n carbon atoms.

Example 2 The same procedure as in Example 1 was repeated, except that 1.50 g of antimony triacetate was used for the 1.36 g of lanthanum sulfate, to o~tain a white powder of crystalline antimony silicate having a composition represented by the formula:
(Sb2o3)-(sio2)lo5(Na2o)o.9s-This crystalline antimony silicate was thensubjected to the ion-exchanging technique as in Example - 20 ~

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l to obtain a proton type crystalline antimony silicate.
The amount of solid acid in this product was 0.376 meq/g, and the maximum solid acid strength was at least -8.2 in terms of ~ammett's acidity function.
The X-ray diffraction pattern of the specimen obtained is shown in Table 3.
Table 3 . . . . . ~
Lattice spacing (A) Relative intensity ~ max) (%) . ~ _ _~
ll.l ~+0.2 ) lO0.0 lO.0 ~+0.2 ) 63.2 6.69 ~+0.05) 6.2 6.34 ~+0.05) 10.9 5098 ~+0.05) 15.7

5.70 ~+0.05) 8.5 5.S~ (+0.05) lO.l 5~02 ~+0.05) 5.5 4.97 (+0.05) 5.2 4.60 ~0.02)3.8 4.35 (+0.02) 5.5 4.25 (+0.02) 8.2 3.84 (+0.02) 58.4 3.71 ~+0.02) 29.g 3.79 (+0.01) 15.3 3.44 ~+0.01) 7.0 3.30 ~+0.01) .

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Table 3 (Cont'd) _,- _ . ..
.05 (+0.01) 5,9 2.98 (+0.01) _ _ _ _ ~

This crystalline antimony silicate was press-molded under a pressure of 160 kg/cm2 to form particles having a size of 10 to 30 meshes. A tubular flow-reactor was filled with 1.5 g of these particles, and methanol and nitrogen were supplied at rates of 3.94 .
g/hr and 1.20 liters/hr (at the normal temperature and normal pressure), respectively, at a temperature of 350C at normal pressure. The results obtained are shown in T~ble 4.

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- Table 4 . . _ _ . . .
Methanol conversion (%)_ 99.3 ~ _ c~ - .]

Aliphatic C3 13.9 Selec-hydrocarbons C4 23.1 ~MVlty~) C5 13.6 C6 or more 18.4 .._ ~

Aromatic hydrocarbon 20.7 ~imethyl ether 0.7 , . . . _ ... _ ~

Note: The table gives the data obtained after 2 hours from the start of the reaction.
Cn signifies a hydrocarbon having n carbon atoms,.

1 Example 3 The same procedure as in Example 1 was repeated, except that the 1.36 g of lanthanum sulfate was replaced by 4.83 g of bismuth acetate, to obtain a white powder of crystalline bismuth silicate having a composition represented by the formula:
(Bi2O3)~(siO2)87-(Na2o)o.97-This crystalline bismuth silicate was sub-jected to the same ion-exchanging technique as in Example 1 to obtain a proton type crystalline bismuth - 23 ~

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silicate. The X-ray diffraction pattern of the specimen thus obtained is shown in Table 5.
Using this crystalline bismuth silicate as a catalyst, methanol was reacted in the same way as in Example 1. The results obtained are shown in Table 6.

Table 5 Lattice spacing ~ (A) RelatiVe intensitY (I/lmax) (%) _ _ . . . . . .. _ llol (+0~2 ) 100~0 lQ~0 (+0~2 ) 64~5

6~70 (t0~05) 6~2 6~3~1s (+O~O~i) 10~3 5~99 (+0~05) 15~0 5~69 (+0~05) 8~5 5O57 (+0.05) 9.1 : 5.37 (+0.05) 2.7 5.03 (+0~05) 4.9 4~9~3 (+0~05) 5~3 4~60 (+0~02) 3.7 4~35 (+0~02) 5.9 4~25 (+0~02) 8.4 3~85 (+0.02) 5606 3.82 (+0~02) 37.0 3.71 (+0.02) 30.8 _ _ . . . _ .

L8~739 Table S (Cont'd) . .. ~ ~
3.65 (~0.02) 12.7 3.~3 (+0.01) 7.0 3.35 (+0.01) 5.9 3.32 (tO.O1) 8.2 3.06 (+0.01) ~.8 2.~9 (+0.01) 11.2 2.94 (~0.01) ~ _ Table 6 _ . _ Methanol conversion (~) 84.0 ~ ~ =

Aliphatic C3 18.4 Selec-tivity hydrocarbons C5 11 5 (Mole %) 6 or more 9.0 ._ . . _ ...... . ~_ Aromatic hydrocarbon 6.4 _ Dim~:hyl e~her 32.0 Note: The table gives the data obtained after 2 hours from the start of the reaction.
Cn signifies a hydrocarbon having n carbon atoms.
' .

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Example 4 Using the same catalyst as in Example 2, dimethyl ether was reacted under the same conditions as in Example 2, except that dimethyl ether was supplied at a rate of 1.4 liters/hr (at the normal temperature and normal pressure), to obtain the results shown in Table 7.

Table 7 . .. _ . ~
Dimethyl ether conversion (%) 99.9 . ,._~ .. ._ _ ~.~

Selec- Aliphatic C3 13.1 tivity hydrocarbons C4 21.9 (Mole %) C5 12,g C6 or more 20.0 ... __ .. _ Aromatic hydrocarbon 22.6 ~ ~ .

Note: The table gives the data obtained after 2 hours from the start o the reaction.
Cn signiies a hydrocarbon having n carbon atoms.

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1 Comparative Example 1 In 32 g of distilled water was dissolved 41 g of water glass (containing 36.6% of SiO2), and con~
centrated sulfuric acid was added dropwise thereto to adjust the pH to 6.5, after whlch the sediment produced was removed by filtration. After repeating 5 times washing with distilled water, the filtrate was put into a beaker, and 50 ml of distilled water was added thereto, after whi~h 1.5 g of antimony triacetate was added thereto. The resulting mixture was stirred at 80C for one hour. The contents in the beaker were transferred to an evaporating dish and evaporated to dryness with stirring, followed by drying overnight at 80C under reduced pressure. The resultant white solid was ground in a mortar and then calcined at 550C for 6 hours.
The X-ray diffraction pattern of the composite oxide thus obtained, antimony silicate, showed no diffraction peak, indicating that the obtained powder was amorphous. The solid acid amount was 0.401 meq/g and the maximum solid strength was greater than -5.6 in terms of Hammett's acidity function.
Using this antimony silicate as a catalyst, methanol and nitrogen were supplied`to the same tubular flow-reactor as in Example 2, under the same conditions as in Example 2, to obtain the results shown in Table 8.

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Table 8 . ~ ~
Methanol conversion (%) 5.9 . .
Selectivity Dimethyl (Mole ~) ether 100 Note: The data given in the table are those obtained after 2 hours from the start of the reactionO

Example 5 A 100-ml autoclave was filled with 1.35 g of the press-molded proton type crystalline antimony sili-cate obtained in Example 2 and 25.0 g of a 37 wt~
aqueous ormaldehyde solution, and then purged with nitrogen~ Then, 34.2 g of isobutene was introduced into the autoclave and the contents in the autoclave were subjected to reaction at 80C for 3 hours. The results obtained are shown in Table 9~

Table 9 . _ . . . _ , ., . _ _ _ . .. _ , .
Formaldahyde conversion (%) 38.3 ... __ . . .... ._ . . _ 3-Methyl-3-butene-1-ol 73~9 S~lec- 3-Methyl-1,3-butenediol 16.5 tivity (wt~) 4,4-Dimethyl-1,3-dioxane 7.8 Others 1.8 ~_ - . _ _ _ .

'73~9 1 Example 6 In a beaker was placed 62.4 g of ethyl sili-ca~e, and heated to 60C with stirring. Then, 16.0 g of tetrapropylammonium bromide and 50 ml of ethanol were added thereto, and the resulting mixture was stirred until it became homogeneous. A solution formed by dis-solving 3.68 g of lanthanum chloride in S g of distilled water was then added to the beaker, and thereafter, an aqueous NaOH solution formed by dissolving 2.4 g of NaOH
in 15 ml of distilled water was added gradually to the beaker while continuing the stirring, whereby the ethyl silicate in the mixture was gradually hydrolyzed, and the mixture became yellow-turbid gradually. Heating and stirring were further continued, and water was added while distilling off ethanol, to obtain 170 ml of a mix-ture completely freed from ethanol.
A 300-ml autoclave was filled with the mixture thus obtained and heated to elevate the temperature from normal temperature to 150C over about 2 hours with stirring, at which temperature the mixture was kept for 48 hours, to effect the reaction. In this case, the stirring rate was 600 r.p.m. and the pressure applied was 5.2 kg/cm2. The reaction product thus obtained was filtered to obtain about 13 g of a light-brown powder of crystalline lanthanum silicate. This was well washed with distilled water, dried overnight at 80C under reduced pressure, and then calcined at 550C for 6 _ 29 -73~

1 hours. The elementary analysis of this product showed that the product had a composition represented by the formula: (La2O3~ (si2)52 (Na2)0.95 The thus obtalned crystalline lanthanum sili-cate was converted into a proton type by the Eollowingion-exchanging technique: The crystalline lanthanum silicate was immersed in 200 ml of a 5 wt% aqueous N~4Cl solution for 6 hrs, the supernatant fluid was removed, and 200 ml of said aqueous solution was added. This operation was repeated 5 times~ The proton type crys-talline lanthanum silicate thus obtained was dried over~
night at 80C under reduced pressure and then calcined at 550C for 6 hours.
The X-ray diffraction pattern of this proton type crystalline lanthanum silicate is shown in Table 10 .
Using proton type crystalline lanthanum silicate as a catalyst, formaldehyde was reacted with isobutene in the same manner as in Example 5, to obtain the results shown in Table 11~

Table ]0 Lattice spacing ~ (A) Relative intenslty (I/ImaX) (%) .
11.2 (+0.2 ) 100.0 10.0 (+0.2 ) 51.4 6.~9 (+0.05) ~.1 6.35 (~0.05) 13.7 6.00 (+0.05) 19.0 5.71 (+0.05) ~.7 5.57 (+0.05) 12.3 5.04 (+0.05) 5,6 4098 (+0.05) 7.3 4.61 (+0.02) 4.2 4.36 (+0.02) 6.3 4.25 (+0.02) 9.8 3.85 (+0.02) 68.2 3.72 (+0.02) 37.5 3.66 (+0.01) 13.6 3,~4 (+0.01) 6.6 3.30 (+0.01) 8.8 3.06 (+0.01) 5.3 2.99 (+0.01) 15.1 2.95 (+0.01) 8.2 ~ ... . .. ... ~

3~

~able 11 .~ . . ~
Formaldehyde conversion (%) 29.1 ~ ._ 3-Methyl-3-butene-1-ol 84.7 Selec- 3-Methyl-1,3-butenediol 11.3 tivity (wt%) 4,4-Dimethyl-1,3-dioxane 3.3 _ Others 0,7

Claims (21)

WHAT IS CLAIMED IS:

1. A crystalline silicate compound represented by the composition formula (1):

(1) wherein M is at least one element selected from the group consisting of antimony, bismuth and lanthanide series rare earth elements, n is the valency of the element M, O is oxygen, x is a number of 1 to 5,000, Y is at least one kind coordinating cation, m is the valency of the cation Y, and y is a number of 0.1 to 1.

2. A crystalline silicate compound according to Claim 1, wherein M is at least one element selected from the group consisting of antimony, bismuth, lanthanum, cerium, praseodymium, and neodymium.

3. A crystalline silicate compound according to Claim 1, wherein M is lanthanum, cerium or antimony.

4. A crystalline silicate compound according to Claim 1, wherein x is a number of 5 to 1,000.

5. A crystalline silicate compound according to Claim 1, wherein Y is an inorganic cation or an organic cation or both of them.

6. A crystalline silicate compound according to claim 5, wherein the inor-ganic cation is selected from the group consisting of hydrogen cation and metal-lic cations.

7. A crystalline silicate compound according to claim 6, wherein the meta-llic cation is the cation of at least one element selected from the group consis-ting of alkali metals, alkaline-earth metals, metals of Group VIII of the Perio-dic Table, copper, silver, zinc, cadmium, manganese, rhenium, chromium, molyb-denum, tungsten and rare-earth elements.

8. A crystalline silicate compound according to claim 5, wherein the orga-nic cation is at least one kind cation selected from ammonium cation and alkyl-ammonium cations.

9. A crystalline silicate compound according to claim 1, 5 or 6, wherein y is a number of 0.4 to 1.

10. A crystalline silicate compound according to claim 1, 5 or 6, wherein y is a number of 0.7 to 1.

11. A process for preparing a hydrocarbon compound which comprises contact-ing methanol or dimethyl ether or both of them with a catalyst containing as its principal ingredient a crystalline silicate compound represented by the composi-tion formula (1):

(1) wherein M is at least one element selected from the group consisting of antimony, bismuth and lanthanide series rare earth elements, n is the valency of the ele-ment M, O is oxygen, x is a number of 1 to 5,000, Y is at least one kind coordin-ating cation, m is the valency of the cation Y, and y is a number of 0.1 to 1, wherein the reaction is carried out at a temperature of 200° to 800°C and under a pressure of 0.1 to 100 kg/cm2.

12. The process according to claim 11, wherein the reaction is carried out at a temperature of 250° to 600°C.

13. The process according to claim 12, wherein the reaction is carried out under a pressure of 0.8 to 20 kg/cm2.

14. A process for preparing an unsaturated alcohol represented by the for-mula (4):

(4) wherein R1, R2, R3 and R4, which may be the same or different, represent hydrogen atoms, alkyl groups having 1 to 8 carbon atoms or alkenyl groups having 2 to 8 carbon atoms, which comprises contacting a catalyst containing as its principal ingredient a crystalline silicate compound represented by the composition formula (1):
(1) wherein M is at least one element selected from the group consisting of antimony, bismuth and lanthanum series rare earth elements, n is the valency of the element M, O is oxygen, x is a number of 1 to 5,000, Y is at least one kind coordinating cation, m is the valency of the cation Y, and y is a number of 0.1 to 1, with an .alpha.-olefin represented by the formula (2):

(2) wherein R1, R2 and R3, which may be the same or different, represent hydrogen atoms, alkyl groups having 1 to 8 carbon atoms or alkenyl groups having 2 to 8 carbon atoms, and an aldehyde represented by the formula (3):

wherein R4 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, wherein the reaction is carried out at a temperature of 20° to 200°C and the molar ratio of the .alpha.-olefin to the aldehyde is 0.25-20.

15. A process according to claim 14, wherein the reaction is carried out at a temperature of 50° to 150°C.

16. A process according to claim 14, wherein the .alpha.-olefin is propylene, iso-butene, 2-methyl-butene-1, 2-methyl-pentene-1, 2-methyl-hexene-1, 2-methyl-hept-ene-1, 2-methyl-octene-1, or 2,3-dimethyl-butene-1.

17. A process according to claim 14, wherein the .alpha.-olefin is isobutene.

18. A process according to claim 16 or 17, wherein the aldehyde is formalde-hyde, acetaldehyde, propionaldehyde or butyraldehyde.

19. The process according to claim 14, wherein the molar ratio of the .alpha.-ole-fin to the aldehyde is 0.4-10.

20. A crystalline silicate compound according to claim 7 or 8, wherein y is a number of 0.4 to 1.

21. A crystalline silicate compound according to claim 7 or 8, wherein y is a number of 0.7 to 1.