U.S. patent application number 10/211413 was filed with the patent office on 2003-01-16 for catalyst for production of epoxides and methods for production thereof and epoxides.
This patent application is currently assigned to Nippon Shokubai Co. Ltd., a Japan Corporation. Invention is credited to Mikawa, Masatsugu, Uchida, Shin-Ichi.
Application Number | 20030013600 10/211413 |
Document ID | / |
Family ID | 17445257 |
Filed Date | 2003-01-16 |
United States Patent
Application |
20030013600 |
Kind Code |
A1 |
Mikawa, Masatsugu ; et
al. |
January 16, 2003 |
Catalyst for production of epoxides and methods for production
thereof and epoxides
Abstract
It provide a catalyst for the production of epoxides by a
vapor-phase oxidation of an unsaturated hydrocarbon having a chain
length of 4-20 carbon atoms and containing no allylic hydrogen
atom, characterized by having a catalytic component containing
silver and at least one element selected from the group consisting
of alkali metals and thallium deposited onto a carrier obtained by
mixing .alpha.-alumina having a sodium content in the range of 1-70
mmol (as reduced to Na) per kg of .alpha.-alumina with an aluminium
compound, a silicon compound, and a sodium compound and calcining
the resultant mixture, the carrier having a silicon content (as
reduced to SiO.sub.2) in the range of 0.3-11.5 mass % based on the
mass of the carrier and a sodium content (as reduced to Na.sub.2O)
in the range of 0.11-2.5 mass % based on the mass of the
carrier.
Inventors: |
Mikawa, Masatsugu;
(Yokohama-shi, JP) ; Uchida, Shin-Ichi;
(Himeji-shi, JP) |
Correspondence
Address: |
Y. ROCKY TSAO
Fish & Richardson P.C.
225 Franklin Street
Boston
MA
02110-2804
US
|
Assignee: |
Nippon Shokubai Co. Ltd., a Japan
Corporation
|
Family ID: |
17445257 |
Appl. No.: |
10/211413 |
Filed: |
August 2, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10211413 |
Aug 2, 2002 |
|
|
|
09664170 |
Sep 18, 2000 |
|
|
|
Current U.S.
Class: |
502/60 ;
549/534 |
Current CPC
Class: |
C07D 303/04 20130101;
C07D 301/10 20130101; B01J 21/12 20130101; B01J 23/66 20130101 |
Class at
Publication: |
502/60 ;
549/534 |
International
Class: |
C07D 301/10; B01J
029/04; B01J 029/87 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 21, 1999 |
JP |
11-267467 |
Claims
1] A catalyst for the production of epoxides by a vapor-phase
oxidation of an unsaturated hydrocarbon having a chain length of
4-20 carbon atoms and containing no allylic hydrogen atom,
characterized by having a catalytic component containing silver and
at least one element selected from the group consisting of alkali
metals and thallium deposited onto a carrier obtained by mixing
.alpha.-alumina having a sodium content in the range of 1-70 mmol
(as reduced to Na) per kg of .alpha.-alumina with an aluminium
compound, a silicon compound, and a sodium compound and calcining
the resultant mixture, the carrier having a silicon content (as
reduced to SiO.sub.2) in the range of 0.3-11.5 mass % based on the
mass of the carrier and a sodium content (as reduced to Na.sub.2O)
in the range of 0.11-2.5 mass % based on the mass of the
carrier.
2] A catalyst according to claim 1, wherein a volume ratio of pores
having diameters of not more than 0.5 .mu.m is not more than 50%,
and not more than 5 .mu.m is more than 65%, based on the
carrier.
3] A catalyst according to claim 1, wherein said carrier has a
specific surface area in the range of 0.1-5 m.sup.2/g based on the
mass of the carrier, a water absorption ratio in the range of
20-50%, and an average pore diameter in the range of 0.3-3.5
.mu.m.
4] A catalyst according to claim 1, wherein the mass ratio of
silicon to sodium compound in said catalyst (SiO.sub.2/Na.sub.2O)
is in the range of 1-20.
5] A catalyst according to claim 1, wherein said a silicon content
of said carrier per unit surface area is in the range of 0.1-20
mass %/(m.sup.2/g) based on the mass of said carrier.
6] A catalyst according to claim 1, which contains silver as a
catalytic component in the range of 5-25% by mass and at least one
element selected from the group consisting of alkali metals and
thallium in the range of 0.001-5% by mass, based on the total mass
of the catalyst.
7] A catalyst according to claim 1, wherein a catalyst component
containing silver and at least one element selected from the group
containing of alkali metals and thallium is deposited on said
carrier and thereafter the resultant composite is eventually
heat-treated in an inert gas containing substantially no oxygen at
an elevated temperature in the range of 400-700.degree. C.
8] A method for the preparation of a catalyst for the production of
an epoxide by the vapor-phase oxidation of an unsaturated
hydrocarbon having a chain length of 4-20 carbon atoms and
containing no allylic hydrogen atom, characterized by causing a
solution containing silver and at least one element selected from
the group consisting of alkali metals and thallium to impregnate a
carrier obtained by adding an aluminum compound, a silicon
compound, and a sodium compound to .alpha.-alumina having a sodium
content (as reduced to Na) in the range of 1-70 mmols per kg of the
.alpha.-alumina and calcining the resultant mixture and having a
silicon content (as reduced to SiO.sub.2) in the range of 0.3-11.5
mass % per mass of the carrier and a sodium content (as reduced to
Na.sub.2O) in the range of 0.11-2.5 mass % per mass of the
carrier.
9] A method according to claim 8, wherein a high-temperature heat
treatment is-performed in an inert gas containing substantially no
oxygen at an elevated temperature in the range of 400-700.degree.
C. after a silver-carrying catalyst is obtained in consequence of
said impregnation.
10] A method for the production of epoxides, which comprises
effecting said production by a vapor-phase oxidation of an
unsaturated hydrocarbon having a chain length of 4-20 carbon atoms
and containing no allylic hydrogen atom with a molecular
oxygen-containing gas in the presence of a catalyst set forth in
any of Items (1)-(7).
11] A method for the production of 3,4-epoxy-1-butene, which
comprising effecting said production by a vapor-phase oxidation of
1,3-butadiene with a molecular oxygen-containing gas in the
presence of a catalyst set forth in any of Items (1)-(7).
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates to a catalyst for the production of
epoxides by catalytic vapor-phase oxidation of an unsaturated
hydrocarbon having a carbon length of 4-20 carbon atoms and
containing no allylic hydrogen atom with a molecular
oxygen-containing gas thereby obtaining epoxides selectively in
high yield.
[0003] 2. Description of Related Art
[0004] Epoxide compounds are enable to use for extent various
reactions because of their high reactivity. For example
3,4-epoxy-1-butene which is one of epoxides of an unsaturated
hydrocarbon having a carbon length of 4-20 carbon atoms and
containing no allylic hydrogen atom, is an intermediate for the
production of tetrahydrofuran (U.S. Pat. No. 5,034,545). Also the
intermediate is used for a production of 1,2-butylene oxide (U.S.
Pat. No. 5,034,545). It has been heretofore known that
3,4-epoxy-1-butene is produced by catalytic a vapor-phase oxidation
of 1,3-butadiene with a molecular oxygen-containing gas in the
presence of a catalyst. It has been also known that alumina,
silicon and so on are used as the carrier thereof and an alkali
metal and a thallium oxide are used as cationic components besides
silver as catalyst component (WO89/07,101, WO93/03,024, U.S. Pat.
Nos. 5,138,077, 5,081,096, and WO94/13,653).
[0005] These methods disclosed above, however, have the
disadvantage that catalysts used therein possess low activity,
exhibit low selectivity for 3,4-epoxy-1-butene, and suffer from a
short catalyst life.
[0006] The catalysts for synthesizing epoxides include such
catalysts as are obtained by depositing silver on porous inorganic
carriers and used for the production of ethylene oxide. Among
others there are silver-carried catalysts have been developed with
a view to offering several years of service life on a commercial
production. When these catalysts are used in the reaction for
producing 3,4-epoxy-1-butene by the catalytic vapor-phase oxidation
of 1,3-butadiene, they generally manifest substantially no
catalytic activity or, if catalytically active at all, offer very
short service lives as a catalyst. The epoxide of an unsaturated
hydrocarbons having a chain length of 4-20 carbon atoms and
containing no allylic hydrogen atom include such compounds as
3,4-epoxy-1-butene which need quantity production. For the
catalysts to be effectively used in the reaction of a vapor-phase
oxidation, it is an extremely important task for the sake of
commercial production to enhance the performance of catalyst and
elongate the service life of catalyst. Since the cause for
degrading these catalysts remains yet to be elucidated, no
effective method for solving this problem of degradation has been
perfected so far.
SUMMARY OF THE INVENTION
[0007] An object of this invention, therefore, is to provide a
novel catalyst for the production of epoxides by a vapor-phase
oxidation of an unsaturated hydrocarbon having a carbon length of
4-20 carbon atoms and containing no allylic hydrogen atom.
[0008] Another object of this invention is to provide a method for
manufacture of a catalyst for the production of epoxides having
high activity, exhibiting high selectivity for epoxides, and
enjoying a long catalyst life.
[0009] Further object of this invention is to provide a method of a
catalyst for producing exoides.
[0010] Still another object of this invention is to provide a
method for the production of 3,4-epoxy-1-butene in high yield by
catalytic vapor-phase oxidation of 1,3-butadiene.
[0011] The objects mentioned above are accomplished by the
following Items (1)-(4).
[0012] (1) A catalyst for the production of epoxides by a
vapor-phase oxidation of an unsaturated hydrocarbon having a chain
length of 4-20 carbon atoms and containing no allylic hydrogen
atom, characterized by having a catalytic component containing
silver and at least one element selected from the group consisting
of alkali metals and thallium deposited onto a carrier obtained by
mixing .alpha.-alumina having a sodium content in the range of 1-70
mmol (as reduced to Na) per kg of .alpha.-alumina with an aluminium
compound, a silicon compound, and a sodium compound and calcining
the resultant mixture, the carrier having a silicon content (as
reduced to SiO.sub.2) in the range of 0.3-11.5 mass % based on the
mass of the carrier and a sodium content (as reduced to Na.sub.2O)
in the range of 0.11-2.5 mass % based on the mass of the
carrier.
[0013] (2) A method for the preparation of a catalyst for the
production of an epoxide by the vapor-phase oxidation of an
unsaturated hydrocarbon having a chain length of 4-20 carbon atoms
and containing no allylic hydrogen atom, characterized by causing a
solution containing silver and at least one element selected from
the group consisting of alkali metals and thallium to impregnate a
carrier obtained by adding an aluminum compound, a silicon
compound, and a sodium compound to .alpha.-alumina having a sodium
content (as reduced to Na) in the range of 1-70 mmols per kg of the
.alpha.-alumina and firing the resultant mixture and having a
silicon content (as reduced to SiO.sub.2) in the range of 0.3-11.5
mass % per mass of the carrier and a sodium content (as reduced to
Na.sub.2O) in the range of 0.11-2.5 mass % per mass of the
carrier.
[0014] (3) A method for the production of epoxides, which comprises
effecting said production by a vapor-phase oxidation of an
unsaturated hydrocarbon having a chain length of 4-20 carbon atoms
and containing no allylic hydrogen atom with a molecular
oxygen-containing gas in the presence of a catalyst set forth in
Item (1).
[0015] (4) A method for the production of 3,4-epoxy-1-butene,
[0016] which comprising effecting said production by a vapor-phase
oxidation of 1,3-butadiene with a molecular oxygen-containing gas
in the presence of a catalyst set forth in Item (1).
[0017] The catalyst of this invention, owing to the construction
thereof described above, excels in activity and selectivity for
epoxide and enjoys a long life time. The use of this catalyst
allows epoxide to be produced with high productivity by catalytic
vapor-phase oxidation of unsaturated hydrocarbon.
[0018] The above and other objects, features and advantages of the
present invention will become clear from the following description
of the preferred embodiments.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] The first aspect of this invention concerns a catalyst for
the production of epoxides by a vapor-phase oxidation of an
unsaturated hydrocarbon having a chain length of 4-20 carbon atoms
and containing no allylic hydrogen atom, characterized by having a
catalytic component containing silver and at least one element
selected from the group consisting of alkali metals and thallium
deposited onto a carrier obtained by mixing .alpha.-alumina having
a sodium content in the range of 1-70 mmol (as reduced to Na) per
kg of .alpha.-alumina with an aluminium compound, a silicon
compound, and a sodium compound and calcining the resultant
mixture, the carrier having a silicon content (as reduced to
SiO.sub.2) in the range of 0.3-11.5 mass % based on the mass of the
carrier and a sodium content (as reduced to Na.sub.2O) in the range
of 0.11-2.5 mass % based on the mass of the carrier.
[0020] The unsaturated hydrocarbon contemplated by this invention
is only required to be a compound which has a chain length of 4-20
carbon atoms and containing no allylic hydrogen atom. The term
"allylic hydrogen" as used in this invention means the two hydrogen
atoms which are bound to the carbon atoms adjoining the double bond
of an allyl group represented by the formula,
CH.sub.2.dbd.CH--CH.sub.2-- and the expression "containing no
allylic hydrogen" means that at least one of the two hydrogen atoms
mentioned above is absent.
[0021] To be specific, the compound in question is represented by
the following formula.
CH.sub.2.dbd.C(R.sub.1)(R.sub.2)
[0022] (wherein R.sub.1 denotes a hydrogen atom or an alkyl group,
R.sub.2 denotes an aryl group or a tertiary alkyl group or
--C(R.sub.3).dbd.CH.sub.2, and R.sub.3 denotes a hydrogen atom or
an alkyl group.)
[0023] The term "chain length" as used herein is to be interpreted
as embracing not only a chain optionally containing a branch but
also a ring. The alkyl groups denoted by R.sub.1 and R.sub.3 are
independently methyl group, ethyl group, butyl group, heptyl group,
octyl group, etc. Then, R.sub.2 is t-butyl group, phenyl group,
etc.
[0024] The unsaturated hydrocarbon having a chain length of 4-20
carbon atoms and containing no allylic hydrogen atom and forming
the target for this invention is an unsaturated hydrocarbon having
a chain length preferably in the range of 4-12, more preferably in
the range of 4-8 carbon atoms and containing no allylic hydrogen.
As concrete examples of the unsaturated hydrocarbon of interest,
such compounds as 1,3-butadiene, tertiary butyl ethylene, and
styrene may be cited. In this invention, it is advantageous to use
1,3-butadiene or tertiary butyl ethylene. In consideration of the
convenience of explanation, the production of 3,4-epoxy-1-butene by
the catalytic a vapor-phase oxidation of 1,3-butadiene will be
described as a typical example.
[0025] The catalyst of the present invention for the production of
epoxides, as described above comprises catalyst components silver
and at least one element selected from the group consisting of
alkali metals and thallium and a carrier thereof for depositing
these elements. The carrier to be deposited catalytic components
comprises mainly .alpha.-alumina. The .alpha.-alumina to be used in
the present invention imposes no particularly restriction except
for having a sodium content in the range of 1-70 mmol (as reduced
to Na) per kg of .alpha.-alumina. The .alpha.-alumina to be on the
market is available in this invention.
[0026] If the sodium content is less than 1 mmol/kg, the shortage
will be at a disadvantage in lowering the selectivity. Conversely,
if the sodium content exceeds 70 mmols/kg, the excess will be at a
disadvantage in degrading both the degree of conversion and the
selectivity without bringing a proportionate addition to the
catalytic activity. That is, the present invention is enabled, by
using .alpha.-alumina having a sodium content in the range of 1-70
mmols/kg, to secure the stability of .alpha.-alumina as a carrier
and, by allowing the .alpha.-alumina to contain sodium in an amount
in the specific range, to acquire exceptionally outstanding
selectivity and degree of conversion as well. The fact that by
varying the sodium content in the carrier as described above, the
catalyst for oxidizing a hydrocarbon compound having a chain length
of 4-20 carbon atoms and containing no allylic hydrogen atom is
enabled to acquire excellent selectivity and degree of conversion
has never been known to the art to date. Particularly in the
catalyst of this invention for the production of an epoxide, since
the .alpha.-alumina is mixed with a sodium compound and then
calcined, the carrier never fails to incorporate therein a sodium
component besides the sodium inherently present in the
.alpha.-alumina. It has been ascertained that notwithstanding the
complete carrier has a fixed sodium content, the carrier is
deficient in either the selectivity or the degree of conversion
when the sodium content (as reduced to Na) in the .alpha.-alumina
itself deviates from the range of 1-70 mmols/kg. Though the reason
for this peculiar mechanism is not clear, the mechanism may be
logically explained by a supposition that the catalyst manifests an
excellent catalytic activity when it incorporates therein sodium or
a sodium compound in a specific amount.
[0027] The carrier to be used in the present invention is obtained
by mixing .alpha.-alumina mentioned above with at least an
aluminium compound, a silicon compound and a sodium compound,
further an organic binder and a pore forming agent and calcining
them, the silicon content (converted into SiO.sub.2) is in the
range of 0.3-11.5 mass % based on the mass of the carrier, more
preferably 0.5-11 mass %, and most preferably 0.5-10 mass %. If the
silicon content is less than this limit, the amount of acid on the
surface of the carrier will be unduly small and the effect due to
the acidity of the surface will manifest with difficulty.
[0028] In contrast, if the silicon content exceeds this limit, the
surface area of the carrier will not be controlled easily.
[0029] The content of the aluminium compound which is added into
.alpha.-alumina except .alpha.-alumina itself imposes no
restriction particularly, but preferably in the range of 0.1-20
mass % based on the mass of the carrier, more preferably 0.5-15
mass %, and most preferably 1-10 mass %. If the aluminium content
exceeds this limit, the excess will be at a disadvantage in
degrading the selectivity.
[0030] On the other hand, the sodium content of the carrier is in
the range of 0.11-2.5 mass % based on the mass of the carrier, more
preferably 0.11-2.3 mass %, and most preferably 0.11-2.0 mass
%.
[0031] If the content of a sodium compound is less than 0.11 mass
%, the shortage will be at a disadvantage in degrading the strength
of the carrier during the reaction of oxidation of an unsaturated
hydrocarbon having a chain length of 4-20 carbon atoms and
containing no allylic hydrogen atom and impairing the selectivity
and the degree of conversion as well. Conversely, if the content
exceeds 2.5 mass %, the excess will be at a disadvantage in
degrading both the selectivity and the degree of conversion. This
invention, by limiting the content of a sodium compound in the
carrier to the range mentioned above in the reaction of oxidation
of an unsaturated hydrocarbon having a chain length of 4-20 carbon
atoms and containing no allylic hydrogen atom, is enabled to
acquire an effect of producing a catalyst having a long service
life and excelling in both the selectivity and the degree of
conversion as well.
[0032] Further, the silicon (as reduced to SiO.sub.2) content per
unit surface area of the carrier is in the range of 0.1-20 mass
%/(m.sup.2/g), preferably 0.15-18 mass %/(m.sup.2/g), and most
preferably 0.2-15 mass %/(m.sup.2/g). If the content of silicon is
less than 0.1 mass %, the shortage will be at disadvantage in
suffering the catalyst to manifest an inferior initial performance
and an inferior strength in the reaction of oxidation of a
hydrocarbon compound having a chain length of 4-20 carbon atoms and
containing no allylic hydrogen atom. Conversely, if this content
exceeds 20 mass %, the excess will be at a disadvantage in
compelling the catalyst to suffer such a large decline in the
selectivity, resulting in ineffective. This invention has
originated in the discovery that, by limiting the content of
silicon in the carrier to the aforementioned range in the reaction
of oxidation of an unsaturated hydrocarbon having a chain length of
4-20 carbon atoms and containing no allylic hydrogen atom, it is
made possible to secure the physical strength of the carrier and
elongate the service life of the catalyst as well.
[0033] The mass ratio of silicon to sodium in the carrier
(SiO.sub.2/Na.sub.2O) is in the range of 1-20, more preferably
2-20, and most preferably 3-18.
[0034] As mentioned above, the sodium compound content (as reduced
to Na.sub.2O) in the carrier, the amount of silicon (as reduced to
SiO.sub.2) per unit surface area, and the mass ratio of silicon (as
reduced to SiO.sub.2) to sodium compound (as reduced to Na.sub.2O)
are important factors which may be depended on by chemical property
of the surface of the carrier (the acidity and basicity) and
physical property of the carrier itself. If the sodium content is
unduly low, the strength of the carrier will be degraded. The
sodium content may depend on the amount of silicon in the carrier.
If the sodium content is unduly large, the surface acidity will be
lost, and the produced catalyst will be deficient in initial
performance and in catalyst life as well. In the reaction of
oxidation of a hydrocarbon compound having a chain length of 4-20
carbon atoms and containing no allylic hydrogen atom, the initial
performance of the catalyst reflects the degree of conversion of
the hydrocarbon compound and the selectivity of the epoxide at a
specific reaction temperature after the start of the reaction. The
decline of the catalyst performance represented by the degree of
conversion manifests in the form of a decrease in either or both of
the degree of conversion and the selectivity and brings about
harm.
[0035] Incidentally, the carrier is confirmed by the X-ray
diffraction analysis to have formed Al.sub.6Si.sub.2O.sub.13
originating in the silica component besides the
.alpha.-Al.sub.2O.sub.3. The presence of this
Al.sub.6Si.sub.2O.sub.13 is believed to bring an influence on the
manifestation of the acidity of the surface of the produced
carrier. When this carrier was tested for acidity, it showed such
acidity as detectable with an indicator (methyl red) of pKa+4.8.
From this fact, it is inferred that the carrier used in this
invention is enabled, by mixing an aluminum compound, a silicon,
and a sodium compound and calcining the resultant mixture, to
manifest eventually such acidity as detectable with an indicator of
pKa+4.8 and further that the catalyst is enabled, by causing the
carrier to bring a synergistic effect with a catalytic component,
i.e. such a cation component as at least one element selected from
the group consisting of alkali metals and thallium, to manifest an
exceptionally high catalytic performance.
[0036] In order that the carrier used in this invention may enable
the catalyst for the production of epoxide contemplated by this
invention to acquire an ability to repress sequential oxidation,
for example, due to the stagnation in the micropores in the
catalyst of the product (such as, for example, 3,4-epoxy-1-butene)
of the oxidation of an unsaturated hydrocarbon having a chain
length of 4-20 carbon atoms and containing no allylic hydrogen atom
by the use of the catalyst of this invention and exhibit high
selectivity, the amount of the micropores constitutes itself an
important factor. It is particularly important to control the
formation of micropores in the catalyst so that the volume ratio of
pores having diameters of not more than 0.5 .mu.m is not more than
50%, more preferably not more than 45%, and most preferably not
more than 40% and the volume ratio of the pores having diameters of
not more than 5 .mu.m exceeds 65%, more preferably exceeds 70%.
Particularly, when the raw material compound is a hydrocarbon
compound having a chain length of 4-20 carbon atoms and containing
no allylic hydrogen atom, the carrier prefers copious presence
therein of micropores having diameters of 0.5-5 .mu.m. If the
volume ratio of pores having diameters of not more than 0.5 .mu.m
exceeds 50%. the excess will induce formation of the by-product by
the sequential reaction and degrade the selectivity. Conversely, if
the. volume ratio of the pores having diameters exceeding 5 .mu.m
in the carrier exceeds 65%, the excess will be at a disadvantage in
degrading the selectivity and the grade of conversion due to the
absence of the retention of the raw material compound in the pores
of the catalyst and preventing the catalyst from attaining an
extension of the service life thereof.
[0037] The specific surface area of the carrier is in the range of
0.1-5 m.sup.2/g, more preferably 0.3-3 m.sup.2/g, and most
preferably 0.5-3 m.sup.2/g. It is difficult to produce a catalyst
with sufficient strength when using a carrier which has a surface
area of more than 5 m.sup.2/g, and such catalyst has only a low
selectivity. In terms of catalyst life, it is important that the
sufficient amount of silver in the form of fine particle is
supported on the carrier. It is difficult to produce a catalyst
having both of above-mentioned factors when using the carrier
having a surface area of less than 0.1 m.sup.2/g.
[0038] The water absorption ratio of the carrier is in the range of
20-50%, more preferably 25-50%, and most preferably 30-45%. If this
absorption ratio is less than 20%, it will be difficult to deposit
the prescribed amount of silver on the carrier. Conversely, if this
water absorption ratio exceeds 50%, the carrier will be deficient
in terms of strength at all.
[0039] The second aspect of this invention concerns a method for
the preparation of a catalyst for the production of an epoxide by
the vapor-phase oxidation of an unsaturated hydrocarbon having a
chain length of 4-20 carbon atoms and containing no allylic
hydrogen atom, characterized by causing a solution containing
silver and at least one element selected from the group consisting
of alkali metals and thallium to impregnate a carrier obtained by
adding an aluminum compound, a silicon compound, and a sodium
compound to .alpha.-alumina having a sodium content (as reduced to
Na) in the range of 1-70 mmols per kg of the .alpha.-alumina and
firing the resultant mixture and having a silicon content (as
reduced to SiO.sub.2) in the range of 0.3-11.5 mass % per mass of
the carrier and a sodium content (as reduced to Na.sub.2O) in the
range of 0.11-2.5 mass % per mass of the carrier.
[0040] The carrier to be used in the invention may be prepared, for
example, by the following method. After .alpha.-alumina powder
mentioned above is mixed with water, an aluminium compound, silicon
and a sodium compound, then added an organic binder. The obtained
composition is mixed and formed according to designated form and
measurement. After drying it, it is calcined at a temperature in
the range of 1,100-1,700.degree. C., preferably 1,150-1,600.degree.
C.
[0041] As the .alpha.-alumina powder to be used in the present
invention, .alpha.-alumina secondary particles which have a
diameter in the range of 20-200 .mu.m, preferably 25-100 .mu.m and
have a specific surface area thereof in the range of 0.1-20
m.sup.2/g, preferably 0.3-15 m.sup.2/g, may be used in the present
invention, wherein the secondary particles are composed by alumina
primary particles having a diameter in the range of 0.1-10 .mu.m,
preferably 1-7 .mu.m. The sizes of the primary particles and the
secondary particles of the raw material .alpha.-alumina powder
bring an influence to bear on the pore distribution in the
completed carrier. The pore distribution of the carrier is
particularly preferred to be such that the volume ratio of the
pores having diameters of not more than 0.5 .mu.m is not more than
50% and the volume ratio of the pores having diameters of not more
than 5 .mu.m is not less than 65%. By using .alpha.-alumina formed
of the secondary particles mentioned above, it is made possible to
obtain readily a carrier having a pore distribution in the range
mentioned above.
[0042] In the present invention, an aluminium compound to be mixed
with .alpha.-alumina includes aluminium oxides such as
.beta.-alumina, .gamma.-alumina, hydroxides such as gibbsite and
boehmite, aluminium salts such as aluminum nitrate and aluminium
sulfate and alminium compound to be oxide by calcining with
.alpha.-alumina particle, but except .alpha.-alumina itself. Among
them, colloidal-alumina such as an aluminasol may be used as
aluminium compound.
[0043] In addition of colloidal-silica, as typical example of the
silicon compound mentioned above, covalent bond compound such as
silicon oxide, silicon nitride, silicon carbide, silane, and
silicon sulfate; silicates such as sodium silicate, ammonium
silicate, sodium alumino-sulicate, ammonium aluminosilicate, sodium
phosphosilicate, and ammonium phosphosilicate; complex salts of
silica containing such silicon as feldspar and clay; and silica
mixture may be cited.
[0044] Furthermore, clay mineral such as silica-alumina, mullite
and zeolite may be used as aluminium compound and silicon
compound.
[0045] As typical example of the sodium compound mentioned above,
inorganic salts such as sodium nitrate, sodium carbonate, sodium
bicarbonate, sodium chloride, sodium fluoride, sodium nitrite,
sodium sulfate; carboxylates such as sodium formate and sodium
acetate; and sodium hydroxide may be cited.
[0046] Sodium component can be introduced to the .alpha.-alumine in
any way, for example, introduced as a component of organic binder
and/or inorganic binder and/or sodium-enriched alumina calcined a
mixture of sodium salt and alumina compounds. Any means can be
employed to add the sodium to the carrier in the carrier
preparation in this invention.
[0047] As typical example of the organic binder mentioned above,
methylcellulose, hydroxymethycellulose, carboxylmethycellulose,
corn starch and so on may be cited.
[0048] As the pore forming agents, particles of walnut seed shell,
particles of peach seed, polymers and so on having the same
particle diameter as .alpha.-alumina may be cited.
[0049] The carrier to be used in this invention can be prepared by
any of the methods heretofore known to the art. One method, for
example, attains the preparation by kneading the .alpha.-alumina
powder with methyl cellulose added thereto as an organic binder,
adding to the resultant mixture granular alumina sol,
colloidal-silica, and further sodium hydroxide, and mixing the
produced mixture with water added thereto. The final mixture is
extrusion molded, then granulated, dried, and subsequently fired.
Though the calcining temperature does not need to be particularly
limited, the calcining is carried out at a temperature in the range
of 1000-1700.degree. C., preferably in the range of
1300-1500.degree. C. The calcining time is in the range of 0.5-5
hours, preferably 1-3 hours. By boiling to clean the granular
product in boiling water several times, the carrier aimed at can be
obtained.
[0050] The silver compound to be used for the formation of silver
as a catalytic component of the catalyst of this invention is only
required to be capable of forming a complex with amine, soluble in
an aqueous solvent and decomposing to separate silver at a
temperature of not higher than 500.degree. C., preferably not
higher than 300.degree. C., and more preferably not higher than
260.degree. C. As typical examples of the silver compound which
answers the description, silver oxide, silver nitrate, silver
carbonate and various silver carboxylates such as silver acetate
and silver oxalate may be cited. Among other silver compounds
mentioned above, silver oxalate proves to be particularly
advantageous. The amine as a complexing agent imposes no
restriction particularly but requires only to be capable of
dissolving the silver compound mentioned above in an aqueous
solvent. Pyridine, acetonitrile, ammonia, and amines of 1-6 carbon
atoms are concrete examples of the amine of this description. Among
them, ammonia, monoamines such as pyridine and butyl amine, alkanol
amines such as ethanol amine, alkylene diamines of 2-4 carbon
atoms, and polyamines prove to be particularly advantageous. It is
particularly preferable to use ethylene diamine and ethanol amine,
either singly or in the form of a mixture.
[0051] In this case, the ratio of the amounts of the silver
compound and amine to be mixed is properly in the range of 1-2 mols
of amine, preferably in the range of 1-1.5 mols of amine, per mol
of the silver compound. In this case, when a plurality of kinds of
silver compound and amine are used, the mol numbers mentioned above
apply to the totals of the kinds of compounds.
[0052] For the purpose of depositing silver on the carrier, it is
most realistic to use the silver compound and the amine in the form
of aqueous solutions thereof. Optionally, water-based solutions of
the silver compound and the amine which incorporate an alcohol
therein may be used. The silver concentration in the aqueous
solution is selected so that the silver as the catalyst component
is eventually deposited in an amount in the range of 5-25 mass %,
preferably 5-20 mass %, based on the total mass of the
catalyst.
[0053] The impregnation to support silver to the carrier is carried
out by well known method in the prior art. Such operations as
reducing pressure, application of heat, spraying the solution to
the carrier and combination thereof are performed, if necessary.
The amine is added in an amount necessary for forming a complex of
the silver compound. Generally it raises a reproducibility of
catalyst preparation by adding in an amount of 5-30% in excess of
the equivalent weight. Heat treatment following to the impregnation
is performed at a temperature and time necessary for deposition of
silver on the carrier. It is most preferable to select the
condition so that silver particles is deposited on the carrier as
uniform and minute as possible. A high temperature and/or a long
duration for the heat treatment are generally unfavorable because
they are liable to promote sintering of silver particles. It is
preferred method, therefore, that the impregnated catalyst is
treated with air (or an inert gas such as nitrogen) preheated to a
temperature in the range of 120.degree. C.-450.degree. C. or
superheated steam for a short duration of 5-60 minutes. The brief
treatment just mentioned is also advantageous from the viewpoint of
curtailing the time for the process of preparation of the
catalyst.
[0054] The at least one element selected from the group consisting
of alkali metals and thallium and deposited as a catalytic
component is preferred to be in the form of a compound soluble in a
water-based solvent and is used in a wholly dissolved state. Part
of the catalytic component may be in a partly undissolved state.
The compounds which answer this description include nitrates,
carbonates, bicarbonates, halogen salts, nitrites, sulfates, and
other inorganic salts, formates and other carboxylates, and
hydroxides of thallium and alkali metals such as lithium, sodium,
potassium, rubidium, cesium, and francium, for example. As more
concrete examples of these compounds, cesium nitrate, cesium
hydroxide, cesium chloride, cesium carbonate, cesium sulfate,
lithium nitrate, lithium hydroxide, lithium chloride, lithium
carbonate, lithium oxalate, lithium sulfate, lithium borate, sodium
nitrate, sodium carbonate, sodium bicarbonate, sodium acetate,
sodium borate, sodium ethoxide, potassium nitrate, rubidium
nitrate, thallium chloride, thallic nitrate, thallium sulfate,
thallium carbonate, and thallium oxalate may be cited.
[0055] The catalyst for the production of an epoxide contemplated
by the present invention may incorporate therein other metal. The
metals usable for this incorporation include alkaline earth metals
such as magnesium, calcium, strontium, and barium, rare earth
metals such as scandium, yttrium, cerium, lanthanum, neodymium,
praseodymium, and europium, metals such as copper, gold, lead,
cadmium, titanium, zirconium, hafnium, germanium, tin, vanadium,
niobium, tantalum, phosphorus, arsenic, antimony, bismuth,
chromium, and molybdenum, and other elements. These metals may be
used either singly or in the form of a combination of two or more
members. As concrete compounds which can be arbitrarily
incorporated, magnesium nitrate, magnesium carbonate, magnesium
oxalate, magnesium ethoxide, calcium nitrate, calcium hydroxide,
calcium chloride, calcium acetate, calcium sulfate, calcium
molybdate, barium nitrate, strontium nitrate, strontium hydroxide,
strontium chloride, yttrium nitrate, yttrium chloride, yttrium
carbonate, yttrium oxalate, yttrium acetate, cerium nitrate, cerium
hydroxide, cerium carbonate, cerium sulfate, lanthanum nitrate,
neodymium nitrate, praseodymium nitrate, europium nitrate, copper
nitrate, copper hydroxide, copper carbonate, copper oxalate, copper
acetate, copper sulfate, copper borate, copper molybdate, lithium
tetrachloroaurate, sodium tetrachloroaurate, zinc nitrate, zinc
chloride, zinc carbonate, zinc nitrate, zinc acetate, zinc borate,
zinc chlorate, zinc molybdate, cadmium nitrate, cadmium hydroxide,
mercurous nitrate, mercurous sulfate, ammonium borate, potassium
borate, gallium hydroxide, gallium chloride, indium nitrate, indium
chloride, indium sulfate, tetralsopropoxy titanium, zirconium
nitrate, zirconium hydroxide, zirconium hydrochloride, zirconium
sulfate, hafnium chloride, lithium zirconate, sodium zirconate,
ethyl silicate, lithium germanate, sodium germanate, potassium
germanate, tin chloride, tin acetate, lithium stannate, potassium
stannate, lead nitrate, lead hydroxide, vanadium chloride, sodium
vanadate, potassium vanadate, niobium oxalate, potassium niobate,
tantalum hydroxide, tantalum chloride, tantal isopropoxide, sodium
tantalate, potassium tantalate, ammonium phosphate, sodium
phsophate, potassium phosphate, sodium hydrogen, phosphate,
potassium hydrogen phosphate, strontium hydrogen phosphate, arsenic
chloride, antimony chloride, antimony tartrate, antimony sulfate,
bismuth nitrate, bismuth chloride, bismuth sulfate, tellurium
chloride, ammonium tellurate, sodium tellurate, lithium tellurite,
sodium tellurite, sodium chromate, lithium chromate, and lithium
molybdate may be cited.
[0056] These elements may be deposited (and simultaneously used for
impregnation) as incorporated in an aqueous silver solution. They
may be deposited prior to the deposition of silver (referred to as
"preimpregnation") or subsequently to the deposition of silver
(referred to as "afterimpregnation"). For the afterimpregnation,
the elements are used in the form of an aqueous solution.
Optionally, the deposition may be accomplished by dissolving the
elements in an alcohol, for example, immersing in the resultant
solution a carrier having silver deposited thereon in advance,
stripping the impregnated carrier of the excess solution, and then
drying the resultant wet carrier.
[0057] The silver catalyst of this invention properly contains
silver in an amount in the range of 5-25 mass %, based on the total
mass of the catalyst and, at the same time, contains at least one
element selected from the group consisting of thallium and alkali
metals in an amount in the range of 0.001-5 mass %, preferably in
the range of 0.005-3 mass %, and particularly preferably in the
range of 0.01-0.2 mass %, based on the mass of the catalyst. As the
alkali metal to be deposited in the catalyst of this invention,
sodium, potassium, rubidium, and/or cesium prove particularly
advantageous among other alkali metals mentioned above. When the
amount of the alkali metal to be deposited is in the range of
0.001-5 mass %, the catalyst of this invention does not need to
contain thallium. The catalyst, however, may contain thallium in
conjunction with the alkali metal. The amount of potassium to be
deposited is particularly preferred to be in the range of 0.01-0.8
mass %, that of rubidium to be in the range of 0.02-1.0 mass %,
that of cesium to be in the range of 0.01-2 mass %, and that of
thallium in the range of 0.001-2 mass % respectively. If the amount
of an alkali metal or thallium to be deposited in the catalyst
falls short of 0.001 mass %, the shortage will possibly lower the
selectivity conspicuously, curtail the service life of the
catalyst, and entail extinction of the catalytic activity during a
protracted use even where the other requirements of the carrier are
fulfilled. Conversely, if the amount exceeds 5 mass %, the excess
will be at a disadvantage in enlarging the degree of conversion
particularly. Such catalytic components are deposited most
advantageously simultaneously with the silver. Commendably, these
catalytic components are added partly or wholly in the form of
halogenides such as chlorides, bromides, or fluorides or nitrates
or sulfates.
[0058] In the method for depositing the cation component mentioned
above by the operation of preimpregnation or afterimpregnation,
when the cation component is added in the form of an aqueous
solution, the deposition is preferred to be attained by drying the
aqueous solution with air heated to 110-200.degree. C. for a period
in the range of 5-60 minutes. Superheated steam may be used in the
place of the air in this drying operation. When an alcohol such as
ethyl alcohol is added as the solvent, the deposition is preferred
to be effected by drying the solution with an inert gas such as air
or nitrogen heated to a temperature not higher than 100.degree. C.,
preferably not higher than 50.degree. C. Consequently, the cation
component is uniformly dispersed on the carrier.
[0059] As the method for heating the catalyst with air or the inert
gas such nitrogen or with the superheated steam in this invention,
the catalyst may be piled in a single layer or a plurality of
layers in the form of a fixed bed or a moving bed and the inert gas
such as air or nitrogen or the superheated steam may be passed
through this bed downward, upward, or sideward. The duration of
this treatment may be properly selected to suit the temperature and
the flow rate of the air or inert gas such as nitrogen or the
superheated steam. As respects the flow rate, the treatment at a
flow rate in the range of 0.3-1 m/second where the catalyst is
treated in a single layer or a plurality of layers as in the
mesh-belt drying device or at a flow rate in the range of 0.7-3
m/second where the catalyst is treated in a tube having a large bed
length as in the shell-and-tube type reaction vessel proves
economical from the practical point of view because of the absence
of uneven silver distribution in the catalyst. When the superheated
steam is used, it may incorporate therein nitrogen or air to a
certain extent.
[0060] This invention prefers depositing the catalyst component
containing silver and at least one element selected from the group
consisting of alkali metals and thallium on the carrier mentioned
above and thereafter heat-treating the resultant composite finally
at an elevated temperature in the range of 400-700.degree. C. in an
inert gas containing substantially no oxygen. The silver catalyst
of this invention serves the purpose of effecting gas phase
oxidation of an unsaturated hydrocarbon having a chain length of
4-20 carbon atoms and containing no allylic hydrogen atom. Since
this catalyst has a short service life and consequently requires
such a procedure as suspending the operation of the apparatus and
packing the apparatus with a fresh supply of the catalyst, the
productivity of the epoxide is degraded. It is believed that this
invention is enabled to stabilize the silver, alkali metal,
thallium, etc. deposited on the carrier by performing in advance
the heat treatment at the elevated temperature in the inert gas for
some unaccountable reason. It is considered that the selectivity is
maintained particularly in consequence of repressing the rise of
the reaction temperature during a protracted use of the catalyst.
In fact, by the treatment mentioned above, the selectivity and the
degree of conversion can be secured stably from the start of the
use of the catalyst onward and, moreover, the service life of the
catalyst can be elongated.
[0061] The expression "the inert gas containing substantially no
oxygen" as used herein means one member or a mixture of two or more
members selected from the group consisting of nitrogen, helium,
argon, carbon dioxide, and neon. Among other inert gases enumerated
above, nitrogen proves particularly advantageous because it is
inexpensive and easy to procure. Then, the term "substantially"
used in the preceding expression means that oxygen may be contained
to the extent of bringing no adverse effect on the property of
oxidation, preferably up to not more than 3 vol. % in
concentration. Though the reason for necessitating substantial
absence of oxygen is not clear, this necessity may be logically
explained by a supposition that when the heat treatment at the
elevated temperature proceeds in the presence of oxygen, the
deposited silver gains so much in particle diameter after this heat
treatment possibly as to degrade the catalytic activity and curtail
the service life of the catalyst. When the heat treatment is
performed in the state containing "substantially" no oxygen,
therefore, the silver shows virtually no change in particle
diameter before and after the treatment. Consequently, the
thermostablity can be improved thereby the stable catalytic
activity can be attained in conjunction with the elongation of the
service life of the catalyst.
[0062] The expression "the heat treatment at an elevated
temperature" as used herein refers to a heating operation performed
at a temperature in the range of 400-700.degree. C., preferably
450-650.degree. C. If this temperature falls short of 400.degree.
C., the aforementioned effect of elongating the service life of the
catalyst will fail to manifest and the heat treatment at the
elevated temperature will require a long time. Conversely, if this
temperature exceeds 700.degree. C., the excess will possibly bring
a decrease in the selectivity. The pressure in this treatment does
not need to be particularly specified. The temperature of the heat
treatment, the duration of the treatment, and the concentration of
oxygen constitute themselves the important factors.
[0063] The duration of the heat treatment at the elevated
temperature is in the range of 5 minutes-30 hours, preferably 30
minutes-20 hours, and particularly preferably 30 minutes-10
hours.
[0064] The heat treatment at the elevated temperature, for the
purpose of imparting activity to the silver compound and the other
metal component deposited on the carrier, is performed after the
catalytic component has been deposited on the carrier.
[0065] In the catalyst which has undergone the heat treatment at
the elevated temperature as described above, the catalytic
component deposited on the produced catalyst is preferred to
contain silver in an amount in the range of 5-25 mass % based on
the mass of the catalyst and, at the same time, contain the at
least one element selected from the group consisting of thallium
and alkali metals in an amount in the range of 0.001-5 mass %,
preferably 0.005-3 mass %, and particularly preferably 0.01-2 mass
%, based on the mass of the catalyst. As the alkali metal to be
deposited in the catalyst of this invention, sodium, potassium,
rubidium, and/or cesium prove particularly advantageous among other
alkali metals mentioned above. When the amount of the alkali metal
to be deposited is in the range of 0.001-5 mass %, the catalyst of
this invention does not need to contain thallium. The catalyst,
however, may contain thallium in conjunction with the alkali metal.
The amount of potassium to be deposited is particularly preferred
to be in the range of 0.01-0.8 mass %, that of rubidium to be in
the range of 0.02-1.0 mass %, that of cesium to be in the range of
0.01-2 mass %, and that of thallium in the range of 0.01-2 mass %
respectively. If the amount of an alkali metal or thallium to be
deposited in the catalyst falls short of 0.001 mass %, the shortage
will possibly lower the selectivity conspicuously, curtail the
service life of the catalyst, and entail extinction of the
catalytic activity during a protracted use even where the other
requirements of the carrier are fulfilled. Conversely, if the
amount exceeds 5 mass %, the excess will be at a disadvantage in
enlarging the degree of conversion particularly.
[0066] The catalyst and the carrier are preferred to be shaped in
the form of spheres, pellets, or rings measuring in the approximate
range of 3-12 mm, particularly 4-10 mm.
[0067] The third aspect of this invention concerns a method for the
production of epoxides, which comprises effecting said production
by the vapor-phase oxidation of an unsaturated hydrocarbon having a
chain length of 4-20 carbon atoms and containing no allylic
hydrogen atom with a molecular oxygen-containing gas in the
presence of the catalyst of this invention described above.
[0068] The compound having a chain length of 4-20 carbon atoms and
containing no allylic hydrogen atom and used as the raw material
herein is an unsaturated hydrocarbon which has a chain length
preferably of 4-12, more preferably 4-8 carbon atoms and contains
no allylic hydrogen atom as mentioned above. As concrete examples
of the compound which answers the description, 1,3-butadiene,
tertiary butyl ethylene, and styrene may be cited. This invention
particularly prefers using 1,3-butadiene or tertiary butyl
ethylene. The catalyst of this invention for the production of an
epoxide is intended to catalyze a vapor-phase oxidation. For the
purpose of enabling the reaction of oxidation to proceed in gas
phase on the surface of the catalyst, this catalyst is preferred to
use as the target thereof a compound having a low boiling point
from the standpoint of the service life of catalyst.
[0069] For this reaction of oxidation, any of the known reaction
vessels which are effectively applicable to the reaction of gas
phase oxidation of an unsaturated hydrocarbon having a chain length
of 4-20 carbon atoms and containing no allylic hydrogen atom can be
adopted.
[0070] To be specific, the total pressure of the feed raw material
containing an unsaturated hydrocarbon having a chain length of 4-20
carbon atoms and containing no allylic hydrogen atom, a molecular
oxygen-containing gas, and a diluent gas and a reaction adjusting
agent which will be described more specifically below is in the
range of 0.01-10 MPa. Preferably 0.01-4 MPa. and more preferably
0.02-3 MPa. The molar ratio of the unsaturated hydrocarbon having a
chain length of 4-20 carbon atoms and containing no allylic
hydrogen atom to 1 mol of oxygen is in the range of 0.001-100,
preferably 0.01-50.
[0071] To the reaction vessel which is packed with the catalyst of
this invention, a mixture of a molecular oxygen-containing gas, an
unsaturated hydrocarbon having a chain length of 4-20 carbon atoms
and containing no allylic hydrogen atom, and one or more diluent
gases selected from among nitrogen, helium, argon, carbon dioxide,
and alkane may be supplied. The partial pressures of these gas
components being supplied to the reaction vessel must be selected
so as to form a gas composition deviating from explosion limits in
the reaction vessel.
[0072] The raw material gas may incorporate therein a reaction
adjusting agent. The reaction adjusting agent is a compound
containing a halogen. As concrete examples of the compound,
chlorinated alkenes of 1-6 carbon atoms such as chlorinated
ethylene, vinyl chloride, methyl chloride, and t-butyl chloride;
chlorinated benzenes such as dichloromethane, dichloroethylene,
trichloroethylene, chloroform, chlorinated biphenyl, and
monochlorobenzene; brominated alkenes of 1-6 carbon atoms such as
dichloropropane, dibromopropane, dichloropropene, dibromopropene,
chlorobutane, bromobutane, dichlorobutane, dibromobutane,
chlorobutene, dibromoethylene, tribromoethylene, brominated
ethylene, vinyl bromide, methyl bromide, and t-butyl bromide; and
brominated benzenes such as dibromomethane, tetrabromo-methane,
brominated biphenyl, and monobomobenzene may be cited. These
reaction adjusting agents may be used either singly or in the form
of a mixture of two or more members. It is particularly
advantageous to use vinyl chloride or chlorinated ethylene among
other reaction adjusting agents enumerated above. The concentration
of the reaction adjusting agent is in the range of 0-1000 volume
ppm, preferably 1-100 volume ppm, and particularly 1-50 volume %,
based on the volume of the raw material gas. It has been
ascertained to the inventors that the reaction adjusting agent,
particularly vinyl chloride, which is used in this concentration
serves the purpose of exalting the selectivity.
[0073] The temperature of the reaction vessel can be properly
selected to suit the kind of unsaturated hydrocarbon having a chain
length of 4-20 carbon atoms and containing no allylic hydrogen atom
and used in the raw material gas. The temperature of the
[0074] reaction vessel in operation is in the range of
150-300.degree. C., preferably 170-250.degree. C.
[0075] The spatial velocity of the raw material gas to be supplied
to the interior of the reaction vessel is in the range of 100-30000
hr.sup.-1, preferably 200-20000 hr.sup.-1. The reaction is only
required to convert 0.1-75 mol %, preferably 1-60 mol %, and
particularly preferably 1-50 mol %, of the unsaturated hydrocarbon
having a chain length of 4-20 carbon atoms and containing no
allylic hydrogen atom in the raw material. The unaltered portion of
the unsaturated hydrocarbon having a chain length of 4-20 carbon
atoms and containing no allylic hydrogen atom may be properly
recycled to the reaction system. If the speed of supply of the raw
material falls short of 100 hr.sup.-1, the shortage will be at a
disadvantage in degrading the efficiency of production. Conversely,
if this speed exceeds 30000 hr.sup.-1, the excess will be at a
disadvantage in lowering the degree of conversion. The actual
retention time which is necessary for accomplishing the expected
level of conversion may be varied in a wide range, depending on
such factors as the kind of the raw material gas to be supplied,
the ratio of the raw material gas to oxygen, the amount of a
co-catalyst or a reaction accelerator to be deposited on the
catalyst, the amount of silver deposited in the catalyst, and
amount of the reaction adjusting agent present in the reaction gas,
the temperature of the reaction, and the pressure of the
reaction.
[0076] Now, the method for producing 3,4-epoxy-1-butene by
catalytic vapor-phase oxidation of 1,3-butadiene with a
oxygen-containing gas by the use of the catalyst described above
will be explained below.
[0077] The reaction is performed by providing 1,3-butadiene, oxygen
and optional organic halogenized compound, an oxygen/1,3-butadiene
mol ratio controlling in the range of 0.01-20, further the organic
halogenized compound being in the range of 0-1000 ppm by volume
based on all of provided materials, preferably about 1-100 ppm.
optionally, gaseous inert dilution agent such as helium, nitrogen,
argon and/or one or more mixture thereof may be used in the
above-mentioned catalytic vapor-phase oxidation.
[0078] The organic halogen compound imposes no particular
restriction and only requires to be capable of retaining a gaseous
state in the reaction gas. As concrete examples of the organic
halogen compound, methyl chloride, methyl bromide, dichloromethane,
dibromomethane, ethyl chloride, ethyl bromide, dichloroethane,
dibromoethane, vinyl chloride, dichloroethylene, dibromoethylene,
trichloroethylene, dichloropropane, dibromopropane,
dichloropropene, dibromopropene, chlorobutane, bromobutane,
dichlorobutane, dibromobutane, and chlorobutene may be cited.
[0079] The reaction pressure may be changed extensively, although
there is a limit of in the range of 0.01-10 MPa (gauge), preferably
about 0.01-4 MPa (gauge), more preferably about 0.02-3 MPa
(gauge).
[0080] The reaction time suitable for enforcement of the present
invention may be changed extensively. The reaction can be carried
out not only in single pass process but also in recycle process
using outlet gas from the reactor. A method for single pass is
described for the sake of convenience. Generally, 1,3-butadiene,
oxygen, organic halogen compound and catalyst obtained by the
present invention are retained for sufficient time such contact
condition that a butadiene conversion is in the range of about
0.1-75 mol % by a single pass. The butadiene conversion is
preferably in the range of about 1-50 mol % for efficient use of
reactor vessel.
[0081] Contact time for achievement of desired conversion in the
reaction may be changed extensively by depending on such factors as
a ratio of 1,3-butadiene/oxygen, the amount of co-catalyst or
stimulator deposited on the catalyst, the amount of silver
deposited on the catalyst, the amount of organic halogen compound
in the reaction gas, reaction temperature, reaction pressure and so
on.
[0082] The space velocity is in the range of about 100-30,000
hr.sup.-1, more preferably 200-20,000 hr.sup.-1, and most
preferably 300-10,000 hr-.sup.1. The most suitable combination of
butadiene convention and product selectivity thereby can be
realized under these space velocity.
[0083] Experiments:
[0084] The present invention will be described more specifically
below with reference to working examples. In Examples 1-11 and
Controls 1-9 to be cited herein below, the relevant experiments
were performed by packing the crushed catalyst in test tubes with a
small inside diameter for demonstrating the effects thereof
precisely and conveniently. The results of these experiments and
the characters of carriers and catalyst used in every Example and
Control are shown in Table 1-3.
[0085] The physical properties which are mentioned throughout the
entire text of this specification represent the magnitudes which
are determined by the following methods.
[0086] (1) Determination of SiO.sub.2, Na.sub.2O and cationic
components: These components are analyzed by X-ray
fluorescence.
[0087] (2) Specific surface area: A carrier is crushed and sieved
in 0.85-1.2 mm range. About 0.2 g of the sieved carrier particles
is weighed accurately. After deaeration at 200.degree. C. for at
least 30 minutes, sample is measured for specific surface area by
the B.E.T. (Brunauer-Emett-Teller) method.
[0088] (3) Average pore diameter: This property is measured by the
mercury porosimeter.
[0089] (4) Water absorption rate: This property is determined as
follows in due respect of the method of JIS R 2205-1998.
[0090] a) A non-crushed carrier (in the shape of pellets, rings or
spheres, etc) is dried in an air oven until a constant mass was
reached, and weighed (dry mass: W, (g)).
[0091] b) The weighed carrier is immersed in water, boiled in the
water for more than 30 minutes, and then cooled in water kept at
room temperature. The cooled carrier is used as a saturated
sample.
[0092] c) The saturated sample is taken out from the water, quickly
wiped with a damp cloth for removal of water drops, and then
weighed (mass of saturated sample: W.sub.2(g)).
[0093] d) The water absorption is calculated in accordance with the
following formula.
[0094] Water absorption
rate(%)=[(W.sub.2-W.sub.1)/W.sub.1].times.100
EXAMPLE 1
[0095] 93 Mass parts of .alpha.-alumina (diameter of alumina
crystal: 1 .mu.m, average particle diameter: 40 .mu.m, BET specific
surface area: 2 m.sup.2/g, sodium content (as reduced to Na): 16
mmol/kg) and 5 mass parts of methylcellulose were added into a
kneader and mixed sufficiently. 4 Mass parts of aluminasol (as
reduced to Al.sub.2O.sub.3) having particle diameter of 2-20 nm, 3
mass parts of colloidal-silica (as reduced SiO.sub.2) having
particle diameter of 2-20 nm; and 0-15 mass part of sodium
hydroxide (as reduced to Na.sub.2O) were added thereto, and mixed
the resultant composition after adding 40 mass parts of water the
composition. The carrier (Carrier A) was obtained by extrusion
molding the resultant mixture, drying, calcining at the temperature
of 1450.degree. C. for 2 hours washing out with boiling water for
30 min of three times and drying thereof.
[0096] To a water slurry containing 30 g of silver oxalate placed
in a beaker and kept cooled in a water bath, 16 ml of
ethylenediamine was added to effect thorough solution of the silver
compound. In this solution, 0.138 g of cesium chloride was
dissolved completely. 100 Gram of carrier preheated in advance to
100.degree. C. was placed in an evaporating dish setting on a
boiling water bath, impregnated by adding silver containing
solution to the carrier. After the silver containing solution was
absorbed to the carrier, a heat treatment was performed in a hot
oven with an air flow at 200.degree. C. for 10 minutes and further
at 400.degree. C. for 10 minutes. Silver content of the obtained
catalyst was 16.2 mass %, cesium content was 0.083 mass % based on
the carrier as cesium atom.
[0097] The obtained silver-containing catalyst (Catalyst A1) was
crushed and sieved in 0.85-1.2 mm in diameter. The sample was
evaluated by the use of a single-pass flow reactor of cylinder
type. The reaction tube is 40 cm in length, 10 mm in outside
diameter, and 8 mm in inside diameter, was made of stainless steel
and packed with a roll of quartz wool adapted to retain the
catalyst at the center thereof. The reaction gas was composed of
helium. 1.3-butadiene and oxygen whose volume ratio was controlled
at 4:1:1 by means of a mass flow controller. Further,
ethylenedichloride was added to the reaction gas in the range of
2-5 ppm by volume. The reaction for the oxidation of butadiene was
carried out at a space velocity of 6,000 hr.sup.-1 and a reaction
temperature of 195.degree. C. The reaction pressure (gauge) was
controlled at 50 kPa. The feed gas and outlet gas form the reactor
was analyzed by a thermal conduction detector with a capillary
column (Pora PLOTQ: 0.53 mm in inside diameter, 50 m in
length).
[0098] The gas chromatography was performed by retaining the oven
temp at 115.degree. C. for four minutes and then heating the oven
to 230.degree. C. at a temperature increasing rate of 7.degree.
C./min. Helium was used as the for the carrier gas
chromatography.
EXAMPLE 2
[0099] A silver-containing catalyst (Catalyst A1) was obtained by
following the procedure of Example 1 while using 0.159 g of cesium
nitrate in the place of cesium chloride. Silver content of the
catalyst obtained was 15.9 mass %, cesium content was 0.082 mass %
as cesium atom.
EXAMPLE 3
[0100] A silver-containing catalyst (Catalyst A3) was obtained by
following the procedure of Example 1 while using 0.217 g of
thallium nitrate in place of cesium chloride. Silver content of the
catalyst, obtained was 15.9 mass %, thallium content was 0.128 mass
% as thallium atom.
EXAMPLE 4
[0101] 93 Mass parts of .alpha.-alumina (diameter of alumina
crystal: 1 .mu.m, average particle diameter: 65 .mu.m, BET specific
surface area: 3 m.sup.2/g, sodium content (as reduced to Na): 16
mmol/kg) and 5 mass parts of sodium carboxymethyl cellulose salt
were added into a kneader and mixed sufficiently. 4 Mass parts of
aluminasol and 3 mass parts of colloidal-silica (as reduced to
SiO.sub.2) and 0.15 mass parts of sodium hydroxide (as reduced to
Na) were added thereto, and mixed the resultant composition after
adding 40 mass parts of water the composition. The carrier (Carrier
B) was obtained by extrusion molding the resultant mixture, drying,
calcining at the temperature of 1450.degree. C. for 2 hours washing
out with boiling water for 30 min of three times and drying
thereof.
[0102] A silver-containing catalyst (Catalyst B1) was obtained by
following the procedure of Example 1 while using a carrier B in
stead of a carrier A and 0.244 g of cesium nitrate. Silver content
of the catalyst obtained was 16.3 mass %, cesium content was 0.130
mass % as cesium atom.
EXAMPLE 5
[0103] A silver-containing catalyst (Catalyst B2) was obtained by
following the procedure of Example 4 while using carrier B and
using 0.325 g of cesium sulfate in place of cesium nitrate. Silver
content of the catalyst obtained was 16.1 mass %, cesium content
was 0.198 mass % as cesium atom.
EXAMPLE 6
[0104] 93 Mass parts of .alpha.-alumina (diameter of alumina
crystal: 0.5 .mu.m, average particle diameter: 80 .mu.m, BET
specific surface area: 3 m.sup.2/g, sodium content (as reduced to
Na): 40 mmol/kg) and 5 mass parts of methyl cellulose were added
into a kneader and mixed sufficiently. Four mass parts of
aluminasol and 3 mass parts of colloidal-silica (as reduced to
SiO.sub.2) and 0.15 mass parts of sodium hydroxide (as reduced to
Na) were added thereto, and mixed the resultant composition after
adding 40 mass parts of water the composition. The carrier (Carrier
C) was obtained by extrusion molding the resultant mixture, drying,
calcining at the temperature of 1450.degree. C. for 2 hours washing
out with boiling water for 30 min of three times and drying
thereof.
[0105] A silver-containing catalyst (Catalyst C) was obtained by
following the procedure of Example 1 while using a carrier C and
using 0.353 g of cesium nitrate. Silver content of the catalyst
obtained was 15.7 mass %, cesium content was 0.196 mass % as cesium
atom.
EXAMPLE 7
[0106] 93 Mass parts of .alpha.-alumina (diameter of alumina
crystal: 4 .mu.m, average particle diameter: 40 .mu.m, BET specific
surface area: 1 m.sup.2/g, sodium content (as reduced to Na): 8
mmol/kg) and 5 mass parts of sodium carboxymethyl cellulose salt
were added into a kneader and mixed sufficiently. Four mass parts
of aluminasol and 3 mass parts of colloidal-silica (as reduced to
SiO.sub.2) and 0.15 mass parts of sodium hydroxide (as reduced to
Na) were added thereto, and mixed the resultant composition after
adding 40 mass parts of water the composition. The carrier (Carrier
D) was obtained by extrusion molding the resultant mixture, drying,
calcining at the temperature of 1450.degree. C. for 2 hours washing
out with boiling water for 30 min of three times and drying
thereof.
[0107] A silver-containing catalyst (Catalyst D) was obtained by
following the procedure of Example 1 while using a carrier D in
place of a carrier A and using 0.121 g of cesium nitrate. Silver
content of the catalyst obtained was 16.0 mass %, cesium content
was 0.064 mass % as cesium atom.
EXAMPLE 8
[0108] 84 Mass parts of .alpha.-alumina (diameter of alumina
crystal: 3 .mu.m, average particle diameter: 40 .mu.m, BET specific
surface area: 1 m.sup.2/g, sodium content (as reduced to Na): 8
mmol/kg) and 10 mass parts of methyl cellulose were added into a
kneader and mixed sufficiently. Four mass parts of aluminasol, 7
mass parts of colloidal-silica (as reduced to SiO.sub.2) and 2.4
mass parts of sodium hydroxide (as reduced to Na) were added
thereto, and mixed the resultant composition after adding 40 mass
parts of water the composition. The carrier (Carrier E) was
obtained by extrusion molding the resultant mixture, drying,
calcining at the temperature of 1450.degree. C. for 2 hours washing
out with boiling water for 30 min of three times and drying
thereof.
[0109] A silver-containing catalyst (Catalyst E) was obtained by
following the procedure of Example 1 while using a carrier E in
place of a carrier A and using 0.091 g of cesium nitrate instead
Silver content of the catalyst obtained was 15.8 mass %, cesium
content was 0.053 mass % as cesium atom.
EXAMPLE 9
[0110] A silver-containing catalyst (Catalyst A4) was obtained by
following the procedure of Example 1 while performing the heat
treatment of the impregnated catalyst with superheated steam at
200.degree. C. for 15 minutes. Silver content of the catalyst
obtained was 16.1 mass %, cesium content was 0.085 mass % as cesium
atom.
EXAMPLE 10
[0111] To a water slurry containing 30 g of silver oxalate placed
in a beaker and kept cooled in a water bath, 16 ml of
ethylenediamine was added to effect thorough solution of the silver
compound. In this solution, 0.81 g of cesium nitrate was dissolved
completely. A hundred gram of carrier (carrier B) obtained by
Example 4 and preheated in advance to 100.degree. C. was placed in
an evaporating dish setting on a boiling water bath, impregnated by
adding silver containing solution to the carrier. After the silver
containing solution was absorbed to the carrier, a heat treatment
was performed in a hot oven with an air flow at 200.degree. C. for
10 minutes and further at 400.degree. C. for 10 minutes. Silver
content of the obtained catalyst was 15.8 mass %, cesium content
was 0.440 mass % based on the carrier as cesium atom.
[0112] Then, the obtained catalyst was filled up in a stainless
steel hermetic container capable of introducing an inactive gas
from the outside of container and placed in a tubular furnace. A
catalyst was prepared by heat treatment at 565 .degree. C. for 3
hrs while supplying nitrogen gas.
[0113] The obtained silver-containing catalyst (Catalyst B3) was
crushed and sieved in 0.85-1.2 mm in diameter. The sample was
evaluated by the use of a single-pass flow reactor of cylinder
type. The reaction tube is 40 cm in length, 9.53 mm in outside
diameter, and 7.53 mm in inside diameter, was made of stainless
steel and packed with a roll of quartz wool adapted to retain the
catalyst at the center thereof. The reaction gas was composed of
helium, 1,3-butadiene and oxygen whose volume ratio was controlled
at 4:1:1 by means of a mass flow controller. Further,
ethylenedichloride was added to the reaction gas in the range of
2-5 ppm by volume. The reaction for the oxidation of butadiene was
carried out at a space velocity of 6,000 hr.sup.-1 and a reaction
temperature of 195.degree. C. The reaction pressure (gauge) was
controlled at 50 kPa. Analysis of raw material gas and resultant
gas as well as gas chromatography were performed by the same manner
of Example 1.
EXAMPLE 11
[0114] A silver-containing catalyst (Catalyst B4) was obtained by
following the procedure of Example 10 while performing the heat
treatment of the impregnated catalyst at 590.degree. C. for 3
hours. The catalyst was used for Oxidation of 1,3-butadien. Silver
content of the catalyst obtained was 15.8 mass %, cesium content
was 0.482 mass % as cesium atom.
CONTROL 1
[0115] A Catalyst was obtained (Catalyst A4) by following the
procedure of Example 1 while omitting the use of an alkali metal.
Silver content of the catalyst obtained was 15.9 mass %.
CONTROL 2
[0116] 93 Mass parts of .alpha.-alumina (diameter of alumina
crystal: 0.5 .mu.m, average particle diameter: 40 .mu.m, BET
specific surface area: 3 m.sup.2/g, sodium content (as reduced to
Na): 8 mmol/kg) and 5 mass parts of methyl cellulose were added
into a kneader and mixed sufficiently. Four mass parts of
aluminasol and 3 mass parts of colloidal-silica (as reduced to
SiO.sub.2) were added thereto, and mixed the resultant composition
after adding 40 mass parts of water the composition. The carrier
(Carrier F) was obtained by extrusion molding the resultant
mixture, drying, calcining at the temperature of 1450.degree. C.
for 2 hours washing out with boiling water for 30 min of three
times and drying thereof.
[0117] A Catalyst (Catalyst F) was obtained by following the
procedure of Example 1 while using a carrier F as shown table 2 and
using 0.338 g of cesium nitrate. Silver content of the catalyst
obtained was 16.3 mass %, cesium content was 0.195 mass % as cesium
atom.
CONTROL 3
[0118] 82 Mass parts of .alpha.-alumina (diameter of alumina
crystal: 0.3 .mu.m, average particle diameter: 5 .mu.m, BET
specific surface area: 10 m.sup.2/g, sodium content (as reduced to
Na): 16 mmol/kg) and 10 mass parts of methyl cellulose were added
into a kneader and mixed sufficiently. Four mass parts of
aluminasol, 14 mass parts of colloidal-silica (as reduced to
SiO.sub.2) and 0.6 mass parts of sodium hydroxide (as reduced to
Na) were added thereto, and mixed the resultant composition after
adding 40 mass parts of water the composition. The carrier (Carrier
G) was obtained by extrusion molding the resultant mixture, drying,
calcining at the temperature of 1450.degree. C. for 2 hours washing
out with boiling water for 30 min of three times and drying
thereof.
[0119] A Catalyst (Catalyst G) was obtained by following the
procedure of Example 1 while using a carrier G and using 0.694 g of
cesium nitrate. Silver content of the catalyst obtained was 15.7
mass %, cesium content was 0.393 mass % as cesium atom.
CONTROL 4
[0120] 93 Mass parts of .alpha.-alumina (diameter of alumina
crystal: 0.5 .mu.m, average particle diameter: 10 .mu.m, BET
specific surface area: 5 m.sup.2/g, sodium content (as reduced to
Na): 96 mmol/kg) and 5 mass parts of methyl cellulose were added
into a kneader and mixed sufficiently. Four mass parts of
aluminasol, 3 mass parts of colloidal-silica (as reduced to
SiO.sub.2) and 3.5 mass parts of sodium hydroxide (as reduced to
Na) were added thereto, and mixed the resultant composition after
adding 40 mass parts of water the composition. The carrier (Carrier
H) was obtained by extrusion molding the resultant mixture, drying,
calcining at the temperature of 1450.degree. C. for 2 hours washing
out with boiling water for 30 min of three times and drying
thereof.
[0121] A Catalyst (Catalyst H) was obtained by following the
procedure of Example 1 while using a carrier H in place of a
carrier A and using 0.148 g of cesium nitrate instead. Silver
content of the catalyst obtained was 15.9 mass %, cesium content
was 0.080 mass % as cesium atom.
CONTROL 5
[0122] 96 Mass parts of .alpha.-alumina (diameter of alumina
crystal: 0.5 .mu.m, average particle diameter: 30 .mu.m, BET
specific surface area: 2 m.sup.2/g, sodium content (as reduced to
Na): 0 mmol/kg) and 5 mass parts of methyl cellulose were added
into a kneader and mixed sufficiently. Four mass parts of
aluminasol was added thereto, and mixed the resultant composition
after adding 40 mass parts of water the composition. The carrier
(Carrier I) was obtained by extrusion molding the resultant
mixture, drying, calcining at the temperature of 1450.degree. C.
for 2 hours washing out with boiling water for 30 min of three
times and drying thereof.
[0123] A catalyst (Catalyst I) was obtained by following the
procedure of Example 1 while using a carrier I and using 0.200 g of
cesium nitrate. Silver content of the catalyst obtained was 15.7
mass %, cesium content was 0.123 mass % as cesium atom.
CONTROL 6
[0124] 84 Mass parts of .alpha.-alumina (diameter of alumina
crystal: 10 .mu.m, average particle diameter: 60 .mu.m, BET
specific surface area: 1 m.sup.2/g, sodium content (as reduced to
Na): 8 mmol/kg) and 5 mass parts of methyl cellulose were added
into a kneader and mixed sufficiently. Four mass parts of
aluminasol and 12 mass parts of colloidal-silica (as reduced to
SiO.sub.2) and 0.30 mass parts of sodium hydroxide (as reduced to
Na) were added thereto, and mixed the resultant composition after
adding 40 mass parts of water the composition. The carrier (Carrier
J) was obtained by extrusion molding the resultant mixture, drying,
calcining at the temperature of 1450.degree. C. for 2 hours washing
out with boiling water for 30 min of three times and drying
thereof.
[0125] A catalyst (Catalyst J) was obtained by following the
procedure of Example 1 while using a carrier J and using 0.093 g of
cesium nitrate. Silver content of the catalyst obtained was 10.6
mass %, cesium content was 0.055 mass % as cesium atom.
CONTROL 7
[0126] 87 Mass parts of .alpha.-alumina (diameter of alumina
crystal: 20 .mu.m, average particle diameter: 80 .mu.m, BET
specific surface area: 0.3 m.sup.2/g, sodium content (as reduced to
Na): 10 mmol/kg) and 5 mass parts of methyl cellulose were added
into a kneader and mixed sufficiently. Four mass parts of
aluminasol and 9 mass parts of colloidal-silica (as reduced to
SiO.sub.2) and 0.30 mass parts of sodium hydroxide (as reduced to
Na) were added thereto, and mixed the resultant composition after
adding 40 mass parts of water the composition. The carrier (Carrier
K) was obtained by extrusion molding the resultant mixture, drying,
calcining at the temperature of 1450.degree. C. for 2 hours washing
out with boiling water for 30 min of three times and drying
thereof.
[0127] A Catalyst (Catalyst K) was obtained-by following the
procedure of Example 1 while using a carrier K in place of a
carrier A and using 0.014 g of cesium nitrate. Silver content of
the catalyst obtained was 15.3 mass %, cesium content was 0.010
mass % as cesium atom.
CONTROL 8
[0128] 87 Mass parts of .alpha.-alumina (diameter of alumina
crystal: 0.3 .mu.m, average particle diameter: 5 .mu.m, BET
specific surface area: 10 m.sup.2/g, sodium content (as reduced to
Na): 16 mmol/kg) and 5 mass parts of methyl cellulose were added
into a kneader and mixed sufficiently. Four mass parts of
aluminasol and 7 mass parts of colloidal-silica (as reduced to
SiO.sub.2) and 0.30 mass parts of sodium hydroxide (as reduced to
Na) were added thereto, and mixed the resultant composition after
adding 40 mass parts of water the composition. The carrier (Carrier
L) was obtained by extrusion molding the resultant mixture, drying,
calcining at the temperature of 1450.degree. C. for 2 hours washing
out with boiling water for 30 min of three times and drying.
thereof.
[0129] A Catalyst (Catalyst L) was obtained by following the
procedure of Example 1 while using a carrier H in place of a
carrier A and using 0.173 g of cesium nitrate instead. Silver
content of the catalyst obtained was 15.9 mass %, cesium content
was 0.622 mass % as cesium atom.
CONTROL 9
[0130] 84 Mass parts of .alpha.-alumina (diameter of alumina
crystal: 0.8 .mu.m, average particle diameter: 55 .mu.m, BET
specific surface area: 3 m.sup.2/g, sodium content (as reduced to
Na): 90 mmol/kg) and 5 mass parts of methyl cellulose were added
into a kneader and mixed sufficiently. 4 Mass parts of aluminasol
and 3 mass parts of colloidal-silica (as reduced to SiO.sub.2) were
added thereto, and mixed the resultant composition after adding 40
mass parts of water the composition. The carrier (Carrier M) was
obtained by extrusion molding the resultant mixture, drying,
calcining at the temperature of 1350.degree. C. for 2 hours washing
out with boiling water for 30 min of three times and drying
thereof.
[0131] A Catalyst (Catalyst M) was obtained by following the
procedure of Example 1 while using a carrier M in place of a
carrier A and using 0.267 g of cesium nitrate instead. Silver
content of the catalyst obtained was 15.8 mass %, cesium content
was 0.090 mass % as cesium atom.
1TABLE 1 SiO.sub.2 per Specific specific Surface surface ave, pore
Water vol, ratio of pores vol, ratio of pores area SiO.sub.2 area
Na.sub.2O SiO.sub.2/ diameter apsorption having a diameter of
having a diameter of carrier (m.sup.2/g) (mass %) (mass %/m.sup.2)
(mass %) Na.sub.2O (.mu.m) rate (%) not more than 0.5 .mu. (%) not
more than 5 .mu. (%) A 0.78 2.43 3.12 0.20 12 1.72 40 18 82 B 1.20
2.91 2.42 0.22 13 0.88 40 33 93 C 1.84 2.27 1.23 0.24 9 0.44 41 37
84 D 0.60 2.70 4.50 0.16 16 1.79 31 13 94 E 0.45 6.70 14.9 2.35 3
2.79 49 10 67 F 1.76 2.6 1.48 0.02 130 0.72 39 26 90 G 3.62 12.4
3.43 0.59 21 0.29 44 52 99 H 0.73 2.8 3.84 3.61 0.8 1.26 32 41 82 I
1.13 0.03 0.03 0.00 -- 1.04 44 38 84 J 0.46 12.12 26.3 0.28 43 4.56
18 1 50 K 0.07 9.11 13.0 0.38 24 3.72 25 6 62 L 5.81 6.52 2.67 0.35
44 0.25 52 58 98 M 1.32 2.70 2.05 0.25 11 0.84 39 30 95
[0132]
2 TABLE 2 characters of carriers mixing ratio for preparing
carriers Diameter of Av. particle Amount of Organic Colloidal
Sodium almina diameter BET Sodium content Alumina bainder
Aluminasol silica hydroxide carrier crystal (.mu.m) (.mu.m)
(m.sup.2/g) (mmol/kg) (mass parts) (mass parts) (mass parts) (mass
parts) (mass parts) A 1 40 2 16 93 5 (MC) 4 3 0.15 B 1 65 3 16 93
.sup. 5 (CMC) 4 3 0.15 C 0.5 80 3 40 93 5 (MC) 4 3 0.10 D 4 40 1 8
93 .sup. 5 (CMC) 4 3 0.15 E 3 40 1 8 84 10 (MC) 4 7 2.4 F 0.5 40 3
8 93 5 (MC) 4 3 0 G 0.3 5 10 16 82 10 (MC) 4 14 0.6 H 0.5 10 5 96
93 5 (MC) 4 3 3.5 I 0.5 30 2 0.0 96 5 (MC) 4 0 0 J 10 60 1 8 84 5
(MC) 4 12 0.30 K 20 80 0.3 10 87 5 (MC) 4 9 0.30 L 0.3 5 10 16 89 5
(MC) 4 7 0.30 M 0.8 55 3 90 93 5 (MC) 4 3 0 MC: methylcellulose
CMC: carboxymethylcellulose sodium salt
[0133]
3 TABLE 3 reaction time for one day after the 100 h after the
silver cation component reaction five hr reaction start reaction
start Cata- content Content temp. C* S** C* S** C* S** lyst Carrier
(mass %) Compound (mass %) (.degree. C.) (mol/%) (mol/%) (mol/%)
(mol/%) (mol/%) (mol/%) Example 1 A1 A 16.2 CsCl 0.083 195 16 92 16
92 Example 2 A2 A 15.9 CsNO.sub.3 0.082 195 19 93 19 93 Example 3
A3 A 15.9 TlNO.sub.3 0.128 195 15 91 13 92 Example 4 B1 B 16.3
CsNO.sub.3 0.130 195 17 93 16 93 Example 5 B2 B 16.1
Cs.sub.2SO.sub.4 0.198 195 13 93 12 92 Example 6 C C 15.7
CsNO.sub.3 0.196 195 18 92 16 91 Example 7 D D 16.0 CsNO.sub.3
0.064 195 12 90 11 90 Example 8 E E 15.8 CsNO.sub.3 0.053 195 7 89
7 89 Example 9 A4 A 16.1 CsCl 0.085 195 12 92 11 91 Example 10 B3 B
15.8 CsNO.sub.3 0.440 195 17 89 17 90 16 90 Example 11 B4 B 16.3
CsNO.sub.3 0.482 195 14 87 15 88 13 87 Control 1 A5 A 15.9 -- --
195 0.2 78 almost no reaction Control 2 F F 16.3 CsNO.sub.3 0.195
195 5 74 almost no reaction Control 3 G G 15.7 CsNO.sub.3 0.393 195
4 75 almost no reaction Control 4 H H 15.9 CsNO.sub.3 0.080 195
almost no reaction Control 5 I I 15.7 CsCl 0.123 195 almost no
reaction Control 6 J J 10.6 CsNO.sub.3 0.055 195 2 82 Control 7 K K
15.3 CsNO.sub.3 0.010 195 almost no reaction Control 8 L L 15.9
CsNO.sub.3 0.622 195 almost no reaction Control 9 M M 15.8
CsNO.sub.3 0.090 195 6 84 0.9 82 C*: conversion ratio S**:
Selectivity ratio
[0134] The entire disclosure of Japanese Patent Application No.
11-267467 filed on Sep. 21, 1999 including specification, claims,
drawing and summary are incorporated herein by reference in its
entirety.
* * * * *