Note: Descriptions are shown in the official language in which they were submitted.
3~
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
-- 1 --
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have been replaced by other elements, and there are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structure in which aluminum has been replaced by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been replaced by germanium.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
-- 2 --
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.
.~ - 3 _
73~
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
' ,.
-- 5
39
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
.
-- 6 --
3~
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
-- 8
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
- 10
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.
; .
- 12 -
73~
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):
- 13 -
73~
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-
- 14 -
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
- 15 -
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-
- 16 -
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.
- 17 -
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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) ~
:
- 18 -
~34173~
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.
-- 19 --
73~
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 ~
73~
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)
.
21 -
73~
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.
- 22 -
473~
- 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 ~
73~
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
_ _ . . . _ .
- 24 -
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.
' .
- 25 -
~L8~73~
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.
- 26 -
73~
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.
~ 27 -
3~
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
~_ - . _ _ _
.
- 28 -
'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~
- 30 -
7391
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
~ ... . .. ... ~
- 31 -
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
- 32 -
