U.S. patent application number 17/237134 was filed with the patent office on 2021-08-19 for catalyst for hydrogenation of carbonyl compound and alcohol production method.
This patent application is currently assigned to Mitsubishi Chemical Corporation. The applicant listed for this patent is Mitsubishi Chemical Corporation. Invention is credited to Takayuki AOSHIMA, Takeshi MATSUO, Yumiko YOSHIKAWA.
Application Number | 20210253505 17/237134 |
Document ID | / |
Family ID | 1000005557082 |
Filed Date | 2021-08-19 |
United States Patent
Application |
20210253505 |
Kind Code |
A1 |
MATSUO; Takeshi ; et
al. |
August 19, 2021 |
CATALYST FOR HYDROGENATION OF CARBONYL COMPOUND AND ALCOHOL
PRODUCTION METHOD
Abstract
Provided is a catalyst including a metal component including a
first component that, is rhenium and one or more second components
selected from the group consisting of silicon, gallium, germanium,
and indium and a carrier on which the metal component is supported,
the carrier including an oxide of a metal belonging to Group 4 of
the periodic table. Also provided is an alcohol production method
in which a carbonyl compound is treated using the above catalyst,
it is possible to produce an alcohol by a hydrogenation reaction of
a carbonyl compound with high selectivity and high efficiency while
reducing 3ide reactions.
Inventors: |
MATSUO; Takeshi;
(Chiyoda-ku, JP) ; YOSHIKAWA; Yumiko; (Chiyoda-ku,
JP) ; AOSHIMA; Takayuki; (Chiyoda-ku, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Mitsubishi Chemical Corporation |
Tokyo |
|
JP |
|
|
Assignee: |
Mitsubishi Chemical
Corporation
Tokyo
JP
|
Family ID: |
1000005557082 |
Appl. No.: |
17/237134 |
Filed: |
April 22, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16563609 |
Sep 6, 2019 |
11014862 |
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17237134 |
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PCT/JP2018/008816 |
Mar 7, 2018 |
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16563609 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B01J 37/08 20130101;
C07C 29/141 20130101; B01J 23/36 20130101; B01J 21/063 20130101;
B01J 27/053 20130101; C07C 29/132 20130101; C07C 29/149 20130101;
B01J 37/18 20130101; C07C 29/136 20130101; B01J 23/6567
20130101 |
International
Class: |
C07C 29/149 20060101
C07C029/149; B01J 21/06 20060101 B01J021/06; B01J 23/36 20060101
B01J023/36; B01J 23/656 20060101 B01J023/656; B01J 27/053 20060101
B01J027/053; B01J 37/18 20060101 B01J037/18; C07C 29/141 20060101
C07C029/141; C07C 29/132 20060101 C07C029/132; C07C 29/136 20060101
C07C029/136 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 8, 2017 |
JP |
2017-043988 |
May 23, 2017 |
JP |
2017-102053 |
Claims
1-26. (canceled)
27. A method for producing a catalyst, the catalyst comprising a
metal component comprising a first component that is rhenium and
one or more second components selected from the group consisting of
silicon, gallium, germanium, and indium, and a carrier on which the
metal component is supported, the carrier comprising an oxide of a
metal belonging to Group 4 of the periodic table, the method
comprising: attaching the metal component the carrier to form a
metal-supporting material; reducing the metal-supporting material
with a reducing gas to form a metal-supporting catalyst; and then
oxidizing the metal-supporting catalyst.
28. The method according to claim 27, wherein the carrier comprises
a sulfate ion, the content of the sulfate ion in the carrier being
0.01% by mass to 10% by mass of the mass of the carrier.
29. A catalyst comprising a metal component comprising a first
component that is rhenium and one or more second components
selected from the group consisting of silicon, gallium, germanium,
and indium, and a carrier on which the metal component is
supported, the carrier comprising an oxide of a metal belonging to
Group 4 of the periodic table.
30. The catalyst according to claim 29, wherein a mass ratio of
elements that are the second components to the rhenium element is
in a range of 0.1 to 10.
31. The catalyst according to claim 29, wherein the oxide of a
metal belonging to Group 4 of the periodic table comprises titanium
oxide and/or zirconium oxide.
32. The catalyst according to claim 29, wherein the catalyst
comprises a sulfate ion, and the sulfate ion content in the
catalyst is 0.01% by mass to 10% by mass of the mass of the
catalyst.
33. The catalyst according to claim 29, wherein the catalyst is
suitable for hydrogenation of a carbonyl compound.
34. A catalyst comprising a metal component comprising a first
component that is rhenium and one or more second components
selected from the group consisting of silicon, gallium, germanium,
and indium, and a carrier on which the metal component is
supported, the mass ratio of elements that are the second
components to the rhenium element being in a range of 0.1 to
10.
35. The catalyst according to claim 34, wherein the second
components comprise germanium.
36. The catalyst according to claim 34, wherein the metal component
further comprises a third component which is a metallic element
belonging to Groups 8 to 10 of the periodic table, the metallic
element being other than iron or nickel, and wherein a mass ratio
of the metallic element to an amount of the rhenium element is less
than 0.2.
37. The catalyst according to claim 36, wherein the metallic
element comprises ruthenium.
38. The catalyst according to claim 34, wherein the carrier is a
carbonaceous carrier or a carrier comprising an oxide of a metal
belonging to Group 4 of the periodic table.
39. The catalyst according to claim 34, wherein the catalyst
comprises a sulfate ion, and the sulfate ion content in the
catalyst is 0.01% by mass to 10% by mass.
40. The catalyst according to claim 34, wherein the catalyst is
suitable for hydrogenation of a carbonyl compound.
Description
TECHNICAL FIELD
[0001] The present invention relates specifically to a catalyst
useful as a catalyst for hydrogenation of a carbonyl compound and
an alcohol production method in which a carbonyl compound is
hydrogenated using the catalyst.
BACKGROUND ART
[0002] Methods in which a carbonyl compound is hydrogenated to form
a corresponding alcohol have long been known. For example, a common
alcohol production method from an organic carboxylic acid is to
esterify a carboxylic acid with a lower alcohol and subsequently
perform reduction using an Adkins catalyst (copper chromite
catalyst).
[0003] However, the production of an alcohol with a copper
catalyst, which is commonly conducted under a severe condition such
as a hydrogen pressure of 200 atmospheres or more, is an
uneconomical process that consumes a large amount of energy for
producing an alcohol and introduces various facility restrictions.
Furthermore, since a copper catalyst is not capable of directly
reducing an organic carboxylic acid, a carboxylic acid needs to be
converted into a carboxylic acid ester before a reduction treatment
is performed. Therefore, multistage reaction processes need to be
conducted in order to produce an intended alcohol. This increases
the complexity of the process.
[0004] Moreover, in the case where the above production method is
used, it becomes considerably difficult to selectively produce a
hydroxycarboxylic acid using, for example, a polyvalent carboxylic
acid as a raw material by converting a part of the carboxylic acid
functional group3 into alcohol functional groups.
[0005] In contrast, a method in which a carboxylic acid is directly
hydrogenated (reduced) in one stage and a corresponding alcohol is
produced with high selectivity is an economically advantageous
process. Even in the case where a polyvalent carboxylic acid is
used as a raw material, it is possible to selectively produce a
corresponding hydroxycarboxylic acid by appropriately controlling
the reaction conditions.
[0006] There have been proposed various metal-supporting catalysts
that include a noble metal belonging to Groups 3 to 10 of the
periodic table as a catalytic activity component, for use in such a
process. Examples of the metal-supporting catalysts include a
catalyst produced by attaching palladium and rhenium to a carrier
and subsequently performing a reduction treatment with hydrogen or
the like (e.g., PTL 1 and NPL 1) and a catalyst produced by
attaching ruthenium and tin to a carrier and subsequently
performing a reduction treatment with hydrogen or the like (e.g.,
PTLs 2 and 3).
[0007] The above catalysts are suitable catalysts that have a high
reaction activity and high reaction selectivity in the reduction of
a carboxylic acid and/or a carboxylic acid eater. There has also
beer, proposed a hydrogenation reaction of a particular carboxylic
acid In which a cobalt catalyst that includes lanthanum and
palladium, which is an example of the above-described catalysts, is
used (e.g., PTL 4).
[0008] On the other hand, there have also been proposed catalysts
that do not include any of the expensive noble metals belonging to
Groups 8 to 10 of the periodic table. For example, a catalyst
including rhenium that serves as a catalytic component has been
reported since a long time ago (e.g., NPL 2). There has also been
proposed a tin-containing rhenium catalyst for use in a
hydrogenation reaction of a particular carboxylic acid (e.g., PTL
5). Recently, there has been reported a method for selectively
producing an intended alcohol under further mild conditions. In the
production method, a metal-supporting catalyst including rhenium
that serves as a catalytic activity component is used (e.g., NPLs 3
and 4).
[0009] However, since catalysts including rhenium that serves as a
catalytic activity component have lower catalytic activity than
catalysts including a noble metal, it is common to use, as a
supported metal, rhenium in combination with a noble metal
belonging to Groups 8 to 10 of the periodic table or to add cobalt,
which belongs to Group 9 of the periodic table, to a carrier (e.g.,
PTLs 6, 7, 8, and 9 and NPL 5).
[0010] PTL 1: Japanese Unexamined Patent Application Publication
No. 63-218636
[0011] PTL 2: Japanese Unexamined Patent Application Publication
No. 2000-007596
[0012] PTL 3: Japanese Unexamined Patent Application Publication
No. 2001-157841
[0013] PTL 4: Japanese Unexamined Patent Application Publication
No. 63-301845
[0014] PTL 5: Japanese Unexamined Patent Application Publication
No. 4-99753
[0015] PTL 6: Japanese Unexamined Patent Application Publication
No. 6-116182
[0016] PTL 7: Japanese Unexamined Patent Application Publication
(Translation of PCT Application) No. 2002-501817
[0017] PTL 8: Japanese Unexamined Patent Application Publication
(Translation of PCT Application) No. 2016-500697
[0018] PTL 9: Japanese Unexamined Patent Application Publication
No. 7-119187
[0019] NFL 1: Topics in Catalysis 55 (2012) 466-473
[0020] NPL 2: Journal of Organic Chemistry 24 (1959) 1847-1854
[0021] NPL 3: Journal of Catalysis 328 (2015) 197-207
[0022] NPL 4: Chemistry A European Journal 23 (2017) 1001-1006
[0023] NPL 5: ACS Catalysis 5 (2015) 7034-7047
SUMMARY OF INVENTION
Technical Problem
[0024] A catalyst including a noble metal belonging to Groups 6 to
10 of the periodic table which serves as a catalytic activity
component, which is produced using an expensive noble metal,
increases the costs of production of a catalyst. In addition, such
a catalyst typically causes side reactions, such as a degradation
reaction that involves decarboxylation, a defunctionalization
reaction associated with dehydration and hydrogenation of the
reaction product, and an esterification reaction of a carboxylic
acid used as a raw material with an alcohol produced. Thus, it is
necessary to reduce the above side reactions.
[0025] For example, as for a palladium metal-supporting catalyst
containing rhenium, the addition of rhenium increases the rate of
catalytic reaction in which succinic acid is converted into the
hydride of succinic acid, that is, butanediol, as described in NPL
1. However, the above-described side reactions also occur, which
reduce the productivity of the reaction product, and increase the
purification costs. In addition, the catalytic activity of such a
catalyst is still at an insufficient level.
[0026] As for the catalysts that include a catalytic component,
such as tin, in addition to a noble metal belonging to Groups 8 to
10 of the periodic table as proposed in PTLs 2 and 3, the addition
of tin or the like increases reaction selectivity. However, the
addition of such catalytic components may disadvantageously reduce
catalytic activity. This results in a necessity to further use a
large amount of expensive noble metal, such as platinum, and
increases the costs of production or a catalyst.
[0027] The catalyst including rhenium that serves as a principal
catalytic activity component allows a highly economical process to
be realized in the sense that the catalyst does not include any
expensive noble metal. However, such catalysts typically have lower
activity than catalysts that include a noble metal. Moreover, an
esterification reaction of a carboxylic acid used as a raw material
with an alcohol produced is likely to occur due to high Lewis
acidity of rhenium and, particularly at a later stage of the
reaction, a defunctionalization reaction may significantly occur
due to the dehydration and hydrogenation of the alcohol produced.
This significantly reduces the selectivity of the alcohol that is
t.c be produced.
[0028] An object of the present Invention is to provide a highly
economical alcohol production method that enables an intended
alcohol to be produced at a high yield with high selectivity by the
hydrogenation reaction of a carbonyl compound while reducing the
above-described various side reactions to a sufficient degree.
[0029] Another object of the present invention is to provide a
high-activity metal-supporting catalyst including rhenium which
enables an intended alcohol to be produced at a high yield with
high selectivity by the hydrogenation reaction of a carbonyl
compound while reducing the side reactions and a method for
producing such a metal-supporting catalyst.
Solution to Problem
[0030] The inventors of the present invention found that the above
issue3 may be addressed by using a catalyst produced by attaching
rhenium and a specific second component to a carrier when an
alcohol is produced by the hydrogenation reaction of a carbonyl
compound and consequently made the present invention.
[0031] The summary of the first aspect of the present invention
(hereinafter, referred to as "first invention") is as follows.
[0032] [1-1] An alcohol production method in which an alcohol is
produced from a carbonyl compound, the method comprising producing
an alcohol by using a catalyst, the catalyst including a metal
component including a first component that is rhenium and one or
more second components selected from the group consisting of
silicon, gallium, germanium, and indium and a carrier or which the
metal component is supported, the carrier including an oxide of a
metal belonging to Group 4 of the periodic table. [0033] [1-2] The
alcohol production method according to [1-1], wherein the mass
ratio of elements that are the second components included in the
catalyst to the rhenium element included in the catalyst is 0.1 or
more and 10 or less. [0034] [1-3] The alcohol production method
according to [1-1] or [1-2], wherein the oxide of a metal belonging
to Group 4 of the periodic table, the oxide being included in the
catalyst, includes titanium oxide and/or zirconium oxide. [0035]
[1-4] The alcohol production method according to any one of [1-1]
to [1-3], wherein the catalyst is a catalyst prepared by a method
including a step in which the metal component is attached to a
carrier including a sulfate ion. [0036] [1-5] The alcohol
production method according to [1-4], wherein the sulfate ion
content in the carrier is 0.01% by mass or more and 10% by mass or
less of the mass of the carrier. [0037] [1-6] The alcohol
production method according to any one of [1-1] to [1-5], wherein
the sulfate ion content in the catalyst is 0.01% by mass or more
and 10% by mass or less of the mass of the catalyst. [0038] [1-7] A
catalyst comprising a metal component including a first component
that is rhenium and one or more second components selected from the
group consisting of silicon, gallium, germanium, and indium, and a
carrier on which the metal component is supported, the carrier
including an oxide of a metal belonging to Group 4 of the periodic
table. [0039] [1-8] The catalyst according to [1-7], wherein the
mass ratio of elements that are the second components to the
rhenium element is 0.1 or more and 10 or less. [0040] [1-9] The
catalyst according to [1-7] or [1-8], wherein the oxide of a metal
belonging to Group 4 of the periodic table includes titanium oxide
and/or zirconium oxide. [0041] [1-10] The catalyst according to any
one of [1-7] to [1-9], wherein the sulfate ion content in the
catalyst is 0.01% by mass or more and 10% by mass or less of the
mass of the catalyst. [0042] [1-11] The catalyst according to any
one of [1-7] to [1-10], the catalyst being a catalyst used for
hydrogenation of a carbonyl compound.
[0043] The summary of the second aspect of the present invention
(hereinafter, referred to as "second invention") is as follows.
[0044] [2-1] An alcohol production method in which an alcohol is
produced from a carbonyl compound, the method comprising producing
an alcohol by using a catalyst, the catalyst including a metal
component including a first component that is rhenium and one or
more second components selected from the group consisting of
silicon, gallium, germanium, and indium and a carrier on which the
metal component is supported, the mass ratio of elements that are
the second components to the rhenium element being 0.1 or more and
10 or less. [0045] [2-2] The alcohol production method according to
[2-1], wherein the second components of the catalyst include
germanium. [0046] [2-3] The alcohol production method according to
[2-1] or [2-2], wherein the mass ratio of a metallic element
belonging to Groups 3 to 10 of the periodic table to the rhenium
element included in the catalyst, the metallic element being other
than iron or nickel, is less than 0.2. [0047] [2-4] The alcohol
production method according to [2-3], wherein the metallic element
belonging to Groups 3 to 10 of the periodic table, the metallic
element being included in the catalyst, the metallic element being
other than iron or nickel, includes ruthenium. [0048] [2-5] The
alcohol production method according to any one of [2-1] to [2-4],
wherein the carrier is a carbonaceous carrier or a carrier
including an oxide of n metal belonging to Group 4 of the periodic
table. [0049] [2-6] The alcohol production method according to any
one of [2-1] to [2-5], wherein the catalyst is a catalyst prepared
by a method including a step in which the metal component is
attached to a carrier including a sulfate ion. [0050] [2-7] The
alcohol production method according to [2-6], wherein the sulfate
ion content in the carrier is 0.01% by mass or more and 10% by mass
or less of the mass of the carrier. [0051] [2-8] The alcohol
production method according to any one of [2-1] to [2-7], wherein
the sulfate ion content in the catalyst is 0.01% by mass or more
and 10% by mass or less of the mass of the catalyst. [0052] [2-9] A
catalyst comprising a metal component including a first component
that is rhenium and one or more second components selected from the
group consisting of silicon, gallium, germanium, and indium and a
carrier on which the metal component is supported, the mass ratio
of elements that are the second components to the rhenium element
being 0.1 or more and 10 or less. [0053] [2-10] The catalyst
according to [2-9], wherein the second components include
germanium. [0054] [2-11] The catalyst according to [2-9] or [2-10],
wherein the mass ratio of a metallic element belonging to Groups 3
to 10 of the periodic table to the amount of the rhenium element,
the metallic element being other than iron or nickel, is less than
0.2. [0055] [2-12] The catalyst according to [2-13], wherein the
metallic element belonging to Groups 8 to 10 of the periodic table,
the metallic clement being other than iron or nickel, includes
ruthenium. [0056] [2-13] The catalyst according to any one of [2-9]
to [2-12], wherein the carrier is a carbonaceous carrier or a
carrier including an oxide of a metal belonging to Group 4 of the
periodic table. [0057] [2-14] The catalyst according to any one of
[2-9] to [2-13], wherein the sulfate ion content in the catalyst is
0.01% by mass or mere and 10% by mass or less. [0058] [2-15] The
catalyst according to any one of [2-9] to [2-14], the catalyst
being a catalyst used for hydrogenation of a carbonyl compound.
[0059] [2-16] A method for producing a catalyst, the method
comprising attaching a metal component including at least a first
component that is rhenium and one or more second components
selected from the croup consisting of silicon, gallium, germanium,
and indium to a carrier including a sulfate ion, the content of the
sulfate ion in the carrier being 0.01% by mass or more and 10% by
mass or less of the mass of the carrier.
Advantageous Effects of Invention
[0060] According to the first invention, there is provided an
alcohol production method in which a carbonyl compound is reduced
into an alcohol with high activity and high selectivity by using a
reduction catalyst including rhenium that serves as a catalytic
activity component, the catalyst further including one or more
catalytic additive components selected from the group consisting of
silicon, gallium, germanium, and indium and a carrier including an
oxide of a metal belonging to Group 4 of the periodic table, the
catalytic additive components being supported on the carrier. Also
provided is the catalyst useful for producing an alcohol. Note that
the term "periodic table" used herein refers to the long form of
periodic table (Nomenclature of Inorganic Chemistry IUPAC
recommendations 2005).
[0061] The catalyst according to the first invention enables an
increase in catalytic activity, which has been an issue for rhenium
catalysts, to be achieved substantially without using noble metals
belonging to Groups 8 to 10 of the periodic table. The catalyst
according to the first Invention also makes it possible to produce
an alcohol from a carbonyl compound while reducing side reactions,
such as an esterification reaction of a carboxylic acid used as a
raw material with an alcohol produced and a defunctionalization
reaction due to the dehydration and hydrogenation of the alcohol
produced, which significantly occurs particularly at a later stage
of the reaction, to a high degree. It becomes also possible to, in
the case where a polyvalent carboxylic acid 13 used as a raw
material, produce a hydroxycarboxylic acid with high selectivity by
converting a part of the carboxylic acid functional groups into
alcohol functional groups.
[0062] According to the second invention, there is provided an
alcohol production method in which a carbonyl compound is reduced
into an alcohol with high activity and high selectivity by using a
reduction catalyst including rhenium that serves as a catalytic
activity component, the catalyst further including one or more
catalytic additive components selected from the group consisting of
silicon, gallium, germanium, and indium at a predetermined
elemental mass ratio and a carrier, the catalytic additive
components being supported on the carrier. Also provided is the
catalyst useful for producing an alcohol.
[0063] The catalyst according to the second invention enables an
increase in catalytic activity, which has been an issue for rhenium
catalysts, to be achieved substantially without using noble metals
belonging to Groups 8 to 10 of the periodic table. The catalyst
according to the second invention also makes it possible to produce
an alcohol from a carbonyl compound while reducing side reactions,
such as the esterification reaction of a carboxylic acid used as a
raw material with an alcohol produced and a defunctionalization
reaction due to the dehydration and hydrogenation of the alcohol
produced, which significantly occurs particularly at a later stage
of the reaction, to a high degree. It becomes also possible to, in
the ease where a polyvalent carboxylic acid is used as a raw
material, produce a hydroxycarboxylic acid with high selectivity by
converting a part of the carboxylic acid functional groups into
alcohol functional groups.
DESCRIPTION OF EMBODIMENTS
[0064] Embodiments of the present, invention are described below in
detail. The elements described below are merely an example (typical
example) of an aspect of the present invention. The present
invention is not limited by the description and may be modified
within the scope of the present invention.
[0065] In the present invention, catalytic components supported on
a carrier (e.g., rhenium; one or more elements selected from the
group consisting of silicon, gallium, germanium, and indium; and
optional metal elements belonging to Groups 8 to 10 of the periodic
table, such as ruthenium) may be referred to collectively as "metal
components".
[0066] A material produced by attaching the metal components to a
carrier may be referred to as "metal-supporting material".
[0067] A catalyst, produced by reducing the metal-supporting
material may be referred to as "metal-supporting catalyst".
[0068] In the present invention, the metal components supported on
the carrier are the same as the metal components included in the
catalyst.
[0069] The content of the supported metal in the catalyst can be
determined by publicly known analysis methods, such as inductively
coupled plasma mass spectrometry (ICP-MS), inductively coupled
plasma atomic emission spectrometry (ICP-AES), atomic absorption
spectrometry (AAS), and X-ray fluorescence analysis (XRK). In the
case where ICP-MS, ICP-AES, and AAS are used, the sample is formed
into a solution in a pretreatment conducted in combination with the
analysis. The type of the analysis method used is not limited since
an appropriate analysis method varies with the element subjected to
the quantitative analysis, the concentration of the element, and
the accuracy required for the analysis. In the present invention,
the quantitative analysis of the supported metal included in the
catalyst is conducted using inductively coupled plasma atomic
emission spectrometry, atomic absorption spectrometry, or both
inductively coupled plasma atomic emission spectrometry and atomic
absorption spectrometry in order to determine the metal content in
the catalyst.
[0070] The mass ratio between the metal components supported on the
carrier is calculated on the basis of the metal components included
in the catalyst as in the description of the method for determining
the content of the supported metal in the catalyst. The mass ratio
between the rhenium element an a the second component element can
be determined using publicly known analysis methods, such as
inductively coupled plasma mass spectrometry (ICP-MS), inductively
coupled plasma atomic emission spectrometry (ICP-AES), atomic
absorption spectrometry and X-ray fluorescence analysis (XRF), as
in the description of the method for determining the content, of
the supported metal in the catalyst.
[0071] In the present invention "% by weight" and "% by mass" are
synonymous with each other, and "element" and "atom" are synonymous
with each other.
[0072] The catalyst according to the present invention can be
suitably used as a hydrogenation catalyst when an alcohol is
produced from a carbonyl compound. In the present invention, a
carbonyl compound is defined as a compound that includes a
carbon-oxygen double bond (C.dbd.O), and
[0073] An alcohol is defined as a compound produced by converting
the carbonyl compound into an alcohol functional group (OH).
[0074] Therefore, in the present invention, in the case where a
carbonyl compound used as a raw material includes a plurality of
carbon-oxygen double bonds, a compound produced by converting at
least one of the carbon-oxygen double bonds of the carbonyl
compound into an alcohol functional group is defined as an
alcohol.
Catalyst According to First Invention
[0075] A catalyst according to the first invention (hereinafter,
may be referred to simply as "first catalyst") is a
metal-supporting catalyst that includes a metal component and a
carrier on which the metal component is supported. Specifically,
the metal components including a first component that is rhenium
arid one or more second components selected from the group
consisting of silicon, gallium, germanium, and indium are supported
on a carrier including an oxide of a metal belonging to Group 4 of
the periodic cable.
[0076] The first catalyst is normally produced by reducing a
metal-supporting material on which the metal component is supported
with a reducing gas and then performing an oxidative stabilization
treatment as needed.
[0077] <Metal Component>
[0078] The metal component supported on the metal-supporting
catalyst according to the first invention includes a first
component that is rhenium and one or more second components
selected from the group consisting of silicon, gallium, germanium,
and indium. Among these, the second components used in combination
with rhenium are preferably one or more elements selected from the
group consisting of silicon, germanium, and indium, are more
preferably one or more elements that include indium end/or
germanium, are further preferably one or more elements that include
germanium, and are particularly preferably germanium.
[0079] As for the ratio between the amounts of the above essential
components supported on the catalyst, the lower limit for the mass
ratio of the second component elements that are one or mere
elements selected from the group consisting of silicon, gallium,
germanium, and indium to the rhenium element is preferably 0.1 or
more and is more preferably 0.5 or more, and the upper limit for
the above mass ratio is preferably 10 or less, is more preferably 5
or less, is further preferably 3 or less, is particularly
preferably 2 or less, and is most preferably 1 or less.
[0080] Appropriately selecting the types of the second components
used in combination with rhenium and/or the proportion of the
second components supported on the carrier increases the catalytic
activity in a hydrogenation reaction of a carbonyl compound and
makes it possible to produce an alcohol while reducing side
reactions, such as the esterification reaction of a carboxylic acid
used as a raw material with an alcohol produced and a
defunctionalization reaction due to the dehydration and
hydrogenation of the alcohol produced, which significantly occurs
particularly at a later stage of the reaction, to a high degree.
Using the above metal components in combination with one another
enables the first catalyst to be handled in the air atmosphere.
This increases ease of operation, such as transportation and
storage of the catalyst and introduction cf the catalyst to a
reactor in the production of an alcohol.
[0081] Using the above metal components in combination with one
another enables an increase in catalytic activity and an increase
in reaction selectivity, which have been Considered contradictory,
to be both achieved presumably for the following reasons: the
addition of the second components enables the electronic state of
rhenium, which is a catalytic activity component of the
hydrogenation catalyst, to be controlled to be in a state suitable
for a reduction reaction of a carbonyl functional group; the
adsorptivity of reactive substrates onto the surface of the
catalyst is enhanced due to the affinity of the reactive substrates
tor the second components; and the orientation of adsorption of the
reactive substrates on the surface of the catalyst is controlled at
a high degree.
[0082] Although the amount of rhenium supported on the first
catalyst is not limited, the mass ratio of the rhenium element, to
the total mass of the metal-supporting catalyst is normally 0.5% by
mass or more, is preferably 1% by mass or more, is more preferably
3% by mass or snore, is normally 20% by mass or less, is preferably
10% by mass or less, and is more preferably 8% by mass or less.
When the amount of rhenium supported on the catalyst is limited to
be equal to or more than the lower limit, sufficiently high
catalytic activity can be achieved. This prevents, for example, an
increase in the volume of the reactor used. When the amount of
rhenium supported on the catalyst is limited to be equal to or less
than the upper limit, an increase in the cost of the catalyst can
be limited, furthermore, in such a case, coagulation of rhenium
supported on the catalyst can be reduced. This reduces the side
reactions, such as a degradation reaction involved by
decarboxylation, a defunctionalization reaction associated with
dehydration and hydrogenation of the reaction product, and an
esterifications reaction of a carboxylic acid used as a raw
material with an alcohol produced, due to high Lewis acidity of
rhenium. As a result, reaction selectivity can be further
increased.
[0083] The first catalyst may further include, as needed, a third
component that is a metal component other than the above metal
components (i.e., rhenium and the second components) and that does
not adversely affect the reactions conducted using the. first
catalyst, such as a reduction reaction. Examples of the other metal
component include metal components belonging to Groups 3 to 10 of
the periodic table except iron and nickel. Examples thereof include
at least one metal selected from the group consisting of ruthenium,
cobalt, rhodium, iridium, palladium, and platinum which are capable
of catalyzing hydrogenation.
[0084] Metals, such as iron and nickel, may elute and enter the
catalyst when a metal reaction container made of SS, SUS, or the
like becomes corroded in the preparation oil the catalyst and/or
the reaction. In the first invention, in the case where the eluted
metal is precipitated on the catalyst and included in the catalyst,
the metal is not defined as a metal component of the first
catalyst. In the case of elution from a reaction container made of
SUS, in addition to iron, the following metals may be detected in
the catalyst in trace amounts at specific contents depending on the
material used.
[0085] For example, when metals enter from SUS201, nickel,
chromium, and manganese may foe detected in addition to iron at
specific contents. When metals enter from SUS202, nickel chromium,
and manganese may foe detected in addition to iron at specific
contents. When metals enter from SUS301, nickel and chromium may be
detected in addition to iron at specific contents. When metals
enter from SUS302, nickel and chromium may be detected in addition
to iron at specific contents. When metals enter from SUS303,
nickel, chromium, and molybdenum may be detected in addition to
iron at specific contents. When metals enter from SUS304, nickel
and chromium may be detected in addition to iron at specific
contents. When metals enter from SUS305, nickel and chromium may be
detected in addition to iron at specific contents. When metals
enter from SUS316, nickel, chromium, and molybdenum may be detected
in addition to iron at specific contents. When metals enter from
SUS317, nickel, chromium, and molybdenum may be detected in
addition to iron at specific contents. When metals enter from
SUS329J1, nickel, chromium, and molybdenum may be detected in
addition to iron at specific contents. When metals enter from
SUS403, chromium may be detected in addition to iron at a specific
content. When metals enter from SUS405, chromium and aluminum may
be detected in addition to iron at specific contents. When metals
enter from SUS420, chromium may be detected in addition to iron at
a specific content. When metals enter from SUS430, chromium may be
detected in addition to iron at a specific content. When metals
enter from 8US430LX, chromium, titanium, or niobium may be detected
in addition to iron at a specific content. When metals enter from
SUS630, nickel, chromium, copper, and niobium may be detected in
addition to iron at specific contents.
[0086] Examples of the metal component that belongs to a group
other than Groups 8 to 10 of the periodic table include at least
one metal selected from the group consisting of silver, gold,
molybdenum, tungsten, aluminum, and boron.
[0087] Among the above third components, at least one metal
selected from ruthenium, cobalt, rhodium, iridium, palladium,
platinum, gold, molybdenum, and tungsten is preferable; at least
one metal selected from ruthenium, cobalt, rhodium, iridium,
palladium, platinum, molybdenum, arid tungsten is more preferable;
at least one metal selected from ruthenium, iridium, palladium, and
platinum is particularly preferable; and ruthenium is most
preferable.
[0088] In the case where the third component is selected from rare
and expensive metals belonging to Groups 8 to 10 of the periodic
table except iron and nickel, the elemental mass ratio of the third
component included in the first catalyst to the rhenium element is
normally less than 0.2, is preferably 0.15 or less, is more
preferably 0.1 or less, is further preferably less than 0.1, and is
most preferably 0 in order to increase reaction selectivity and
economical efficiency in terms of the costs for producing the
catalyst. That is, it is preferable that the first catalyst
substantially do not include any of the rare and expensive metals
belonging to Groups 8 to 10 of the periodic table other than iron
or nickel.
[0089] In the case where the third component is selected from
metals other than the noble metals belonging to Groups 8 to 10 of
the periodic table, the elemental mass ratio of the third component
to the rhenium element is normally 10 or less, is preferably 5 or
less, is more preferably 1 or less, and is further preferably 0.5
or less. When the above additional metal components are used in an
appropriate combination at adequate contents, it is possible to
achieve high catalytic activity while maintaining high
selectivity.
[0090] In the case where a metal, such as iron or nickel, becomes
eluted and enters the catalyst due to the corrosion of a reaction
container made of SS, SUS, or the like, in the first invention, the
content of iron and the contents of the above metals included at
specific contents, which are determined on the basis of the type of
material constituting the reaction container, are not taken into
account in the calculation of the content of the metal components
in the catalyst.
[0091] In order to further increase the activity of the catalyst,
reaction selectivity, and the like, the first catalyst may include
compounds of one or more alkali metal elements selected from the
group consisting of lithium, sodium, potassium, rubidium, and
cesium; compounds of one or more alkaline-earth metal elements
selected from the group consisting of magnesium, calcium,
strontium, and barium; and compounds of one or more halogen
elements selected from the group consisting of fluorine, chlorine,
bromine, and iodine, in addition to the metal components described
above. In such a case, the ratio between the additional components
and the rhenium component is nor. limited.
[0092] <Carrier>
[0093] The carrier used in the first invention is a carrier that
includes an oxide of a metal belonging to Group 4 of the periodic
table. In particular, an inert carrier can be used. The term "inert
carrier" used herein refers to a carrier that does not have a
catalytic activity in a hydrogenation or a carbonyl compound alone.
Specifically, the inert carrier is defined as a carrier that
substantially does not include any of the metals belonging to Group
8 to 12 of the periodic table which is selected from the group
consisting oi iron, ruthenium, cobalt, rhodium, iridium, nickel,
palladium, platinum, copper, and zinc, chromium, and rhenium, which
are metals having catalytic activity.
[0094] A carrier that substantially does not include any cf the
above metals is a carrier that does not primarily include any of
the above metals. That is, the amount of the above metals included
in the carrier to the total mass of the carrier is 5% by mass or
less, is preferably 1% by mass or less, and is mere preferably 0.1%
by mass or less. The content of the above metals in the carrier can
be determined as in the analysis of the content of the supported
metal in the catalyst, using publicly known analysis methods, such
as inductively coupled plasma mass spectrometry (ICP-MS),
inductively coupled plasma atomic emission spectrometry (ICP-AES),
atomic absorption spectrometry (AAS), and X-ray fluorescence
analysis (XRF).
[0095] In the first invention, a carrier that includes an oxide of
a metal belonging to Group 4 of the periodic table, such as
titanium oxide (titania), zirconium oxide (zirconia), or hafnium
oxide, is used in order to increase catalytic activity and reaction
selectivity achieved particularly when a carboxylic acid is used as
a raw material and ease of regeneration of the catalyst and reduce
the elution of metals. Among the oxides of metals belonging to
Group 4 of the periodic table, titanium oxide and zirconium oxide
are preferable in order to increase catalytic activity and produce
an intended alcohol with high selectivity. Among these, titanium
oxide may be particularly preferable in order to readily produce
carrier particles having a large specific surface area. The oxides
of metals belonging to Group 4 of the periodic table may be used
alone or in combination of two or more. In the case where the
oxides of metals belonging to Group 4 of the periodic table are
used in combination of two or more, the combination of the oxides
arid the mixing ratio between the oxides are not limited. The
oxides can be used in a form similar to a mixture of the individual
compounds or a composite oxide.
[0096] It may be preferable that the carrier used in the first
invention contain a sulfate ion. In particular, in the case where
titanium oxide is used as a carrier, it may fee preferable that the
carrier contain a sulfate ion.
[0097] In the first invention, using a carrier including a sulfate
ion may markedly reduce a degradation reaction involved by
decarboxylation and a defunctionalization reaction associated with
dehydration and hydrogenation of the reaction product, that is, an
alcohol, which occur simultaneously with a catalytic reaction of
hydrogenation of a carbonyl compound. In addition, when the metal
components that include rhenium and the second components are
supported on such a carrier, the catalytic activity of the
hydrogenation catalyst may be markedly increased. When the metal
components are used in combination with the carrier, the catalyst
can be handled in the air atmosphere. This increases ease of
operation of the catalyst, such as transportation and storage of
the catalyst and introduction of the catalyst to a reactor in the
production of an alcohol.
[0098] It is considered that the functions of the catalyst are
enhanced for the following reasons: when the carrier contains a
sulfate ion, sulfate ions present in the surface of the carrier may
form acid sites on the surface of the catalyst. Furthermore, the
dispersibility of the supported metal may be increased due to the
interaction between the supported metal and the sulfate ion or a
substitution reaction of the supported metal with the sulfate ion
which occurs when the metal components are supported on the
carrier. Moreover, the electronic state of rhenium, which is a
catalytic activity component of the hydrogenation catalyst, can be
controlled to be in a state suitable for a reduction reaction of a
carbonyl functional group. The above factors may synergistically
increase the reaction selectivity of the catalyst and the activity
of the catalyst.
[0099] The mass ratio of the amount of the sulfate ion included in
the carrier to the total mass of the carrier used is preferably
0.01% by mass or more, is more preferably 0.1% by mass or more, and
is particularly preferably 0.2% by mass or more. The mass ratio of
the amount of the sulfate ion to the total mass of the carrier used
is preferably 10% by mass or less, Is more preferably 7% by mass or
less, and is particularly preferably 5% by mass or less.
[0100] When the content of the sulfate ion in the carrier used is
limited to be equal to or more than the lower limit, the
advantageous effects of adding the above components are achieved at
a sufficient level and high catalytic activity can be achieved,
furthermore, the occurrence of the defunctionalization reaction can
be further reduced. This limits an increase in the complexity of
the process for purifying the reaction product and an increase in
the purification costs and consequently enables an economically
advantageous alcohol production process to be provided. Limiting
the content of the sulfate ion in the carrier used to he equal to
or less than the upper limit reduces, for example, corrosion of the
reactor caused by sulfate ions included in the carrier becoming
eluted during the reaction depending on the solvent used and side
reactions of the target product caused by the liberated acid
catalyst and therefore eliminates the need to use materials having
high corrosion resistance. This limits increases in the costs for
constructing reaction facilities and the costs for purifying the
product and enables an economically advantageous alcohol production
process to be provided.
[0101] In the case where a carrier including a sulfate ion is used
in the first invention, the carrier is not limited and may be any
carrier that includes a sulfate ion. An appropriate commercial
product may be used directly. In the case where the carrier is
composed of a metal oxide, the carrier may be prepared by, for
example, dissolving a corresponding metal sulfate in water and
subsequently performing neutralization or pyrohydrolysis, or by
treating a corresponding metal hydroxide or a baked metal oxide
with a sulfatizing agent and subsequently performing baking in an
oxidizing atmosphere, such as the air atmosphere. The treatment
using a sulfatizing agent is to introduce sulfate ions into the
carrier. This treatment nay be performed in the step of producing
the carrier or nay be performed after the production of the
carrier. Examples of the sulfatizing agent include sulfuric acid,
persulfuric acid, and the salts thereof. Sulfuric acid, a sulfuric
acid salt, and a persulfuric acid salt are preferable. The sulfuric
acid salt is not limited and may be any sulfuric acid salt capable
of providing sulfate ions when dissolved. Examples of the sulfuric
acid salt include ammonium sulfate, sodium sulfate, and potassium
sulfate. The same applies to the persulfuric acid salt, and
examples thereof include ammonium persulfate, sodium persulfate,
and potassium persulfate. The above salts may be in the form of an
anhydride or hydrate. Such salts may be preferable in some cases
because they are less hazardous than acids and easy to handle.
[0102] A preparation example of the carrier including a sulfate ion
according to the first invention is described below, taking
titanium oxide and zirconium oxide as an example.
[0103] Titanium oxide containing a sulfate ion car. be prepared by
dissolving titanium sulfate or titanyl sulfate in water,
subsequently performing neutralization at a low temperature or
pyrohydrolysis, and then performing baking. Titanium oxide
containing a sulfate ion can also be prepared by dissolving
titanium ore in sulfuric acid, subsequently performing heating to
produce metatitanic acid or titanium hydroxide, and then performing
baking.
[0104] In another case, titanium oxide containing a sulfate ion may
be produced by passing dilute sulfuric acid through titanium
hydroxide, which is a starting material, prepared from titanium
tetraisopropoxide or the like and subsequently performing baking in
the air atmosphere. Alternatively, a baked titanium oxide may also
be used as a starting material instead of titanium hydroxide.
Instead of passing sulfuric acid, a sulfuric acid salt, such as
ammonium 3ulfate, may be supported on the carrier.
[0105] The titanium oxide that has been subjected to the
sulfatizing treatment is subsequently baked. The baking temperature
is preferably 350.degree. C. to 700.degree. C. and is more
preferably 450.degree. C. to 600.degree. C. It is not preferable to
set the baking temperature to be excessively high because, if the
baking temperature is excessively high, the sulfate ions included
in the catalyst become volatilized and the surface area of the
titanium oxide decreases disadvantageous. The amount of baking time
during which the baking is performed is not limited. It is
appropriate to set the baking time to about 3 hours.
[0106] Examples of a commercial product, of the titanium oxide
containing a sulfate ion include MC-50, MC-90, and MC-150 produced
by Ishihara Sangyo Kaisha, Ltd., which are also described in
Examples of the first Invention below.
[0107] Zirconium oxide containing a sulfate ion can be prepared by,
&.& in the preparation example of the titanium oxide,
adding sulfuric acid, a sulfate, a persulfate, or the like to a
starting material that is, for example, zirconium hydroxide
prepared by adding ammonia wafer to an aqueous solution of a
zirconium compound, such as zirconium oxychloride, zirconium
oxynitrate, zirconium propoxide, or the like, and subsequently
performing baking in the air atmosphere. Alternatively, a baked
zirconium oxide may also be used instead of zirconium hydroxide.
Instead of passing dilute sulfuric acid, a sulfuric acid, such as
ammonium sulfate, may be supported on the carrier.
[0108] The zirconium oxide that has been subjected to the
sulfatizing treatment is subsequently baked. The baking temperature
is preferably 350.degree. C. to 700.degree. C. and is more
preferably 450.degree. C. to 600.degree. C. It is not preferable to
set the baking temperature to be excessively high because, if the
baking temperature is excessively high, the sulfate ions included
in the catalyst become volatilized and the surface area of the
zirconium oxide decreases disadvantageously. The amount of baking
tine during which the baking is performed is not limited. It is
appropriate to set the baking time to about 3 hours.
[0109] In the case where the carrier is a commercial carrier, the
content of sulfate ion in the carrier has been published by the
manufacturer, and the sulfate ion content falls within the
above-described range of sulfate ion content specified in the first
invention, the carrier is considered to correspond to the carrier
according to the first invention. Examples of such a commercial
carrier include MC-50, MC-90, and MC-130 produced by Ishihara
Sangyo Kaisha, Ltd.
[0110] In the case where it is clear that the sulfur element
Component of the carrier is derived from a sulfate ion,
alternatively, the content of sulfate ion in the carrier or
catalyst may be determined using a publicly known high-frequency
furnace combustion-infrared detection method (carbon sulfur
analyzer) by combusting the catalyst in a high-frequency induction
heating furnace under an oxygen atmosphere and converting the
content of sulfur in the combustion gas into the mass of sulfate
ion, which is determined by an infrared detection method.
[0111] In the case where the catalyst according to the first
invention contains a sulfate ion, the content of the sulfate ion in
the catalyst is not limited and the mass ratio of the amount of
sulfate ion to the total mass of the catalyst is preferably 0.01%
by mass or more, is more preferably 0.1% by mass or more, is
particularly preferably 0.2% by mass or wore, is normally 10% by
mass or less, is preferably 7% by mass or less, is more preferably
5% by mass or less, is particularly preferably 2% by mass or less,
and is most preferably 1% by mass or less. The mass ratio of the
amount of sulfur element to the total mass of the catalyst is
preferably 0.01% by mass or more, is more preferably 0.1% by mass
or more, is normally 3% by mass or less, is preferably 2% by mass
or less, is more preferably 1% by mass or less, and is particularly
preferably 0.6% by mass or less.
[0112] Using a catalyst containing a sulfate ion or sulfur may
markedly reduce a degradation reaction involved by decarboxylation
and a defunctionalization reaction associated with dehydration and
hydrogenation of the reaction product, that is, an alcohol, which
occur simultaneously with a catalytic reaction of hydrogenation of
a carbonyl compound. Limiting the content of sulfate ion in the
catalyst to be equal to or more than the lower limit, may increase
catalytic activity to a sufficient degree and reduce the occurrence
of the defunctionalization reaction to a sufficient degree. This
limits an increase in the complexity of the process for purifying
the reaction product and an increase in the purification coats and
consequently enables an economically advantageous alcohol
production process to be provided. Limiting the content of sulfate
ion in the catalyst according to the present invention to be equal
to or more than the lower limit also enhances the stability of the
catalyst in the air atmosphere. This increases ease of operation of
the catalyst, such as transportation and storage of the catalyst
and introduction cf the catalyst to a reactor in the production of
an alcohol. Limiting the content of the sulfate ion m the catalyst
to be equal to or less than the upper limit reduces, for example,
corrosion of the reactor caused by sulfate ions included in the
catalyst becoming eluted during the reaction and side reactions of
the target product caused by the liberated acid catalyst. This
limits increases in the costs for constructing reaction facilities
and the costs for purifying the target product and enables an
economically advantageous alcohol production process to be
provided.
[0113] In the first invention, the content of the sulfate ion in
the carrier or catalyst is determined by publicly known ion
chromatography after the sulfate ion has been extracted from the
catalyst in a pretreatment 3tep.
[0114] The content of the sulfur in the carrier or catalyst is
determined using a publicly known high-frequency furnace
combustion-infrared detection method (carbon sulfur analyzer) by
combusting the catalyst in a high-frequency induction heating
furnace under an oxygen atmosphere and calculating the content of
sulfur in the combustion gas by an infrared detection method.
[0115] The carrier used in the first invention is preferably
composed primarily of the oxide of a metal belonging to Group 4 of
the periodic table. The expression "composed primarily of" used
herein means that the mass ratio of the oxide of a metal belonging
to Group 4 of the periodic table to the total mass of the carrier
is normally 50% by mass or more, is preferably 70% by mass or more,
and is more preferably 90% to 100% by mass.
[0116] The carrier used in the first invention may include a
carrier component other than the oxide of a metal belonging to
Group 4 of the periodic table. Examples of the other carrier
component include one or more compounds selected from graphite,
active carbon, silicon carbide, silicon nitride, aluminum nitride,
boron nitride, boron oxide, aluminum oxide (alumina), silicon oxide
(silica), lanthanum oxide, cerium oxide, yttrium oxide, niobium
oxide, magnesium silicate, calcium silicate, magnesium aiuminate,
calcium aluminate, aluminosilicate, aluminosilicophosphate,
aluminophosphate, magnesium phosphate, calcium phosphate, strontium
phosphate, apatite hydroxide (calcium hydroxyphosphate), apatite
chloride, apatite fluoride, calcium sulfate, barium sulfate, and
barium carbonate.
[0117] The specific surface area of the carrier particles used in
the first invention varies by the type of the carrier used and is
not limited. The specific surface area of the carrier particles
used in the first invention is normally 50 m.sup.2/g or more, is
preferably 80 m.sup.2/g or more, is more preferably 100 m.sup.2/g
or more, is normally 3000 m.sup.2/g or less, and is preferably 2000
m.sup.2/g or less. In particular, in the first invention in which
the oxide of a metal belonging to Group 4 of the periodic table is
used, the specific surface area of the carrier particles is
normally 50 m.sup.2/g or more, is preferably 80 m.sup.2/g or more,
is more preferably 100 m.sup.2/g or more, is normally 1000
m.sup.2/g or less, and is preferably 800 m.sup.2/g or less. The
larger the specific surface area of the carrier particles, the
higher the catalytic activity. Therefore, carrier particles having
a larger specific surface area are suitably used. The specific
surface area of the carrier particles is generally calculated from
the amount of nitrogen adsorbed on the carrier particles using the
BET equation.
[0118] The shape and size of the carrier particles used in the
first invention are not limited. When the shape of the carrier
particles is converted into a spherical shape, the average particle
size of the carrier is normally 0.1 .mu.m or more, is preferably 3
.mu.m or more, is more preferably 5 .mu.m or more, is further
preferably 50 .mu.m or more, is normally 5 mm or less, and is
preferably 4 mm or less. The particle size of the carrier is
measured in accordance with Test sieving described in JIS Standard
JIS Z8815 (1894). In the case where the shape of a carrier particle
is not spherical, the volume of the carrier particle is measured,
the diameter of a spherical particle having the same volume as the
carrier particle is calculated, and the diameter of the spherical
particle is considered the diameter of the carrier particle. When
the average particle size of the carrier falls within the above
range, the activity of the catalyst per unit mass is increased, and
ease of handling of the catalyst is further increased.
[0119] In the case where the reaction conducted using the first
catalyst is a complete mixing reaction, the average particle size
of the carrier is normally 0.1 .mu.m or more, is preferably 1 .mu.m
or more, is more preferably 5 .mu.m or more, is further preferably
50 .mu.m or more, is normally i ism or less, and is preferably 2 mm
or less. It is preferable to reduce the average particle size of
the carrier because the smaller the average particle size of the
carrier, the higher the activity of the catalyst per unit mass.
However, setting the average particle size of the carrier to be
excessively smaller than the above lower limit may make it
difficult to separate the reaction liquid and the catalyst from
each other.
[0120] In the case where the reaction conducted using the first
catalyst is a fixed-bed reaction, the average particle size of the
carrier is normally 0.5 mm or snore and 5 mm or less, is preferably
4 mm or less, and is more preferably 3 mm or less. If the particle
size of the carrier is excessively smaller than the above lower
limit, it may become difficult to operate a reaction facility due
to pressure difference. If the particle size of the carrier is
excessively larger than the above upper limit, reaction activity
may be reduced.
Catalyst According to Second Invention
[0121] A catalyst according to the second invention (hereinafter,
may be referred to simply as "second catalyst") is a
metal-supporting catalyst that includes a metal component and a
carrier on which the metal component is supported. Specifically,
the metal components including a first component that is rhenium
and one or more second components selected from the group
consisting of silicon, gallium, germanium, and indium are supported
on a carrier. The mass ratio of the amount of the second components
to the amount of rhenium is set to a predetermined value.
[0122] The second catalyst is normally produced by reducing a
metal-supporting material on which the metal component is supported
with a reducing gas and then performing an oxidative stabilization
treatment as needed.
[0123] <Metal Component>
[0124] The metal component supported on the metal-supporting
catalyst according to the second invention includes a first
component that is rhenium and one or more second components
selected from the group consisting of silicon, gallium, germanium,
and indium. Among these, the second components used in combination
with rhenium are preferably one or more elements selected from the
group consisting of silicon, germanium, and indium, are more
preferably one or more elements that include indium and/or
germanium, are further preferably one or more elements that include
germanium, and are particularly preferably germanium.
[0125] As for the ratio between the amounts of the above essential
components supported on the catalyst, the lower limit for the mass
ratio of the second component elements that are one or more
elements selected from the group consisting of silicon, gallium,
germanium, and indium to the rhenium element is preferably 0.1 or
more and is more preferably 0.5 or more, and the upper limit for
the above mass ratio is preferably 30 or less, is more preferably 5
or less, is further preferably 3 or less, is particularly
preferably 2 or less, and is most preferably 3 or less.
[0126] Appropriately selecting the types of the second components
used in combination with rhenium and/or the proportion of the
second components supported on the carrier increases the catalytic
activity in a hydrogenation reaction of a carbonyl compound and
makes it possible to produce an alcohol while reducing side
reactions, such as an esterification reaction of a carboxylic acid
used as a raw material with an alcohol produced, and a
defunctionalization reaction due to the dehydration and
hydrogenation of the alcohol produced, which significantly occurs
particularly at a later stage of the reaction, to a high degree.
Using the above metal components in combination with one another
enables the second catalyst to be handled in the air atmosphere.
This increases ease of operation, such as transportation and
storage of the catalyst and introduction of the catalyst to a
reactor in the production of an alcohol.
[0127] Using the above metal components in combination with each
other enables an increase in catalytic activity and an increase in
reaction selectivity, which have been considered contradictory, to
be both achieved presumably for the following reasons: the addition
of the second components enables the electronic state of rhenium,
which is a catalytic activity component of the hydrogenation
catalyst, to be controlled to be in a state suitable for a
reduction reaction of a carbonyl functional group; the adsorptivity
of reactive substrates onto the surface of the catalyst is enhanced
due to the affinity of the reactive substrates for the second
components; and the orientation of adsorption of the reactive
substrates on the surface of the catalyst is controlled at a high
degree.
[0128] Although the amount of rhenium, supported on the second
catalyst is not limited, the mass ratio of the rhenium element to
the total mass of the metal-supporting catalyst is normally 0.5% by
mass or more, is preferably 1% by mass or more, is more preferably
3% by mass or more, is normally 20% by mass or less, is preferably
10% by mass or. less, and is more preferably 8% by mass or less.
When the amount of rhenium supported on the catalyst is limited to
be equal to or more than the lower limit, sufficiently high
catalytic activity can be achieved. This prevents, for example, an
increase in the sire of the reactor used. When the amount of
rhenium supported on the catalyst is limited to be equal to or less
than the upper limit, an increase in the cost of the catalyst can
be limited. Furthermore, in such a case, coagulation of rhenium
supported on the catalyst can be reduced. This reduces the side
reactions, such as a degradation reaction involved fey
decarboxylation, a defunctionalization reaction associated with
dehydration and hydrogenation of. the reaction product, and an
esterification reaction of a carboxylic acid used as a raw material
with an alcohol produced, due to high Lewis acidity of rhenium. As
a result, reaction selectivity can be further increased.
[0129] The second catalyst may further include, as needed, a third
component that is a metal component other than the above metal
components (i.e., rhenium and the second components) and that does
not adversely affect the reactions conducted using the second
catalyst, such as a reduction reaction. Examples of the Other metal
component include metal components belonging to Groups 8 to 10 of
the periodic table except iron and nickel. Examples thereof include
at least one metal selected from the group consisting of ruthenium,
cobalt, rhodium, iridium, palladium, and platinum, which are
capable of catalyzing hydrogenation. Note that the term "periodic
table" used herein refers to the long form of periodic table
(.Nomenclature of Inorganic Chemistry IUPAC Recommendations
2005).
[0130] Metals, such as iron and nickel, may elute and enter the
catalyst when a metal reaction container made of SS, SUS, or the
like becomes corroded in the preparation of the catalyst and/or the
reaction. In the second invention, in the case where the eluted
metal is precipitated on the catalyst and included in the catalyst,
the metal is not defined as a metal component of the second
catalyst. In the case of elution from a reaction container made of
SUS, in addition to iron, the following metals may be detected in
the catalyst in trace amounts at specific contents depending on the
material used.
[0131] For example, when metals enter from SUS201, nickel,
chromium, and manganese may be detected in addition to iron at
specific contents. When metals enter from SUS202, nickel chromium,
and manganese may tee detected in addition to iron at specific
contents. When metals enter from SUS301, nickel and chromium may be
detected in addition to iron at specific contents. When metals
enter from SUS302, nickel and chromium may be detected in addition
to iron at specific contents. When metals enter from SUS202,
nickel, chromium, and molybdenum may be detected in addition to
iron at specific contents. When metals enter from SUS304, nickel
and chromium may be detected in addition to iron at. specific
contents. When metals enter from SUS305, nickel and chromium may be
detected in addition to iron at specific contents. When metals
enter from SUS316, nickel, chromium, and molybdenum may be detected
in addition to iron at specific contents. When metals enter from
SUS317, nickel, chromium, and molybdenum may be detected in
addition to iron at specific contents. When metals enter from
SUS329J1, nickel, chromium, and molybdenum may be detected in
addition to iron at specific contents. When metals enter from
SUS403, chromium may be detected in addition to iron at a specific
content. When metals enter from SUS405, chromium and aluminum may
be detected in addition to iron at specific contents. When metals
enter from SUS420, chromium may be detected in addition to iron at
a specific content. When metals enter from SUS430, chromium may be
detected in addition to iron at a specific content. When metals
enter from SUS430LX, chromium, titanium, or niobium may be detected
in addition to iron at a specific content. When metals enter from
SUS630, nickel, chromium, copper, and niobium may be detected in
addition to iron at specific contents.
[0132] Examples of the metal component that belongs to a group
other than Groups 8 to 10 of the periodic table include at least
one metal selected from the group consisting of silver, gold,
molybdenum, tungsten, aluminum, and boron.
[0133] Among the above third components, at least one metal
selected from ruthenium, cobalt, rhodium, iridium, palladium,
platinum, gold, molybdenum, and tungsten is preferable; at least
one metal selected from ruthenium, cobalt, rhodium, iridium,
palladium, platinum, molybdenum, and tungsten is more preferable;
at least one metal selected from ruthenium, iridium, palladium, and
platinum is particularly preferable; and ruthenium is most
preferable.
[0134] In the case where the third component is selected from rare
and expensive metals belonging to Groups 8 to 10 of the periodic
table except iron and nickel, the elemental mass ratio of the third
component included in the second catalyst to the rhenium element is
normally less than 0.2, is preferably 0.15 or less, is more
preferably 0.1 or less, is further preferably less than 0.1, and is
most preferably 0 in order to increase reaction selectivity and
economical efficiency in terns of the costs for producing the
catalyst. That is, it is preferable that the second catalyst
substantially do not include any of the rare and expensive metals
belonging to Groups 8 to 10 of the periodic table ether than iron
or nickel.
[0135] In the case where the third component is selected from
metals other than the noble metals belonging to Groups 8 to 10 of
the periodic table, the elemental mass ratio of the third component
to the rhenium element is normally 10 or less, is preferably 5 or
less, is more preferably 1 or less, and is further preferably 0.5
or less. When the above additional metal components are used in an
appropriate combination at adequate contents, it rs possible to
achieve high catalytic activity while maintaining high
selectivity.
[0136] In the case where a metal, such as iron or nickel, becomes
eluted and enters the catalyst due to the corrosion of a reaction
container made of SS, SUS, or the like, in the second invention,
the content of iron and the contents of the above metals included
at specific contents, which are determined on the basis of the type
of material constituting the reaction container, are not taken into
account in the calculation of the content of the metal components
in the catalyst.
[0137] In order to further increase the activity of the catalyst,
reaction selectivity, and the like, the second catalyst may include
compounds of one or more alkali metal elements selected from the
group consisting of lithium, sodium, potassium, rubidium, and
cesium; compounds of one or more alkaline-earth metal elements
selected from the group consisting of magnesium, calcium,
strontium, and barium; and compounds of one or mere halogen
elements selected from the group consisting of fluorine, chlorine,
bromine, and iodine, in addition to the metal components described
above. In such a case, the ratio between the additional components
and the rhenium component is not limited.
[0138] <Carriar>
[0139] The carrier used in the second invention is not limited. In
particular, an inert carrier can be used. The term "inert carrier"
used herein refers to a carrier that does not have a catalytic
activity in a hydrogenation of a carbonyl compound alone.
Specifically, the inert, carrier is defined as a carrier that
substantially does not include any of the metals belonging to Group
8 to 12 of the periodic table which is selected from the group
consisting of iron, ruthenium, cobalt, rhodium, iridium, nickel,
palladium, platinum, copper, and zinc, chromium, and rhenium, which
are metals having catalytic activity.
[0140] In the second invention, a carrier that substantially does
not include any of the -above metals is a carrier that does not
primarily include any of the above metals. That is, the amount of
the above metals included in the carrier to the total mass of the
carrier is 5% by mass or less, is preferably 1% by mass or less,
and is more preferably 0.1% by mass or less. The content of the
above metals in the carrier can be determined as in the analysis of
the content of the supported metal in the catalyst, using publicly
known analysis methods, such as inductively coupled plasma mass
spectrometry (ICP-MS), inductively coupled plasma atomic emission
spectrometry (ICP-AES), atomic absorption spectrometry (AAS), and
X-ray fluorescence analysis (XRF).
[0141] Examples of the inert carrier used in the second invention
includes a carrier composed primarily of an element other than the
metals belonging to Groups 8 to 12 of the periodic cable, such as
iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium,
platinum, copper, and zinc, chromium, or rhenium; a carrier
composed primarily of a carbide, a nitride, an oxide, a hydroxide,
a sulfuric acid salt, a carbonic acid salt, or a phosphoric acid
salt of the element; and a carrier composed primarily of a mixture
of the above substances. The expression "composed primarily of"
used herein means that the mass ratio of the substance to the total
mass of the carrier is normally 50% by mass or more, is preferably
70% by mass or more, and is more preferably 90% by mass or
more.
[0142] Specific examples of the carrier according to the second
invention include graphite, active carbon, silicon carbide, silicon
nitride, aluminum nitride, boron nitride, boron oxide, aluminum
oxide (alumina), silicon oxide (silica), titanium oxide (titania),
zirconium oxide (zirconia), hafnium oxide, lanthanum oxide, cerium
oxide, yttrium oxide, niobium oxide, magnesium silicate, calcium
silicate, magnesium aluminate, calcium aluminate, aluminosilicate,
aluminosilicophosphate, aluminophosphate, magnesium phosphate,
calcium phosphate, strontium phosphate, apatite hydroxide (calcium
hydroxyphosphate), apatite chloride, apatite fluoride, calcium
sulfate, barium sulfate, and barium carbonate.
[0143] Among these, a carbonaceous carrier, titanium oxide,
zirconium oxide, niobium oxide, and cerium oxide are preferable in
order to increase catalytic, activity and reaction selectivity
achieved particularly when a carboxylic acid is used as a raw
material and reduce the elution of metals. Among the above
substances, titanium oxide, zirconium oxide, niobium oxide, and
cerium oxide are preferable in order to increase case of the
regeneration treatment of the catalyst. Among the above substances,
titanium oxide and zirconium oxide, which are oxides of metals
belonging to Group 4 of the periodic table, are more preferable.
Titanium oxide may be particularly preferable in order to readily
produce carrier particles having a large specific surface area.
[0144] The above carriers may be used alone or in combination of
two or more. In the case where the carriers are used in combination
of two or more, the combination of the carriers and the mixing
ratio between the carriers are not limited. The carriers can be
used in a form similar to a mixture of the individual compounds, a
composite compound, or a double salt.
[0145] The carrier may be used directly or may be subjected to a
pretreatment in which the carrier particles are formed into a shape
suitable for supporting the metal components thereon. For example,
in the case where a carbonaceous carrier is used, the carbonaceous
carrier may be subjected to a heating treatment using nitric acid
before use, as described in Japanese Unexamined Patent Application
Publication No. 10-71332. It is preferable to use the above method
in order to enhance the dispersibility of the metal components on
the carrier and thereby increase the activity of the catalyst.
[0146] It may be preferable that the carrier used in the second
invention contain a sulfate ion. In particular, in the case where
titanium oxide is used as a carrier, it may be preferable that the
carrier contain a sulfate ion.
[0147] In the second invention, using a carrier including a sulfate
ion may markedly reduce a degradation reaction involved by
decarboxylation and a defunctionalization reaction associated with
dehydration and hydrogenation of the reaction product, that is, an
alcohol, which occur simultaneously with a catalytic reaction of
hydrogenation of a carbonyl compound. In addition, when the metal
components that include rhenium and the second components are
supported on such a carrier, the catalytic activity of the
hydrogenation catalyst may be markedly increased. When the metal
components are used in combination with the carrier, the catalyst
can be handled in the air atmosphere. This increases ease of
operation of the catalyst, such as transportation and storage of
the catalyst and introduction of the catalyst to a reactor in the
production of an alcohol.
[0148] It is considered that the functions of the catalyst are
enhanced for the following reasons: when the carrier contains a
sulfate ion, sulfate ions present in the surface of the carrier may
form acid 3ites on the surface of the catalyst. Furthermore, the
dispersibility of the supported metal may be increased due to the
interaction between the supported metal and the sulfate ion or a
substitution reaction of the supported metal with the sulfate ion
which occurs when the metal components are supported on the
carrier. Moreover, the electronic state of rhenium, which is a
catalytic activity component oI the hydrogenation catalyst, can be
controlled to be in a state suitable for a reduction reaction of a
carbonyl functional group. The above factors may synergistically
increase the reaction selectivity of the catalyst and the activity
of the catalyst.
[0149] The mass ratio of the amount of the sulfate ion included in
the carrier to the total mass of the carrier used is preferably
0.01% by mass or more, is more preferably 0.1% by mass or more, and
is particularly preferably 0.2% by mass or more. The mass ratio of
the amount of the sulfate ion to the total mass of the carrier used
is preferably 10% by mass or less, is more preferably 7% by mass or
less, and is particularly preferably 5% by mass or less.
[0150] When the content of the sulfate ion in the carrier used is
limited to be equal to or more than the lower limit, the
advantageous effects of adding the above components are achieved
at. a sufficient level and high catalytic activity can be achieved.
Furthermore, the occurrence of the defunctionalization reaction can
be further reduced. This limits an increase in the complexity of
the process for purifying the reaction product and an increase in
the purification costs and consequently enables an economically
advantageous alcohol production process to be provided. Limiting
the content of the sulfate ion in the carrier used to be equal to
or less than the upper limit reduces, for example, corrosion of the
reactor caused by sulfate ions included in the carrier becoming
eluted during the reaction depending on the solvent used and side
reactions of the target product caused by the liberated acid
catalyst and therefore eliminates the need to use materials having
high corrosion resistance. This limits increases in the costs for
constructing reaction facilities and the costs for purifying the
product and enables an economically advantageous alcohol production
process to be provided.
[0151] In the case where a carrier, including a sulfate ion is used
in the 3eccnd invention, the carrier is not limited and may be any
carrier that includes a sulfate ion. An appropriate commercial
product may be used directly. In the case where the carrier is
composed of a metal oxide, the carrier may be prepared by, for
example, dissolving a corresponding metal sulfate in water and
subsequently performing neutralization or pyrohydrolysis, or by
treating a corresponding metal hydroxide or a baked metal oxide
with a sulfatizing agent and subsequently performing baking in an
oxidizing atmosphere, such as the air atmosphere. The treatment
using a sulfatizing agent is to introduce sulfate ions into the
carrier. This treatment may foe performed in the step of producing
the carrier or may be performed after the production of the
carrier. Examples of the sulfatizing agent include sulfuric acid,
persulfuric acid, and the salts thereof. Sulfuric acid, a sulfuric
acid salt, and a persulfuric acid salt are preferable. The sulfuric
acid salt is not limited and may be any sulfuric acid salt capable
of providing sulfate ions when dissolved. Examples cf the sulfuric
acid salt include ammonium sulfate, sodium sulfate, and potassium
sulfate. The same applies to the persulfuric acid salt, and
examples thereof include ammonium persulfate, sodium persulfate,
and potassium persulfate. The above salts may be in the form of an
anhydride or hydrate. Such salts may be preferable in some cases
because they are Ie3s hazardous than ac.id3 and easy to handle.
[0152] A preparation example of the carrier including a sulfate ion
according to the second invention is described below, taking
titanium oxide and zirconium oxide as an example.
[0153] Titanium oxide containing a sulfate ion can be prepared by
dissolving titanium sulfate or titanyl sulfate in water,
subsequently performing neutralization at a low temperature or
pyrohydrolysis, and then performing baking. Titanium oxide
containing a sulfate ion can also be prepared by dissolving
titanium ore in sulfuric acid, subsequently performing heating to
produce metatitanic acid or titanium hydroxide, and then performing
baking.
[0154] In another case, titanium oxide containing a sulfate ion may
be produced by passing dilute sulfuric acid through titanium
hydroxide, which is a starting material, prepared from titanium
tetraisopropoxide or the like and subsequently performing baking in
the air atmosphere. Alternatively, a baked titanium oxide may also
be used as a starting material instead of titanium hydroxide.
Instead of passing sulfuric acid, a sulfuric acid salt, such as
ammonium sulfate, may be supported on the carrier.
[0155] The titanium oxide that has been subjected to the
sulfatizing treatment is subsequently baked. The baking temperature
is preferably 350.degree. C. to 700.degree. C. and is mere
preferably 450.degree. C. to 600.degree. C. It is not preferable to
set the baking temperature to be excessively high because, if the
baking temperature is excessively high, the sulfate ions included
in the catalyst become volatilized and the surface area of the
titanium oxide decreases disadvantageously. The amount of baking
time during which the baking is performed is not limited. It is
appropriate to set the baking time to about 3 hours.
[0156] Examples of a commercial product of the titanium oxide
containing a sulfate ion include MC-30, MC-90, and MC-150 produced
by Ishihara Sangyo Kaisha, Ltd., which are also described in
Examples of the second invention below.
[0157] Zirconium oxide containing a sulfate ion can be prepared by,
as in the preparation example of the titanium oxide, adding
sulfuric acid, a sulfate, a persulfate, or the like to a starting
material that is, for example, zirconium hydroxide prepared by
adding ammonia water to an aqueous solution of a zirconium
compound, such as zirconium oxychloride, zirconium oxynitrate,
zirconium propoxide, or the like, and subsequently performing
baking in the air atmosphere. Alternatively, a baked zirconium
oxide may also be used instead of zirconium hydroxide. Instead of
passing dilute sulfuric acid, a sulfuric acid, such as ammonium
sulfate, may be supported on the carrier.
[0158] The zirconium oxide that has been subjected to the
sulfatizing treatment is subsequently baked. The baking temperature
is preferably 350.degree. C. to 700.degree. C. and is more
preferably 450.degree. C. to 600.degree. C. It is not preferable to
set the baking temperature to be excessively high because, it the
baking temperature is excessively high, the sulfate ions included
in the catalyst become volatilized and the surface area of. the
zirconium oxide decreases disadvantageously. The amount of baking
time during which the baking is performed is not limited. It is
appropriate to set the baking time to about 3 hours.
[0159] In the case where the carrier is a commercial carrier, the
content of sulfate ion in the carrier has been published by the
manufacturer, and the sulfate ion content falls within the
above-described range of sulfate ion content specified in the
second invention, the carrier is considered to correspond to the
carrier according to the second invention. Examples of such a
commercial carrier include MC-50, MC-90, and MC-150 produced by
Ishihara Sangyo Kaisha, Ltd.
[0160] In the case where it is clear that the sulfur element
component of the carrier is derived from a sulfate ion,
alternatively, the content of sulfate ion in the carrier or
catalyst may be determined using a publicly known high-frequency
furnace combustion-infrared detection method (carbon sulfur
analyzer) by combusting the catalyst in a high-frequency induction
heating furnace under an oxygen atmosphere and converting the
content of sulfur in the combustion gas into the mass of sulfate
ion, which is determined by an infrared detection method.
[0161] In the case where the catalyst according to the second
invention contains a sulfate ion, the content of the sulfate ion
,i.n the catalyst is not limited and the mass ratio of the amount
of. sulfate ion to the total mass of the catalyst is preferably
0.01% by mass or more, is more preferably 0.1% by mass or more, is
particularly preferably 0.2% by mass or more, is normally 10% by
mass or less, is preferably 1% by mass or leas, is more preferably
5% by mass or less, is particularly preferably 2% by mass or less,
and is most preferably 1% by mass or less. The mass ratio of the
amount of sulfur element to the total mass of the catalyst is
preferably 0.01% fey mass or more, is more preferably 0.1% by mass
or more, is normally 3% by mass or less, is preferably 2% by mass
or less, is more preferably 1% by mass or less, and is particularly
preferably 0.6% by mass or less.
[0162] Using a catalyst containing a sulfate ion or sulfur may
markedly reduce a degradation reaction involved by decarboxylation
and a defunctionalization reaction associated with dehydration and
hydrogenation of the reaction product, that is, an alcohol, which
occur simultaneously with a catalytic reaction of hydrogenation of
a carbonyl compound. Limiting the content of sulfate ion in the
catalyst to be equal to or more than the lower limit may increase
catalytic activity to a sufficient degree and reduce the occurrence
of the defunctionalization reaction to a sufficient degree. This
limits an increase in the complexity of the process for purifying
the reaction product and an increase in the purification costs and
consequently enables an economically advantageous alcohol
production process to be provided. Limiting the content of sulfate
ion in the catalyst according to the present invention to be equal
to or more than the lower limit also enhance, the stability of the
catalyst in the air atmosphere. This increases ease of operation of
the catalyst, such as transportation and storage of the catalyst
and introduction of the catalyst to a reactor in the production of
an alcohol. Limiting the content of the sulfate ion in the catalyst
to be equal to or less than the upper limit reduces, for example,
corrosion of the reactor caused by sulfate ions included in the
catalyst becoming eluted during the reaction and side reactions of
the target product caused by the liberated acid catalyst. This
limits increases in the costs tor constructing reaction facilities
and the costs for purifying the target product and enables an
economically advantageous alcohol production process to be
provided.
[0163] In the second invention, the content of the sulfate ion in
the carrier or catalyst is determined by publicly known ion
chromatography after the sulfate ion has been extracted from the
catalyst in a pretreatment step.
[0164] The content of the sulfur in the carrier or catalyst is
determined using a publicly known high-frequency furnace
combustion-infrared detection method (carbon sulfur analyzer) by
combusting the catalyst in a high-frequency induction heating
furnace under an oxygen atmosphere and calculating the content of
sulfur in the combustion gas by an infrared detection method.
[0165] The specific surface area of the carrier particles used in
the second invention varies by the type of the carrier used and is
not limited. The specific surface area of the carrier particles
used in the second invention is normally 50 m.sup.2/g or more, is
preferably 80 m.sup.2/g or more, is more preferably 100 m.sup.2/g
or more, is normally 3000 m.sup.2/g or loss, and is preferably 2000
m.sup.2/g or leas. In the case where a metal oxide is used as a
carrier, the specific surface area of the carrier particles is
normally 50 m.sup.2/g or more, is preferably 80 m.sup.2/g or more,
is more preferably 100 m.sup.2/g or more, is normally 1000
m.sup.2/g or less, and is preferably 800 m.sup.2/g or less. The
larger the specific surface area of the carrier particles, the
higher the catalytic activity. Therefore, carrier particles having
a larger specific surface area are suitably used. The .specific
surface area of the carrier particles is generally calculated from
the amount of nitrogen adsorbed on the carrier particles using the
BET equation.
[0166] The shape and size of the carrier particles used in the
second invention are not limited. When the shape of the carrier
particles is converted into a spherical shape, the average particle
size of the carrier is normally 0.1 .mu.m or more, is preferably 1
.mu.m or more, is more preferably 5 .mu.m or more, is further
preferably 50 .mu.m or mere, is normally 5 mm or less, and is
preferably 4 mm or less. The particle size of the carrier is
measured in accordance with Test sieving described in JIS Standard
JIB Z8815 (1994). In the case where the shape of a carrier particle
is not spherical, the volume of the carrier particle is measured,
the diameter of a spherical particle having the same volume as the
carrier particle is calculated, and the diameter of the spherical
particle is considered the diameter of the carrier particle. When
the average particle size of the carrier falls within the above
range, the activity of the catalyst per unit mass is increased, and
ease of handling of the catalyst rs further increased.
[0167] In the case where the reaction conducted using the second
catalyst is a complete mixing reaction, the average particle size
of the carrier is normally 0.1 .mu.m or more, is preferably 1 .mu.m
or more, is more preferably 5 .mu.m or more, is further preferably
50 .mu.m or more, is normally 3 .mu.m or less, and is preferably 2
nun or less. It is preferable to reduce the average particle size
of the carrier because the smaller the average particle size of the
carrier, the higher the activity of the catalyst per unit mass.
However, setting the average particle size of. the carrier to be
excessively smaller than the above lower limit may make it
difficult to separate the reaction liquid and the catalyst from
each other.
[0168] In the case where the reaction conducted using the second
main catalyst is a fixed-bed reaction, the average particle size of
the carrier is normally 0.5 mm or mere and 5 mm or less, is
preferably 4 mm or less, and is more preferably 3 mm or less. If
the particle size of the carrier is excessively smaller than the
above lower limit, it may become difficult to operate a reaction
facility due to pressure difference. If the particle size of the
carrier is excessively larger than the above upper limit, reaction
activity may be reduced.
[0169] [Method for Producing This Catalyst]
[0170] The method for producing the first catalyst and the second
catalyst (hereinafter, they are referred to as "this catalyst")
normally includes the following steps.
[0171] (i) a step in which, the metal components are attached to
the carrier (hereinafter, this step is referred to as "metal
attachment step"))
[0172] (ii) a step in which the resulting metal-supporting material
is subjected to a reduction treatment using a reducing gas
(hereinafter, this step is referred to as "reduction treatment
step"))
[0173] (iii) a step in which oxidation is performed as needed
subsequent to the reduction treatment, (hereinafter, this step is
referred to as "oxidative stabilization step"))
[0174] Each of the above steps is described below.
[0175] <(i) Metal Attachment Step>
[0176] The metal attachment step is a step in which required
amounts of the above-described metal components are attached to the
above-described carrier in order to prepare a metal-supporting
material. The method for attaching the metal components to the
carrier is not limited, and publicly known methods can be used. For
attaching the metal components to the carrier, a solution or
dispersion liquid containing metal-containing compounds that are
raw materials tor the metal components can be used.
[0177] The method for attaching the metal components to the carrier
is not limited. Normally, various impregnation methods may be used.
Examples thereof include an adsorption method in which metal ions
are caused to adsorb to the carrier in an amount equal to or less
than the salutation amount of the metal ions adsorbed by using the
ability of the metal ions to adsorb to the carrier; an equilibrium
adsorption method in which the carrier is immersed in the solution
containing an amount of metal ions which is equal to or more than
the saturation amount of the metal ions adsorbed and the excess
solution is removed; a pore-filling method in which the solution
having the same, volume as the pores formed in the carrier is added
to the carrier and the whole amount of the solution is caused to
adsorb to the carrier; an incipient wetness method in which the
solution is added t.o the carrier until the volume of the solution
added is appropriate to the water absorption capacity of the
carrier and the treatment is terminated when the surfaces of the
carrier particles become uniformly wet and excess solution is not
present on the surfaces of the carrier particles; an
evaporation-to-dryness method in which the carrier is impregnated
with the solution and the solvent is removed by evaporation while
the solution is stirred; and a spray method in which the carrier is
dried and the solution is sprayed to the dried carrier. Among
these, the pore-filling method, the incipient wetness method, the
evaporation-to-dryness method, and the spray method are preferable,
and the pore-filling method, the incipient wetness method, and the
evaporation-to-dryness method are more preferable. Using the above
preparation methods enables rhenium, the above-described second
component, and the optional third component and the other metal
components which may be added to the catalyst as needed to be
supported on the carrier while being relatively uniformly dispersed
on the carrier. As described in the first and second inventions
above, it may be preferable that the carrier include a sulfate ion.
In such a case, it is preferable to attach the metal components to
a carrier that includes an amount of sulfate ion which is 0.01% by
mass or more and 10% by mass or less of the mass of the
carrier.
[0178] The metal-containing compounds used are not limited and may
be selected appropriately in accordance with the attaching method
used. Examples thereof include halides, such as a chloride, a
bromide, and an iodide; mineral acid salts, such as a nitric acid
salt and a sulfuric acid salt; metal hydroxides; metal oxides;
metal-containing ammonium salts; organic-group-containing
compounds, such as an acetic acid salt and a metal alkoxide; and
metal complexes. Among these, halides, mineral acid salts, metal
hydroxides, metal oxides, metal-containing ammonium salts, and
organic-group-containing compounds are preferable, and halides,
mineral acid salts, metal oxides, metal-containing ammonium salts,
and organic-group-containing compounds are more preferable. The
above compounds may be used alone or in combination of two or more
in a required amount.
[0179] When the metal-containing compounds are attached to the
carrier, the metal-containing compounds may be dissolved or
dispersed in a solvent and the resulting solutions and dispersion
liquids may be used in any of the above attaching methods. The type
of the solvent used in this step is not limited and may be any type
of solvent in which the metal-containing compounds can be dissolved
or dispersed and which does not adversely affect the baking and
hydrogen reduction of the metal-supporting material and the
hydrogenation reaction in which this catalyst is used, which are
conducted in the subsequent step. Examples of the solvent include
ketone solvents, such as acetone, alcohol solvents, such as
methanol and ethanol, ether solvents, such as tetrahydrofuran and
ethylene glycol dimethyl ether, and water. The above solvents may
be used alone or in the form of a mixed solvent. Among the above
solvents, water is preferably used because water is inexpensive and
the solubility of the raw materials, that is, the metal-containing
compounds, in water is high.
[0180] When the metal-containing compounds are dissolved or
dispersed in the solvent, various additives may be optionally used
in addition to the solvent. For example, using a solution of
carboxylic acid and/or a carbonyl compound may improve the
dispersibility of each of the metal components on the carrier which
is achieved when the metal components are attached to the carrier,
as described in Japanese Unexamined Patent Application Publication
No. 10-15366.
[0181] The metal-supporting material may be dried as needed. It is
preferable to subject the metal-supporting material to a .reduction
treatment step after the metal-supporting material has been dried
and subsequently baked as needed, for the following reason: if the
metal-supporting material is subjected to the subsequent reduction
treatment without being dried, the catalyst may have low reaction
activity.
[0182] The method for drying the metal-supporting material is not
limited and may be any method capable of removing the solvent and
the like used for attaching the metal components to the carrier.
Normally, the metal-supporting material is dried in a stream of
inert gas or at a reduced pressure.
[0183] The pressure at which the metal-supporting material is dried
is nor, limited. Normally, the metal-supporting material is dried
at normal pressure or a reduced pressure.
[0184] The temperature at which the metal-supporting material is
dried is normally, but not limited to, 300.degree. C. or less, is
preferably 250.degree. C. or less, is more preferably 200.degree.
C. or less, and is normally 80.degree. C. or more.
[0185] After the metal-supporting material has been dried, the
metal-supporting material may be baked as needed. Baking the
metal-supporting material increases the likelihood of the catalyst
having a high catalytic activity and excellent reaction
selectivity. The baking of the metal-supporting material may be
performed in the air atmosphere. For example, the baking of the
metal-supporting material may be performed by heating the
metal-supporting material in an air stream at a predetermined
temperature for a predetermined amount of time.
[0186] The temperature at which the metal-supporting material is
baked is normally, but not limited to, 100.degree. C. or more, is
preferably 250.degree. C. or more, is more preferably 400.degree.
C. or more, is normally 1000.degree. C. or less, is preferably
700.degree. C. or less, and is more preferably 600.degree. C. or
less. The amount of time during which the metal-supporting material
is baked, which varies with the baking temperature, is normally 30
minutes or more, is preferably 1 hour or more, is more preferably 2
hours or more, is normally 40 hours or less, is preferably 30 hours
or less, and is more preferably 10 hours or less.
[0187] <(ii) Reduction Treatment Step>
[0188] The metal-supporting material is normally subjected to a
reduction treatment using a reducing gas. In the reduction
treatment, a publicly known method, such as liquid-phase reduction
or a gas-phase reduction, may be used.
[0189] The reducing gas used in the reduction treatment step is not
limited and may be any gas having a reducing power. Examples of the
reducing gas include hydrogen, methanol, and hydrazine. The
reducing gas is preferably hydrogen.
[0190] In the case where a hydrogen-containing gas is used as a
reducing gas, the hydrogen concentration in the hydrogen-containing
gas is not limited. The hydrogen concentration in the
hydrogen-containing gas may be 100% by volume. Ir. another case,
the hydrogen-containing gas may be diluted with an inert gas. The
term "inert gas" used herein refers to a gas unreactive with the
metal-supporting material or a hydrogen ga3, such as nitrogen or
water vapor. Normally, nitrogen is used as an inert gas. The
hydrogen concentration in the reducing gas (hydrogen-containing
gas) diluted with an inert gas is normally 5% by volume or more, is
preferably 15% by volume or more, is more preferably 30% by volume
or more, and is further preferably 50% by volume or more relative
to the all the gas components. It is possible to use a
hydrogen-containing gas having a low hydrogen concentration at the
initial stage of reduction and gradually increase the hydrogen
concentration in the hydrogen-containing gas over the course of
reduction.
[0191] The amount of time required for the reduction treatment,
which varies with the amounts of the metal-supporting material and
the like that are to be treated and the type of the apparatus or
the like used, is normally 7 minutes or more, is preferably 15
minutes or more, is more preferably 30 minutes or more, is normally
40 hours or less, is preferably 30 hours or leas, and is more
preferably 10 hours or less. The temperature at which the reduction
treatment is performed is normally 130.degree. C. or more, is
preferably 200.degree. C. or more, is more preferably 250.degree.
C. or more, is normally 700.degree. C. or less, is preferably
600.degree. C. or less, and is more preferably 500.degree. C. or
less. If the reduction treatment is performed at an excessively
high temperature, for example the supported metal may b sintered
and, consequently, the activity of the. catalyst may be
reduced.
[0192] In the reduction treatment, the reducing gas may be enclosed
in the reactor or may be passed through the reactor. It is
preferable to pass the reducing gas through the reactor. This is
because passing the reducing gas through the reactor prevents the
occurrence of local hydrogen deficiency. In the reduction
treatment, water, ammonium chloride, and the like may be produced
as by-products in the rector depending on the raw materials used,
and the by-products may adversely affect the metal-supporting
material that has not been subjected to the reduction treatment or
the metal-supporting catalyst, which has been subjected to the
reduction treatment. Passing the reducing gas through the reactor
enables the by-products to be discharged to the outside of the
reaction system.
[0193] The amount of the reducing gas required by the reduction
treatment is not limited and may be set such that the objects of
the first to third inventions are achieved. The amount of the
reducing gas required by the reduction treatment can be set
appropriately in accordance with the apparatus used, the size of
the reactor used for reduction, the method for passing the reducing
gas through the reactor, the method for fluidizing the catalyst,
and the like.
[0194] The size of the metal-supporting catalyst, which has been
subjected to the reduction treatment, is net limited and basically
the same as the site of the carrier.
[0195] Examples of a preferable method for performing the reduction
treatment include a method in which the reducing gas is passed
through the metal-supporting material with a fixed bed; a method in
which the reducing gas is passed through the metal-supporting
material that is disposed to stand on a tray or a belt; and a
method in which the metal-supporting material is caused to fluidize
and the reducing gas is passed through the fluidized
metal-supporting material.
[0196] <(iii) Oxidative Stabilization Step>
[0197] In the production of this catalyst, as needed, the
metal-supporting catalyst, which is produced by reducing the
metal-supporting material, is subjected to an oxidative
stabilization treatment in order to control the oxidation state.
Performing the oxidative stabilization treatment enables the
production of a catalyst that has excellent activity and excellent
selectivity and that can be handled in the air atmosphere.
[0198] The method for performing oxidative stabilization is not
limited. Examples thereof include a method in which water is added
to the metal-supporting catalyst, a method in which the
metal-supporting catalyst is charged into water, a method in which
oxidative stabilization is performed using a gas having a low
oxygen concentration which is diluted with an inert gas, and a
method in which stabilization is performed using carbon dioxide.
Among the above methods, the method .in which water is added to the
metal-supporting catalyst, the method in which the metal-supporting
catalyst is charged into water, and the method in which oxidative
stabilization is performed using the gas having a low oxygen
concentration are preferable, the method in which oxidative
stabilization (slow oxidation) is performed using the gas having a
low oxygen concentration (hereinafter, this method is referred to
as "slow-oxidation method") is more preferable, and a method in
which oxidative stabilization is performed in a stream of the gas
having a low oxygen concentration is particularly preferable.
[0199] The initial oxygen concentration with which oxidative
stabilization is performed using the gas having a low oxygen
concentration is not limited. The oxygen concentration with which
the slew oxidation is started is normally 0.2% by volume or more,
is preferably 0.5% by volume or more, is normally 10% by volume or
less, is preferably 8% by volume or less, and is further preferably
7% by volume or less. If the oxygen concentration is excessively
lower than the lower limit, it takes a considerable amount of time
to complete the oxidative stabilization and stabilization may fail
to be achieved at a sufficient level. If the oxygen concentration
is excessively higher than the upper limit, the temperature of the
catalyst may be excessively increased and the catalyst may become
deactivated.
[0200] The gas having a low oxygen concentration is preferably
prepared by diluting air with an inert gas. The inert, gas used for
diluting air is preferably nitrogen.
[0201] Examples of a method for performing the oxidative
stabilization using the gas having a low oxygen concentration
include a method in which the gas having a low oxygen concentration
is passed through the catalyst with a fixed bed; a method in which
the gas having a low oxygen concentration is passed through the
catalyst that is disposed to stand on a tray or a belt; and a
method in which the catalyst is caused to fluidize and the gas
having a low oxygen concentration is passed through the fluidized
catalyst.
[0202] The higher the dispersibility of the supported metal or. the
metal-supporting catalyst, the higher the rate at which the
oxidative stabilization is performed and the larger the amount of
oxygen used in the reaction. Therefore, the method in which the gas
having a low oxygen concentration is passed through the catalyst
with a fixed bed and the method in which the catalyst is caused to
fluidize and the gas having a low oxygen concentration is passed
through the fluidized catalyst are preferable.
[0203] The method for producing this catalyst is not limited to the
above-described production method and may be any method capable of
producing this catalyst. For example. the method for producing this
catalyst nay include another publicly known step such that this
catalyst can be produced.
[0204] [Production of Alcohol With This Catalyst]
[0205] This catalyst is suitable as a catalyst used in the
reduction reaction (hydrogenation) of a carbonyl compound. An
alcohol can be produced by treating a carbonyl compound with this
catalyst.
[0206] Preferable examples of the reduction reaction conducted with
this catalyst include an alcohol production method which includes a
step in which at least one carbonyl compound selected from the
group consisting of a ketone, an aldehyde, a carboxylic acid, a
carboxylic acid ester, a carboxylic acid amide, a carboxylic acid
halide, and a carboxylic anhydride is reduced to produce an alcohol
derived from the compound. Among the above compounds, a carboxylic
acid can be directly reduced with this catalyst to form an
alcohol.
[0207] The carbonyl compound that is to be subjected to the
reduction reaction nay be. any carbonyl compound that is
industrially readily available. Specific examples of the carboxylic
acid and/or the carboxylic acid eater include aliphatic chain
monocarboxylic acids, such as acetic acid, butyric acid, decancic
acid, lauric acid, oleic acid, linoleic acid, linolenic acid,
stearic acid, and palmitic acid; aliphatic cyclic monocarboxylic
acids, such as cyclohexanecarboxylic acid, naphthenic acid, and
cyclopentanecarboxylic acid; aliphatic polycarboxylic acids, such
as oxalic acid, malonic acid, succinic acid, methylsuccinic acid,
glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic
acid, cyclohexanedicarboxylic acid, 1,2,4-butanetricarboxylic acid,
1,3,4-cyclohexanetricarboxylic acid, bicyclohexyldicarboxylic acid,
and decahydronaphthalenedicarboxylic acid; aromatic carboxylic
acids, such as phthalic acid, isophthalic acid, terephthalic acid,
and trimesic acid; carboxylic acids including a furan skeleton,
such as furancarboxylic acid and furandicarboxylic acid; carboxylic
acid esters, such as methyl esters, ethyl esters, propyl esters,
and butyl esters of the above carboxylic acids and esters of an
alcohol produced by reducing a carboxylic acid; and lactones, such
as .gamma.-butyrolactone, .delta.-valerolacton(r), and
.epsilon.-caprolactone.
[0208] Specific examples of the carboxylic acid amide include
methyl amides and ethyl amides of the above carboxylic acids.
[0209] Specific examples of the carboxylic acid halide include
chlorides and bromides of the above carboxylic acids.
[0210] Specific examples of the carboxylic anhydride include acetic
anhydride, succinic anhydride, maleic anhydride, and phthalic
anhydride.
[0211] Examples of the aldehyde and the ketone include
benzaldehyde, propionaldehyde, acetaldehyde,
3-hydroxypropionaldehyde, furfural, hydroxymethylfurfural, acetone,
benzophenone, glucose, xylose, lactose, and fructose.
[0212] The carboxylic acid and carboxylic acids constituting the
carboxylic acid ester, the carboxylic acid amide, the carboxylic
acid halide, and/or the carboxylic anhydride are preferably, but
not limited to, chain or cyclic saturated aliphatic carboxylic
acids, are more preferably carboxylic acids a portion of which
excluding carboxyl groups has 20 or less carbon atoms. The number
of the carbon atoms included in the carboxylic acids is more
preferably 14 or less.
[0213] In the present invention, among the above carbonyl compounds
that are to be subjected to the reduction reaction, the carboxylic
acid, the carboxylic acid ester, the carboxylic anhydride, and the
aldehyde are preferable, the carboxylic acid, the carboxylic acid
ester, the carboxylic anhydride, and the aldehyde are more
preferable, and the carboxylic acid arid the carboxylic acid ester
are particularly preferable from the viewpoint of ease of
availability of the raw materials. However, the carbonyl compounds
that are to be subjected to the reduction reaction are not limited
to the above carbonyl compounds.
[0214] The carboxylic acid is preferably a dicarboxylic acid and is
further preferably a dicarboxylic acid represented by Formula (1)
below the portion of which except carboxyl groups includes 20 or
less carbon atoms.
HOOC--R.sup.1--COOH (2)
[0215] (in Formula (1), R.sup.1 represents an aliphatic or
alicyclic hydrocarbon group that may have a substituent, the
portion of the hydrocarbon group except the substituent including 1
to 20 carbon atoms)
[0216] This catalyst enables a polyvalent carboxylic acid, such as
the above dicarboxylic acid, to be converted into a corresponding
hydroxycarboxylic acid, lactone, or polyhydric alcohol with high
selectivity at a high yield. Appropriately selecting the production
conditions, 3uch as the type of catalyst used, the reaction
pressure, the reaction temperature, and the amount of time the raw
materials are retained, enables the ratio between the amount of the
hydroxycarboxylic acid or lactone produced and the amount, of the
polyhydric alcohol produced to be controlled.
[0217] Other examples of particularly preferable carbonyl compounds
include carboxylic acids having a furan skeleton which are derived
from biomass resources, such as furandicarboxylic acid, and
aldehydes, such as hydroxymethylfurfural.
[0218] Although the reduction reaction using this catalyst may be
conducted in a liquid phase or gas phase, the reduction reaction
using this catalyst is preferably conducted in a liquid phase.
Although the reduction reaction using this catalyst in a liquid
phase may be conducted without using a solvent or in the presence
of a solvent, the reduction reaction using this catalyst in a
liquid phase is normally conducted in the presence of a
solvent.
[0219] Examples of the solvent include, normally, water; lower
alcohols, such as methanol and ethanol; alcohols that are the
reaction products; ethers, such as tetrahydrofuran, dioxane, and
ethylene glycol dimethyl ether; and hydrocarbons, such as hexane,
decalin, and methylcyclohexane. The above solvents may be used
alone or in a mixture of two or more.
[0220] In particular, in the case where a carbonyl compound is to
foe reduced, it is preferable to use a water solvent from the
viewpoints of solubility and the like. The amount, of the solvent
used is normally, but not limited to, about 0.1 to 20 times by
mass, is preferably 0.5 to 10 times by mass, and is more preferably
about 1 to 10 times by mass the amount of the carbonyl compound
used as a raw material.
[0221] The reduction reaction using this catalyst is normally
conducted in a pressurized hydrogen gas. The reaction is normally
conducted at 100.degree. C. to 300.degree. C. and is preferably
conducted at 120.degree. C. to 250.degree. C. The reaction pressure
is normally 1 to 30 MPaG, .is preferably 1 to 25 MPaG, and is
further preferably 5 to 25 MPaG.
[0222] After the reaction has been terminated, the product of the
reduction reaction using this catalyst is normally recovered by
solvent distillation, solvent distillation followed by extraction
using an organic solvent, distillation, sublimation,
crystallization, chromatography, or the like, which depends on the
physical properties of the product. In the case where the product
is liquid at handling temperature, it is preferable to recover the
product, while purifying the product by distillation. In the case
where the product is solid at handling temperature, it is
preferable to recover the product while purifying the product by
crystallization. It is preferable to purify the solid product by
washing.
EXAMPLES
[0223] The present invention is described below further in detail
with reference to Examples. The present invention is not limited by
Examples below without departing from the scope of the present
invention.
[0224] (Measurement of Sulfate Ion Content)
[0225] A 0.2 M-aqueous sodium hydroxide solution was added to the
sample. The resulting mixture was irradiated with ultrasonic wave
and subsequently subjected to centrifugal separation. The resulting
liquid was analyzed by ion chromatography in order to determine the
content of sulfate ions in the sample.
[0226] (Measurement of Sulfur Content)
[0227] The content, of sulfur in the sample was determined in
accordance with a high-frequency furnace combustion-infrared
detection method (carbon sulfur analyzer) by combusting the sample
in a high-frequency induction heating furnace under an oxygen
atmosphere and calculating the content of sulfur in the combustion
gas by an infrared detection method.
Examples and Comparative Examples of First Invention
Example I-1
[0228] Ammonium perrhenate and tetraethoxygermanium(IV) were
dissolved in water. Titanium oxide particles (Catalysis Society of
Japan, Reference catalyst JRC-TIO-14 produced by Ishihara Sangyc
Kaisha, Ltd.) having a specific surface area of 308 m.sup.2/g were
added to the resulting solution. The solution was stirred at room
temperature for 20 minutes. Subsequently, water was removed using
an evaporator. Then, drying was performed at 100.degree. C. for 4
hours. The resulting material was charged into a vertical baking
tube. While air was passed through the tube, a baking treatment was
performed at 500.degree. C. for 3 hours. The resulting solid was
charged into a vertical baking tube. While a hydrogen gas was
passed through the tube, a reduction treatment was performed at
500.degree. C. for 30 minutes. Subsequently, the temperature was
reduced to 30.degree. C. After purging with an argon gas had been
performed, a 6-volume % oxygen/nitrogen gas was passed through the
tube. Hereby, 5% rhenium-5% germanium/titanium oxide catalyst
particles having stabilized surfaces (the ratio of the amount of
rhenium supported to the total mass of the catalyst: 5 mass %, the
ratio of the amount of germanium supported to the total mass of the
catalyst: 5 mass % (Ge/Re=1)) were prepared. The sulfate ion
contents in the titanium oxide particles (Catalysis society of
Japan, Reference catalyst JRC-TIO-14) and the catalyst were 0.2% by
mass and 0.14% by mass, respectively. The sulfur content in the
catalyst was 0.078% by mass.
[0229] Into a 70-mL high-pressure reactor, 100 mg of the catalyst
prepared by the above method, 500 mg of sebacic acid, 2 g of water,
and a stirrer chip were charged. After the reactor had been purged
with nitrogen, a hydrogen gas (7 MPaG) was introduced into the
reactor at room temperature. Subsequently, a hydrogenation reaction
was conducted at 220.degree. C. for 7.5 hours. The reaction
pressure at 220.degree. C. was 13 MPaG. After the reaction had
beer, terminated, the temperature was reduced to room temperature
and the pressure was then reduced. An analysis of the reaction
liquid by gas chromatography confirmed that the molar yields of
1,10-decanediol and 10-hydroxydecanoic acid in the reaction were
5.9% and 48.1%, respectively, and the molar ratio of the
by-products (1-nonanol, 1-aecanol, 1-nonanoic acid, and 1-decanoic
acid) to the target components (1,10-decanediol and
10-hydroxydecancic acid) was 0.016.
Example I-2
[0230] A hydrogenation reaction was conducted as in Example I-1
with the catalyst prepared in Example I-1, except that the amount
of time during which the hydrogenation reaction was conducted was
changed to 18 hours. The molar yields of 1,10-decanediol and
10-hydroxydecanoic acid in the reaction were 89.3% and 6.5%,
respectively. The molar ratio of the by-products (1-nonanol,
1-decanol, 1-nonanoic acid, and 1-decanoic acid) to the target
components (1,10-decanediol and 10-hydroxydecanoic acid) was
0.017.
Example I-3
[0231] A hydrogenation reaction was conducted as in Example I-1
with a catalyst prepared as in Example I-3, except that the
treatment in which the surfaces of the catalyst particles were
stabilized by passing a 6-volume % oxygen/nitrogen gas through the
tube was not performed after the reduction treatment had been
performed while a hydrogen gas was passed through the tube. The
molar yields of 1,10-decanediol and 10-hydroxydecancic acid in the
reaction were 74.7% and 2.6%, respectively. The molar ratio of the
by-products (1-nonanol, 1-decanol, 1-nonanoic acid, and 1-decanoic
acid) to the target components (1,10-decanediol and
10-hydroxydecanoic acid) was 0.004.
Example I-4
[0232] A 5% rhenium-5% germanium/titanium oxide catalyst was
prepared by the same catalyst preparation method as in Example I-1,
except that the titanium oxide particles were changed to titanium
oxide particles having a specific surface area of 302 m.sup.2/g and
a sulfate ion content of 4.8% by mass (MC-150, produced by Ishihara
Sangyo Kaisha, Ltd.). The sulfate ion content in the catalyst was
0.63% by mass. The sulfur content in the catalyst was 0.57% by
mass. A hydrogenation reaction was conducted as in Example I-1 with
this catalyst. The molar yields of 1,10-decanediol and
10-hydroxydecanoic acid in the reaction were 81.7% and 0.6%,
respectively. The molar ratio of the by-products (I-nonanol,
1-decanol, 1-nonanoic acid, and 1-decanoic acid) to the target,
components (10-hydroxydecanoic acid and 1,10-decanediol) was
0.006.
Example I-5
[0233] A 5% rhenium-5% germanium/titanium oxide catalyst was
prepared by the same method as in Example I-1. except that the
titanium oxide particles were changed to titanium oxide particles
having a specific surface area of 90 m.sup.2/g and a sulfate ion
content of 3.6% by mass (MC-90, produced by Ishihara Sangyo Kaisha,
Ltd.). The sulfate ion content in the catalyst was 0.30% by mass.
The sulfur content in the catalyst was 0.35% by mass, A
hydrogenation reaction was conducted as in Example I-1 with this
catalyst. The molar yields of 1,10-decanodiol and
10-hydroxydecanoic acid in the reaction were 4.5% and 36.8%,
respectively. The molar ratio of the by-products (1-nonanol,
1-decanol, 1-nonanoic acid, and 1-decanoic acid) to the target
components (10-hydroxydecanoic acid and 1,10-decanediol) was
0.011.
Example I-6
[0234] A 5% rheniuns-5% indium/titanium, oxide catalyst, was
prepared by the same catalyst preparation method as in Example I-1,
except that indium(III) chloride tetrahydrate was used instead of
tetraethoxygermanium(IV). Subsequently, a hydrogenation reaction
was conducted as in Example I-1. The molar yields of
1,10-decanediol and 10-hydroxydecanoic acid in the reaction were
9.0% and 43.5%, respectively. The molar, ratio of the by-products
(1-nonanol, 1-decanol, 1-nonanoic acid, and 1-decanoic acid) to the
target, components 10-hydroxydecanoic acid and 1,10-decanediol) was
0.034.
Example I-7
[0235] A 5% rheniuns-5% silicon/titanium oxide catalyst was
prepared by the same catalyst preparation method as in Example I-1,
except that tetraethoxysilane(IV) was used instead of
tetraethoxygermanium(IV) and ethanol was used instead of water for
preparing the solution. Subsequently, a hydrogenation reaction was
conducted as in Example I-1. The molar yields or 1,10-decanediol
and 10-hydroxydecanoic acid in the reaction were 1.7% and 23.1%,
respectively. The molar ratio of the by-products (1-nonanol,
3-docanol, 1-nonanoic acid, and 1-decanoic acid) to the target
components (10-hydroxydecanoic acid and 1,10-decanediol) was
0.039.
Example I-8
[0236] A 5% rhenium-1% germanium/titanium oxide catalyst was
prepared by the same catalyst preparation method as in Example I-1,
except that the ratio between the amounts of ammonium perrhenate
and tetraethoxygermanium(IV) used as metal raw materials was
changed and the surfaces of the catalyst particles were not
stabilized by passing the 6-volume % oxygen/nitrogen gas through
the tube subsequent to the reduction treatment. A hydrogenation
reaction was conducted as in Example I-1 with this catalyst, except
that the amount of time during which the reaction was conducted was
changed to 3 hours. The molar yields of 1,10-decanediol and
10-hydroxydecanoic acid in the reaction were 38.7% and 10.8%,
respectively. The moinr ratio of the by-products (1-nonanol,
1-decanol, 1-nonanoic acid, and 1-decanoic acid) to the target
components (10-hydroxydecanoic acid and 1,10-decanediol) was
0.009.
Example I-9
[0237] A hydrogenation reaction was conducted with the catalyst
prepared in Example I-3 as in Example I-1, except that the amount
of time during which the reaction was conducted was changed to 3
hours. The molar yields of 1,10-docanediol and 10-hydroxydecanoic
acid in the reaction were 35.3% and 32.9%, respectively. The molar
ratio of the by-products (1-nonanol, 1-decanol, 1-nonanoic acid,
and 1-decanoic acid) to the target components (10-hydraxydecanoic
acid and 1,10-decanediol) was 0.005.
Example I-10
[0238] A 5% rheniuns-5% germanium-0.5% ruthenium/titanium oxide
catalyst was prepared by the same catalyst preparation method as in
Example I-1, except that ammonium perrbenate,
tetraethoxygermanium(IV), and ruthenium(III) chloride were used as
metal raw materials and the surfaces of the catalyst particles were
not stabilized by passing the 6-volume % oxygen/nitrogen gas
through the tube subsequent to the reduction treatment.
Subsequently, a hydrogenation reaction was conducted as in Example
I-1. The molar yields of 1,10-decanediol and 10-hydroxydecancic
acid in the reaction were 72.0% and 3.6%, respectively. The molar
ratio of the by-products (1-nonanol, 1-decanol, 1-nonanoic acid,
and 1-decanoic acid) to the target components (10-hydroxydecanoic
acid and 1,10-decanediol) was 0.006.
Example I-11
[0239] A 5% rhenium-5% germaniunt-5% ruthenium/titanium oxide
catalyst was prepared by the same catalyst preparation method as in
Example I-10, except that the ratio between the amounts of ammonium
perrhenate, tetraethoxygermanium(IV), and ruthenium(III) chloride
used as metal raw materials was changed. Subsequently, a
hydrogenation reaction was conducted as in Example I-1. The molar
yields of 1,10-decanediol and 10-hydroxydecanoic acid in the
reaction were 89.0% and 0.4%, respectively. The molar ratio of the
by-products (1-nonanol, 1-decanol, 1-nonanoic acid, and 1-decanoic
acid) to the target components (10-hydroxydecanoic acid and
1,10-decanediol) was 0.020.
Comparative Example I-1
[0240] A 5% rhenium/titanium oxide catalyst was prepared by the
same catalyst preparation method as in Example I-1, except that
tetraethoxygermanium was not used. Subsequently, a hydrogenation
reaction was conducted as in Example I-1. The molar yields of
1,10-decanediol and 10-hydroxydecanoic acid in the reaction were
0.1% and 21.0%, respectively. The molar, ratio of the by-products
(1-nonanol, 1-decanol, 1-nonanoic acid, and 1-decanoic acid) to the
target components (1,10-decanediol and 10-hydroxydecanoic acid) was
0.060.
Comparative Example I-2
[0241] A 5% rhenium-5% palladium/titanium oxide catalyst was
prepared by the same catalyst preparation method as in Example X-1,
except that ammonium perrhenate and
dichlorotetraamminepalladium(II) were used as metal raw materials.
Subsequently, a hydrogenation reaction was conducted as in Example
I-1. The molar yields of 1,10-decanediol and 10-hydroxydecanoic
acid in the reaction were 33.1% and 0.0%, respectively. The molar
ratio of the by-products (1-nonanol, 1-decanol, 1-nonanoic acid,
and 1-decanoic acid) to the target components (10-hydroxydecanoic
acid and 1,10-decanediol) was 0.325.
Comparative Example I-3
[0242] A 5% rhenium-5% ruthenium/titanium oxide catalyst was
prepared by the same catalyst preparation method as in Example I-3,
except that ammonium perrhenate and ruthenium(III) chloride were
used as metal raw materials. Subsequently, a hydrogenation reaction
was conducted as in Example I-1. The molar yields of
1,10-decanediol and 10-hydroxydecanoic acid in the reaction were
45.0% and 11.1%, respectively. The molar ratio of the by-products
(1-nonanol, 1-decanol, 1-nonanoic acid, and 1-decanoic acid) to the
target components (10-hydroxydecanoic acid and 1,10-decanediol) was
0.063.
[0243] Table 1 summarizes the results obtained in Examples I-1 to
I-11 and Comparative examples I-1 to I-3.
TABLE-US-00001 TABLE 1 Reaction results Hydrogenation Yield of
1,10- Yield of 10- By-product/target reaction time decanediol
hydroxydecanoic component molar Catalyst (hour) (mol %) acid (mol
%) ratio Example 5%Re 5%Ge/TiO.sub.2 7.5 5.9 48.1 0.016 I-1 Example
5%Re 5%Ge/TiO.sub.2 18 89.3 6.5 0.017 I-2 Example 5%Re
5%Ge/TiO.sub.2 7.5 74.7 2.6 0.004 I-3 Example 5%Re 5%Ge/TiO.sub.2
7.5 81.7 0.6 0.006 I-4 Example 5%Re 5%Ge/TiO.sub.2 7.5 4.5 36.8
0.011 I-5 Example 5%Re 5%In/TiO.sub.2 7.5 9.0 43.5 0.034 I-6
Example 5%Re 5%Si/TiO.sub.2 7.5 1.7 23.1 0.039 I-7 Example 5%Re
1%Ge/TiO.sub.2 3 38.7 10.8 0.009 I-8 Example 5%Re 5%Ge/TiO.sub.2 3
35.3 32.9 0.005 I-9 Example 5%Re 5%Ge 7.5 72.0 3.6 0.006 I-10 5%Ru/
TiO.sub.2 Example 5%Re 5%Ge 7.5 89.0 0.4 0.020 I-11 5%Ru/ TiO.sub.2
Comparative 5%Re/TiO.sub.2 7.5 0.1 21.0 0.060 example I-1
Comparative 5%Re 5%Pd/TiO.sub.2 7.5 33.1 0.0 0.825 example I-2
Comparative 5%Re 5%Ru/TiO.sub.2 7.5 45.0 11.1 0.063 example I-3
Example I-12
[0244] Ammonium perrhenate and tetraethoxygexmanium(XV) were
dissolved in water. Titanium oxide particles (MC-150, produced by
Ishih&ra Sangyo Kaisha, Ltd.>having a specific surface area
of 302 m.sup.2/g and a sulfate ion content of 4.8% by mass were
added to the resulting solution. The solution was stirred at room
temperature for 20 minutes.
[0245] Subsequently, water was removed using an evaporator. Then,
drying was performed at 100.degree. C. for 4 hours. The resulting
material was charged into a vertical baking tube, while air was
passed through the tube, a baking treatment was performed at
500.degree. C. for 3 hours. The resulting solid was charged into a
vertical baking tube. While a hydrogen gas was passed through the
tube, a reduction treatment was performed at 500.degree. C. for 30
minutes. Hereby, a 5% rhenium-5% germanium/titanium oxide catalyst
(the ratio of the amount of rhenium supported to the total mass of
the catalyst: 5 mass %, the ratio of the amount of germanium
supported to the total mass of the catalyst: 5 mass % (Ge/Re=1))
was prepared.
[0246] Into a 70-mL high-pressure reactor, 70 mg of the catalyst
prepared by the above method, 260 mg of decanoic acid, 1.2 mL of
methanol, and a stirrer chip were charged. After the reactor had
been purged with nitrogen, a hydrogen gas (7 MPaG) was introduced
into the reactor at room temperature. Subsequently, a hydrogenation
reaction -was conducted at 220.degree. C. for 3 hours. The reaction
pressure at 220.degree. C. was 13 MPaG. After the reaction had been
terminated, the temperature was reduced to room temperature and the
pressure was then reduced. An analysis of the reaction liquid by
gas chromatography confirmed that the molar yield of 10-decanol in
the reaction was 76.5% and the molar ratio of the by-products
(nonane and decane) to the target component (10-decanol) was
0.004.
Example I-13
[0247] A 5% rheniura-5% germanium/zirconium oxide catalyst was
prepared by the same catalyst preparation method as in Example I-6,
except that zirconium oxide particles having a specific surface
area of 97 m.sup.2/g which did not include a sulfate ion was used
instead of the titanium oxide particles. Subsequently, a
hydrogenation reaction was conducted as in example I-8, except that
a water solvent was used instead of methanol. The molar yield of
10-decanol in the reaction was 23.2% and the molar ratio of the
by-products (nonane and decane) to the target component
(10-decanol) was 0.001.
[0248] A comparison between the results obtained in Examples I-1 to
I-11 and the results obtained in Comparative examples I-1 to I-3,
where a catalyst including a carrier composed of titanium oxide was
used, confirms that using a catalyst produced by attaching the
specific second component to a catalyst including rhenium and an
oxide of a metal belonging to Group 4 of the periodic table
increases the total amount of 1,10-decanediol and
10-hydroxydecanoic acid produced in a hydrogenation reaction of a
earboxylic acid per unit specific surface area and enhances
catalytic activity. Furthermore, the occurrence of side reactions,
such as a defunctionalization reaction associated with dehydration
and hydrogenation, can fee markedly reduced. The advantageous
effects become significant particularly when a catalyst including
germanium is used. Note that, the total amount of 1,10-decanediol
and 10-hydroxydecanoic acid produced is used as a measure of
catalytic activity because 10-hydroxydecancic acid is considered a
reaction intermediate of the 1,10-decanediol product and can be
derived into 1,10-decanediol when the reaction time is further
prolonged. A comparison between the results obtained in Examples
I-12 and I-13 confirms that a catalyst including a carrier composed
of zirconium oxide also has the same advantageous effects as a
catalyst including a carrier composed of titanium oxide.
Specifically, it is confirmed that a catalyst including a zirconium
oxide carrier has a catalytic activity comparable to that of a
catalyst including a titanium oxide carrier in terms of catalytic
activity per unit specific surface area. A comparison between the
results obtained in Examples I-1 and I-2 confirms that reaction
selectivity car. be maintained by using a catalyst that includes
germanium even under high-inversion-rate reaction conditions, which
have been an issue for rhenium catalysts. In addition, a comparison
between the results obtained in Examples I-1, I-4, and I-5 confirms
that the higher the sulfate ion content in the catalyst, the higher
the degree of reduction in the defunctionalization reaction, the
higher the reaction selectivity, and the higher the degree of
increase in the catalytic activity of the hydrogenation catalyst
per unit specific surface area of the carrier. The remarkable
reduction in the side reactions enables the production of an
alcohol with a high purity and a reduction in the costs of
purification of the alcohol produced.
Examples and Comparative Examples of Second Invention
Example II-1
[0249] Ammonium perrnenate and tetraethoxygermanium(IV) were
dissolved in water. Titanium oxide particles (Catalysis Society of
Japan, Reference catalyst JRC-TIO-14 produced by Ishihare Sangyo
Kaisha, Ltd.) having a specific surface area of 308 m.sup.2/g were
added to the resulting solution. The solution was stirred at room
temperature for 20 minutes. Subsequently, water was removed using
an evaporator. Then, drying was performed at 100.degree. C. for 4
hours. The resulting material was charged into a vertical baiting
tube. While air was passed through the tube, a baking treatment was
performed at 500.degree. C. for 3 hours. The resulting solid was
charged into a vertical baking tube. While a hydrogen gas was
passed through the tube, a reduction treatment was performed at
500.degree. C. for 30 minutes. Subsequently, the temperature was
reduced to 30.degree. C. After purging with an argon gas had been
performed, a 6-volume % oxygen/nitrogen gas was passed through the
tube. Hereby, 5% rhenium-5% germanium/titanium oxide catalyst
particles having stabilized surfaces (the ratio of the amount of
rhenium supported to the total mass of the catalyst: 5 mass %, the
ratio of the amount of germanium supported to the total mass of the
catalyst: 5 mass % (Ge/Re=1)) were prepared. The sulfate ion
contents in the titanium oxide particles (Catalysis Society of
Japan, Reference catalyst JRC-TIO-14) and the catalyst were 0.2% by
mass and 0.14% by mass, respectively. The sulfur content in the
catalyst was 0.078% by mass.
[0250] Into a 70-mL high-pressure reactor, 100 mg of the catalyst
prepared by the above method, 500 mg of sebacic acid, 2 g of water,
and a stirrer chip were charged. After the reactor had been purged
with nitrogen, a hydrogen gas (7 MPaG) was introduced into the
reactor at room temperature. Subsequently, a hydrogenation reaction
was conducted at 220.degree. C. for 7.5 hours. The reaction
pressure at. 220.degree. C. was 13 MPaG. After the reaction had
been terminated, the temperature was reduced to room temperature
and the pressure was then reduced. An analysis of the reaction
liquid by gas chromatography confirmed that the molar yields of
1,10-decanediol and 10-hydroxydecanoic acid in the reaction were
5.9% and 48.1%, respectively, and the molar ratio of the
by-products (1-nonanol, 1-decanol, 1-nonanoic acid, and 1-decanoic
acid) to the target components (1,10-decandiol and
10-hydroxydecanoic acid) was 0.016.
Example II-2
[0251] A hydrogenation reaction was conducted as in Example II-1
with the catalyst prepared in Example II-1, except that the amount
of time during which the hydrogenation reaction was conducted was
changed to 18 hours. The molar yields or 1,10-decanediol and
10-hydroxydecanoic acid in the reaction were 89.3% and 6.5%,
respectively. The molar ratio of the by-products (1-nonanol,
1-decanol, 1-nonanoic acid, and 1-decanoic acid) to the target
components (1,20-decanediol and 10-hydroxydecanoic acid) was
0.017.
Example II-3
[0252] A hydrogenation reaction was conducted as in Example II-1
with a catalyst prepared as in Example II-1, except that the
treatment in which the surfaces of the catalyst particles were
stabilized by passing a 6-volume % oxygen/nitrogen gas through the
tube was not performed after the reduction treatment had been
performed while a hydrogen gas was passed through the tube. The
molar yields of 1,10-docanediol and 10-hydroxydecanoic acid in the
reaction wore 74.7% and 2.6%, respectively. The molar ratio of the
by-products (1-nonanol, 1-decanol, 1-nonanoic acid, and 1-decanoic
acid) to the target components (1,10-decanediol and
10-hydroxydecanoic acid) was 0.004.
Example II-4
[0253] A 5% rhenium-5% germanium/titanium oxide catalyst was
prepared by the same catalyst preparation method as in Example
II-1, except that the titanium oxide particles were changed to
titanium oxide particles having a specific surface area of 302
m.sup.2/g and a sulfate ion content of 4.8% by mass (MC-150,
produced by Ishihara Sangyo Kaisha, Ltd.). The sulfate ion content
in the catalyst was 0.63% by mass. The sulfur content in the
catalyst was 0.57% by mass, a hydrogenation reaction was conducted
as in Example II-1 with this catalyst. The molar yields of
1,10-decanediol and 10-hydroxydecanoic acid in the reaction were
81.7% and 0.6%, respectively. The molar ratio of the by-products
(1-nonanol, 1-decanol, 1-nonanoic acid, and 1-decanoic acid) to the
target components (10-hydroxydecanoic acid and 1,10-decanediol) was
0.006.
Example II-5
[0254] A 5% rhenium-5% germanium/titanium oxide catalyst was
prepared by the same method as in Example II-1, except that the
titanium oxide particles were changed to titanium oxide particles
having a specific surface area of 90 m.sup.2/g and a sulfate ion
content of 3.6% by mass (MC-90, produced by Ishihare Sangyo Kaisha,
Ltd.). The sulfate ion content in the catalyst was 0.30% by mass.
The sulfur content in the catalyst was 0.35% by mass. A
hydrogenation reaction was conducted as in Example II-1 with this
catalyst. The molar yields of 1,10-decanedioi and
10-hydroxydecanoic acid in the reaction were 4.5% and 36.8%,
respectively. The molar ratio of the by-products (1-nonanol,
1-decanol, 1-nonanoic acid, and 1-decanoic acid) to the target
components (10-hydroxyclecanoic acid and 1,10-decanediol) was
0.011.
Example II-6
[0255] A 5% rhenium-5% indium/titanium oxide catalyst was prepared
by the same catalyst preparation method as in Example II-1, except,
that indium(III) chloride tetrahydrate was used instead of
tetraethoxygermanium(IV). Subsequently, a hydrogenation reaction
was conducted as in Example II-1. The molar yields of
1,10-decanediol and 10-hydroxydecanoic acid in the reaction were
9.0% and 43.5%, respectively. The molar ratio of the by-products
(1-nonanol, 1-decanol, 1-nonanoic acid, and 1-decaroic acid) to the
target components (10-hydroxydecanoic acid and 1,10-decanediol) was
0.034.
Example II-7
[0256] A 5% rhenium-5% silicon/titanium oxide catalyst was prepared
by the same catalyst preparation method as in Example II-1, except
that tetraethoxysilane(IV) was used instead of
tetraethoxygermanium(IV) and ethanol was used instead of water for
preparing the solution. Subsequently, a hydrogenation reaction was
conducted as in Example II-1. The molar yields of 1,10-decarediol
and 10-hydroxydecanoic acid in the reaction were 1.7% and 23.1%,
respectively. The molar ratio of the by-products (1-nonanol,
1-decanol, 1-nonanoic acid, and 1-decanoic acid) to the target
components (10-hydroxydecanoic acid and 1,10-decanediol) was
0.039.
Example II-6
[0257] A 5% rhenium-1% germanium/titanium oxide catalyst was
prepared by the same catalyst preparation method as in Example
II-1, except that the ratio between the amounts of ammonium
perrhenate and tetraethoxygermanium(IV) used as metal raw materials
was changed and the surfaces of the catalyst particles were not
stabilized by passing the 6-volume % oxygen/nitrogen gas through
the tube subsequent to the reduction treatment. A hydrogenation
reaction was conducted as in Example II-1 with this catalyst,
except that the amount of time during which the reaction was
conducted was changed to 3 hours. The molar yields of
1,10-decanediol and 10-hydroxydecanoic acid in the reaction were
36.7% and 10.8%, respectively. The molar ratio of the by-products
(1-nonanol, 1-decanol, 1-nonanoic acid, and 1-decanoic acid) to the
target components (10-hydroxydecanoic acid and 1,10-docanediol) was
0.009.
Example II-9
[0258] A hydrogenation reaction was conducted with the catalyst
prepared in Example 11-3 as in Example II-1, except that the amount
of time during which the reaction was conducted was changed to 3
hours. The molar yields of 1,10-decanediol and 10-hydroxydecanoic
acid in the reaction were 35.3% and 32.9%, respectively. The molar
ratio of the by-products (1-nonanol, 1-decanol, 1-nonanoic acid,
and 1-decanoic acid) to the target components (10-hydroxydecanoic
acid and 1,10-decanediol) was 0.005.
Example II-10
[0259] A 5% rhenium-5% germanitxm-0.5% ruthenium/titanium oxide
catalyst was prepared by the same catalyst preparation method as in
Example II-1, except that ammonium perrhenate,
tetraethoxygermanium(IV), and ruthenium(III) chloride were used as
metal raw materials and the surfaces of the catalyst particles w-re
not stabilized by passing the 6-volume % oxygen/nitrogen gas
through the tube subsequent to the reduction treatment.
Subsequently, a hydrogenation reaction was conducted as in Example
II-1. The molar yields of 1,10-decanediol and 10-hydroxydecanoic
acid in the reaction were 72.0% and 3.6%, respectively. The molar
ratio of the by-products (1-nonanol, 1-decanol, 1-norsanoic acid,
and 1-decanoic acid) to the target, components (10-bydroxydecanoic
acid and 1,10-decanediol) was 0.006.
Example II-11
[0260] A 5% rhenium-5% germanium-5% ruthenium/titanium oxide
catalyst was prepared by the same catalyst preparation method as in
Example II-10, except that the ratio between the amounts of
ammonium perrhenate, tetraethoxygermanium(XV) and ruthenium(III)
chloride used as metal raw materials was changed. Subsequently, a
hydrogenation reaction was conducted as in Example II-1. The molar
yields of 1,10-decanediol and 10-hydroxydecanoic acid in the
reaction wore 39.0% and 0.4%, respectively. The molar ratio of the
by-products (1-nonanol, 1-decanol, 1-nonanoic acid, and 1-decanoic
acid) to the target components (10-hydroxydecanoic acid and
1,10-decanediol) was 0.020.
Comparative Example II-1
[0261] A 5% rhenium/titanium oxide catalyst was prepared by the
same catalyst preparation method as in Example II-1, except chat
tetraethoxygermanium was not used. Subsequently a hydrogenation
reaction was conducted as in Example II-1. The molar yields of
1,10-decanediol and 10-hydroxydecanoic acid in the reaction were
0.1% and 21.0%, respectively. The molar ratio of the by-products
(1-nonanol, 1-decanol, 1-nonanoic acid, and 1-decanoic acid) to the
target components (1,10-decanediol and 10-hydroxydecanoic acid) was
0.060.
Comparative Example II-2
[0262] A 5% rhenium-5% palladium/titanium oxide catalyst was
prepared by the same catalyst preparation method as in Example
II-1, except that ammonium perrhenate and
dichlorotetraanuninepalladium(II) were used as metal raw materials.
Subsequently, a hydrogenation reaction was conducted as in Example
I-1. The molar yields of 1,10-decanediol and 10-hydroxydecanoic
acid m the reaction were 33.1% and 0.0%, respectively. The molar
ratio of the by-products (1-nonanol, 1-decanol, 1-nonanoic acid,
and 1-decanoic acid) to the target components (10-hydroxydecanoic
acid and 1,10-decanediol) was 0.825.
Comparative Example II-3
[0263] A 5% rhenium-5% ruthenium/titanium oxide catalyst was
prepared by the same catalyst preparation method as in Example
II-1, except that ammonium perrhenate and ruthenium (III) chloride
were used as metal, raw materials. Subsequently, a hydrogenation
reaction was conducted as in Example II-1. The molar yields of
1,10-decanediol and 10-hydroxydecanoic acid in the reaction were
45.0% and 11.1%, respectively. The molar ratio of the by-products
(1-nonanol, 1-decanol, 1-nonanoic acid, and 1-decanoic acid) to the
target components (10-hydroxydecanolc acid and 1,10-decanediol was
0.063.
[0264] Table 2 summarizes the results obtained in Examples II-1 to
II-11 and Comparative examples II-1 to II-3.
TABLE-US-00002 TABLE 2 Reaction results Hydrogenation Yield of
1,10- Yield of 10- By-product/target reaction time decanediol
hydroxydecanoic component molar Catalyst (hour) (mol %) acid (mol
%) ratio Example 5%Re 5%Ge/TiO.sub.2 7.5 5.9 48.1 0.016 II-1
Example 5%Re 5%Ge/TiO.sub.2 18 89.3 6.5 0.017 II-2 Example 5%Re
5%Ge/TiO.sub.2 7.5 74.7 2.6 0.004 II-3 Example 5%Re 5%Ge/TiO.sub.2
7.5 81.7 0.6 0.006 II-4 Example 5%Re 5%Ge/TiO.sub.2 7.5 4.5 36.8
0.011 II-5 Example 5%Re 5%In/TiO.sub.2 7.5 9.0 43.5 0.034 II-6
Example 5%Re 5%Si/TiO.sub.2 7.5 1.7 23.1 0.039 II-7 Example 5%Re
1%Ge/TiO.sub.2 3 38.7 10.8 0.009 II-8 Example 5%Re 5%Ge/TiO.sub.2 3
35.3 32.9 0.005 II-9 Example 5%Re 5%Ge 7.5 72.0 3.6 0.006 II-10
5%Ru/ TiO.sub.2 Example 5%Re 5%Ge 7.5 89.0 0.4 0.020 II-11 5%Ru/
TiO.sub.2 Comparative 5%Re/TiO.sub.2 7.5 0.1 21.0 0.060 example
II-1 Comparative 5%Re 5%Pd/TiO.sub.2 7.5 33.1 0.0 0.825 example
II-2 Comparative 5%Re 5%Ru/TiO.sub.2 7.5 45.0 11.1 0.063 example
II-3
Example II-12
[0265] Ammonium perrhenate and tetraethoxygermanium(IV) were
dissolved in water. Titanium oxide particles (MC-150, produced by
Ishihara Sangyo Kalsha, Ltd.) having a specific surface area of 302
m.sup.2/g and a sulfate ion content of 4.8% by mass were added to
the resulting solution. The solution was stirred at room
temperature for 20 minutes.
[0266] Subsequently, water was removed using an evaporator. Then,
drying was performed at 100.degree. C. for 4 hours. The resulting
material was charged into a vertical baking tube, while air was
passed through the tube, a baking treatment was performed at
500.degree. C. for 3 hours. The resulting solid was charged into a
vertical baking tube. While a hydrogen gas was passed through the
tube, a reduction treatment was performed at 500.degree. C. for 30
minutes. Hereby, a 5% rhenium-5% germanium/titanium oxide catalyst
(the ratio of the amount of rhenium supported to the total mass of
the catalyst: 5 mass %, the ratio of the amount of germanium
supported to the total mass of the catalyst: 5 mass % (Ge/Re=1))
was prepared.
[0267] Into a 70-mL high-pressure reactor, 70 mg of the catalyst
prepared by the above method, 260 mg of decanoic acid, 1.2 mL of
methanol, and a stirrer chip were charged. After the reactor had
been purged with nitrogen, a hydrogen gas (7 MPaG) was introduced
into the reactor at room temperature. Subsequently, a hydrogenation
reaction -was conducted at 220.degree. C. for 3 hours. The reaction
pressure at 220.degree. C. was 13 MPaG. After the reaction had been
terminated, the temperature was reduced to room temperature and the
pressure was then reduced. An analysis of the reaction liquid by
gas chromatography confirmed that the molar yield of 10-decanol in
the reaction was 76.5% and the molar ratio of the by-products
(nonane and decane) to the target component (10-decanol) was
0.004.
Example II-13
[0268] A 5% rhenium-5% germanium/zirconium oxide catalyst was
prepared by the same catalyst preparation method as in Example
II-8, except that zirconium oxide particles having a specific
surface area of 97 m.sup.2/g which did not include a sulfate ion
was used instead of the titanium oxide particles. Subsequently, a
hydrogenation reaction was conducted as in Example II-8, except
that a water solvent was used instead of methanol. The molar yield
of 10-decanol in the reaction was 23.2% and the molar ratio of the
by-products (nonane and decane) to the target component
(10-decanol) was 0.001.
[0269] A comparison between the results obtained in Examples II-1,
to II-3, and the results obtained in Comparative examples II-1 to
II-3, where a catalyst including a carrier composed of titanium
oxide was used, confirms that using a catalyst including rhenium
and a specific amount of second component increases the total
amount of 1,10-decanediol and 10-hydroxydecanoic acid produced in a
hydrogenation reaction of a carboxylic acid per unit specific
surface area and enhances catalytic activity per unit specific
surface area. Furthermore, the occurrence of side reactions, such
as a defunctionalization reaction associated with dehydration and
hydrogenation, can be markedly reduced. The advantageous effects
become significant particularly when a catalyst including germanium
is used. Note chat, the total amount of 1,10-decanediol and
10-hydroxydecancic acid produced is used as a measure of catalytic
activity because 10-hydroxydecanoic acid is considered a reaction
intermediate of the 1,10-decanediol product and can be derived into
1,10-decanediol when the reaction times is further prolonged. A
comparison between the results obtained in Examples II-12 and II-13
confirms that a catalyst including a carrier composed of zirconium
oxide also has the same advantageous effects as a catalyst,
including a carrier composed of titanium oxide.
[0270] Specifically, it is confirmed that a catalyst including a
zirconium oxide carrier has a catalytic activity comparable to that
of a catalyst including a titanium oxide carrier in terms of
catalytic activity per unit specific surface area. A comparison
between the results obtained in Examples II-1 and II-2 confirms
that reaction selectivity can be maintained by using a catalyst
that includes germanium even under high-inversion-rate reaction
conditions, which have been an issue for rhenium catalysts. In
addition, a comparison between the results obtained in Examples
II-1, II-4, and II-5 confirms that the higher the sulfate ion
content in the catalyst, the higher the degree of reduction in the
defunctionalization reaction, the higher the reaction selectivity,
and the higher the degree of increase in the catalytic activity of
the hydrogenation catalyst per unit specific surface area of the
carrier. The remarkable reduction in the side reactions enables the
production of an alcohol with a high purity and a reduction in the
costs of purification of the alcohol produced.
INDUSTRIAL APPLICABILITY
[0271] This catalyst is industrially useful as a catalyst for
directly synthesizing an alcohol from a carbonyl compound. This
catalyst enables an intended alcohol to fee produced with high
activity and high selectivity and reduces increases in the costs of
purification of the product and the costs of production of the
catalyst. Therefore, this catalyst is industrially highly
valuable.
[0272] Although the present invention has been described in detail
with reference to particular embodiments, it is apparent to a
person skilled in the art that various modifications can be mace
therein without departing from the spirit and scope of the present
invention.
[0273] The present application is based on Japanese Patent
Application No. 2017-043988 filed on Mar. 8, 2017, and Japanese
Patent Application No. 2017-102053 filed on May 2 2017, which are
incorporated herein by reference in their entirety.
* * * * *