U.S. patent application number 09/737894 was filed with the patent office on 2001-07-26 for catalyst for preparing lactone and a method for preparing lactone.
This patent application is currently assigned to DAIREN CHEMICAL CORPORATION. Invention is credited to Chen, Shien-Chang, Hsu, Liang-An, Lin, Fu-Shen, Tsai, Cheng-Lin.
Application Number | 20010009964 09/737894 |
Document ID | / |
Family ID | 21658464 |
Filed Date | 2001-07-26 |
United States Patent
Application |
20010009964 |
Kind Code |
A1 |
Chen, Shien-Chang ; et
al. |
July 26, 2001 |
Catalyst for preparing lactone and a method for preparing
lactone
Abstract
The present invention relates to a catalyst for preparing a
lactone, which is prepared by supporting a cupric compound, a zinc
compound and at least one alkaline earth metal compound on the
supporter. The present invention also relates to a method for
preparing a lactone, which comprises a dehydrocyclization reaction
of a diol under a gas phase in the presence of the aforementioned
catalyst after activating said catalyst. The catalyst for preparing
lactone of the present invention is quite economic because of its
high activity, long lifetime and high selectivity of products.
Inventors: |
Chen, Shien-Chang; (Taipei,
TW) ; Lin, Fu-Shen; (Kaohsiung, TW) ; Hsu,
Liang-An; (Kaohsiung, TW) ; Tsai, Cheng-Lin;
(Kaohsiung, TW) |
Correspondence
Address: |
Dr. Teresa J. Welch
Michael Best & Friedrich LLP
One South Pinckney Street, Suite 700
P. O. Box 1806
Madison
WI
53701-1806
US
|
Assignee: |
DAIREN CHEMICAL CORPORATION
7th Floor, No. 301
Taipei
TW
|
Family ID: |
21658464 |
Appl. No.: |
09/737894 |
Filed: |
December 15, 2000 |
Current U.S.
Class: |
549/266 ;
502/243; 549/273; 549/295 |
Current CPC
Class: |
B01J 23/78 20130101;
B01J 23/80 20130101; C07D 315/00 20130101 |
Class at
Publication: |
549/266 ;
549/295; 549/273; 502/243 |
International
Class: |
C07D 37/58; C07D
39/38 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 14, 2000 |
TW |
89100512 |
Claims
What is claimed is:
1. A catalyst for preparing a lactone, which is prepared by
supporting a cupric compound, a zinc compound and at least one
alkaline earth metal compound on the supporter.
2. A catalyst according to claim 1, wherein the material of said
supporter is selected from a group consisting of silica, alumina,
and their mixture.
3. A catalyst according to claim 1, wherein said cupric compound is
selected from a group consisting of copper (II) nitrate, copper
(II) carbonate, copper (II) acetate, copper (II) chloride, copper
(II) hydroxide, copper (II) phosphate and copper (II) sulfate.
4. A catalyst according to claim 1, wherein said zinc compound is
selected from a group consisting of zinc nitrate, zinc carbonate,
zinc acetate, zinc chloride, zinc hydroxide and zinc sulfate.
5. A catalyst according to claim 1, wherein said alkaline earth
metal compound is selected from a group consisting of carbonate,
hydroxide, silicate and phosphate of beryllium, magnesium, calcium,
strontium or barium.
6. A catalyst according to claim 1, wherein the ratio of cupric
compound to zinc compound is 6:1 to 1:2 by weight in terms of
copper (II) oxide and zinc oxide.
7. A catalyst according to claim 1, wherein the amount of alkaline
earth metal compound is 0.01 to 10 wt % based on the total weight
of copper (II) oxide and zinc oxide in terms of oxides, when one of
the alkaline earth metal compounds selected from a group consisting
of magnesium, calcium and barium is used.
8. A catalyst according to claim 1, wherein the amount of alkaline
earth metal compound is 0.5 to 20 wt % based on the total weight of
copper (II) oxide and zinc oxide in terms of oxides, when two of
the alkaline earth metal compounds selected from a group consisting
of magnesium, calcium and barium are used.
9. A method for preparing a lactone, which comprises a
dehydrocyclization reaction of a diol under a gas phase in the
presence of a catalyst according to any one of claim 1 to claim 8
after activating said catalyst.
10. A method according to claim 9, wherein said lactone is selected
from a group consisting of .beta.-propiolactone,
.beta.-butyrolactone, .gamma.-butyrolactone, .gamma.-valerolactone,
.delta.-butyrolactone, .gamma.-caprolactone,
.epsilon.-caprolactone, .delta.-hydroxyoctylic acid lactone,
.delta.-hydroxynonylic acid lactone, .gamma.-hydroxydecylic acid
lactone and .delta.-hydroxydecylic acid lactone.
11. A method according to claim 9, wherein said diol is selected
from a group consisting of 1,3-propylene glycol, 2-methyl-
1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol,
1,5-pentanediol, 1,4-petanediol, 1,5-hexanediol, 1,6-hexanediol,
1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol and
1,10-decanediol.
12. A method according to claim 9, wherein said lactone is
.gamma.-butyrolactone and said diol is 1,4-butylene glycol.
13. A method according to claim 9, wherein said catalyst is reduced
to activate at a temperature ranging from 180 to 250.degree. C. for
6 to 20 hours with hydrogen gas.
14. A method according to claim 9, wherein said dehydrocyclization
reaction is carried out at a temperature ranging from 160 to
280.degree. C..
15. A method according to claim 12, wherein said dehydrocyclization
reaction is carried out in a molar ratio of hydrogen gas to
1,4-butylene glycol ranging from (12 to 1):1.
16. A method according to claim 12, wherein said dehydrocyclization
reaction is carried out with the gas hourly space velocity of
1,4-butylene glycol ranging from 1to 20,000 hr.sup.-1.
17. A method according to claim 9, wherein the catalyst bed used
for said dehydrocyclization reaction is a fixed bed.
18. A method according to claim 9, wherein the catalyst bed used
for said dehydrocyclization reaction is a fluid bed.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a catalyst for preparing a
lactone, which is prepared by supporting a cupric compound, a zinc
compound and at least one alkaline earth metal compound on the
supporter. The present invention also relates to a method for
preparing a lactone, which comprises a dehydrocyclization reaction
of a diol under a gas phase in the presence of the aforementioned
catalyst after activating said catalyst.
BACKGROUND OF THE INVENTION
[0002] Lactone, such as .gamma.-butyrolactone, may be used as a
herbicide, used in the pharmaceutical composition, or used for
preparing an intermediate; this intermediate is used to prepare
pyrrolidone (such as N-methylpyrrolidone, 2-pyrrolidone and
N-vinylpyrrolidone), piperidine, phenylbutyric acid and thiobutyric
acid. Thus, developing an economic method for preparing
.gamma.-butyrolactone is a common industrial requirement.
[0003] Previously, .gamma.-butyrolactone was commonly produced by a
hydrogenation reaction with maleic anhydride or maleic acid ester
under liquid phase or gas phase. However, this is an undesirable
industrial process because the process needs a lot of hydrogen gas
and its catalyst has a short lifetime.
[0004] Recently, .gamma.-butyrolactone was produced by a
dehydrocyclization reaction with 1,4-butanediol, where a hydrogen
by-product was generated as a raw material and as fuel. This method
for preparing .gamma.-butyrolactone through the dehydrocyclization
reaction of 1,4-butanediol is disclosed in Japanese Patent
Unexamined Publication No. Sho-58-13575, wherein the
dehydrocyclization reaction is carried out under liquid phase using
a platinum/lead catalyst; however, the activity of said catalyst is
low and the selectivity of .gamma.-butyrolactone is also low. The
method disclosed in Japanese Patent Unexamined Publication No.
Sho-61-246173 describes that .gamma.-butyrolactone is obtained by
passing 1,4-butanediol vapor through a copper/chromium/zinc
catalyst; however, this method may generate many tetrahydrofuran
and butanol by-products, and the selectivity and yield of
.gamma.-butyrolactone is usually low. The method disclosed in
Japanese Patent Unexamined Publication No. Hei-3-232874 describes
that .gamma.-butyrolactone is produced by passing 1,4-butanediol
vapor through a copper/chromium/maniganese or barium catalyst; the
method disclosed in U.S. Pat. No. 5,110,954 describes that
.gamma.-butyrolactone is obtained by adding 1,4-butanediol into the
solution of copper/chromium catalyst; and the method disclosed in
Japanese Patent Unexamined Publication No. Hei-2-255668 describes
that .gamma.-butyrolactone is produced by passing 1,4-butanediol
vapor through a copper/zinc/alkali metal catalyst. However, the
activity of these catalysts may decay quickly, and the conversion
of 1,4-butylene glycol may become lower after reacting over a long
period. Therefore, it is undesirable as an industrial process.
[0005] The present inventors have deeply studied the above defects
of the traditional technique and found more effective catalyst for
preparing a lactone in the catalyst supporting a cupric compound, a
zinc compound and at least one alkaline earth metal compound. The
process for preparing lactone through the dehydrocyclization
reaction of diol using the above catalyst under gas phase may
increase the activity and lifetime of catalyst, while the
selectivity may be up to 99 mol % or more; therefore the beneficial
economic effect of industrial processes may be substantially
increased. We have hereby accomplished the present invention.
SUMMARY OF THE INVENTION
[0006] The present invention relates to a catalyst for preparing a
lactone, which is prepared by supporting a cupric compound, a zinc
compound and at least one alkaline earth metal compound on the
supporter. The present invention also relates to a method for
preparing a lactone, which comprises a dehydrocyclization reaction
of a diol under a gas phase in the presence of the aforementioned
catalyst after activating said catalyst. The catalyst for preparing
lactone of the present invention is quite economic because of its
high activity, long lifetime and high selectivity of products.
DETAILED DESCRIPTION OF THE INVENTION
[0007] The catalyst of the present invention used for preparing a
lactone is prepared by supporting a cupric compound, a zinc
compound and at least one alkaline earth metal compound on the
supporter. The suitable materials for the supporter used in the
catalyst of the present invention are silica, alumina, or their
mixture, more preferably the mixture of silica and alumina.
[0008] In the catalyst of the present invention used for preparing
lactone, the cupric compound may be various cupric salts, of which
the examples are copper (II) nitrate
(Cu(NO.sub.3).sub.2.3H.sub.2O), copper (II) carbonate
(Cu.sub.2(OH).sub.2CO.sub.3), copper (II) acetate
(Cu(CH.sub.3COO).sub.2), copper (II) chloride
(CuCl.sub.2.2H.sub.2O), copper (II) hydroxide (Cu(OH).sub.2),
copper (II) phosphate (Cu.sub.3(PO.sub.4).sub.2.3H.sub.2O), copper
(II) sulfate (CuSO.sub.4.5H.sub.2O), etc. The zinc compound used in
the catalyst of the present invention may be various zinc salts, of
which the example are zinc nitrate (Zn(NO.sub.3).sub.2.6H.sub.2O),
zinc carbonate (ZnCO.sub.3), zinc acetate
(Zn(CH.sub.3COO).sub.2.2H.sub.2O), zinc chloride (ZnCl.sub.2), zinc
hydroxide (Zn(OH).sub.2), zinc sulfate (ZnSO.sub.4.7H.sub.2O), etc.
The alkaline earth metal compound used in the catalyst of the
present invention is at least one selected from a metal compound
consisting of beryllium, magnesium, calcium, strontium and barium,
and more preferably at least one selected from a metal compound
consisting of magnesium, calcium and barium, which comprises their
carbonate, hydroxide, silicate, phosphate, etc.
[0009] The catalyst of the present invention used for preparing a
lactone is prepared according to the following method. The
supporter is immersed in the above aqueous cupric salt and zinc
salt solutions, and the value of pH is adjusted between 8 and 11
using ammonia water, while the hydroxides of copper and zinc are
precipitated on the supporter. The precipitate is washed with water
and dried. The precipitate is immersed in the above aqueous salts
solution selected from one or two alkaline earth metal compound(s)
consisting of magnesium, calcium and barium, and then calcined for
3 to 5 hours at 400 to 500.degree. C. If it is necessary, a
mold-aid agent such as graphite may be added, and a predeterminate
shape is molded by a molding machine. In such resultant catalyst,
each metal component exists in the form of oxide. Therefore, before
the dehydrogenation reaction of diol, the catalyst must be reduced
and be activated at a temperature ranging from 180 to 250.degree.
C. for 6 to 20 hours with hydrogen gas wherein the ratio of
hydrogen gas to nitrogen gas starts between 1:20 and 1:10 by
volume, then gradually adjusts to all hydrogen gas.
[0010] In the catalyst of the present invention used for preparing
lactone, the ratio of copper (II) oxide to zinc oxide is usually
6:1 to 1:2 by weight, preferably 5:1 to 1:1. When any one of the
alkaline earth metal compounds selected from a group consisting of
magnesium, calcium and barium is used, its amount is preferably
0.01 to 10 wt %, more preferably 0.05 to 5 wt %, based on the total
weight of copper (II) oxide and zinc oxide in terms of oxides. When
any two of the alkaline earth metal compounds selected from a group
consisting of magnesium, calcium and barium is used, their amounts
are preferably 0.5 to 20 wt %, more preferably 1 to 10 wt %, based
on the total weight of copper (II) oxide and zinc oxide in terms of
oxides. The amount of support is preferably 0.5 to 20 wt %, more
preferably 1 to 10 wt %, based on the total weight of copper (I)
oxide and zinc oxide in terms of silica.
[0011] The present invention also relates to a method for preparing
a lactone, which comprises a dehydrocyclization reaction of a diol
under a gas phase in the presence of the aforementioned catalyst
after activating said catalyst.
[0012] The example of the lactone used in the method for preparing
lactone of the present invention includes, for instance,
.beta.-propiolactone, .beta.-butyrolactone, .gamma.-butyrolactone,
.gamma.-valerolactone, .delta.-butyrolactone, .gamma.-caprolactone,
.epsilon.-caprolactone, .delta.-hydroxyoctylic acid lactone,
.delta.-hydroxynonylic acid lactone, .gamma.-hydroxydecylic acid
lactone, .delta.-hydroxydecylic acid lactone, etc.
[0013] The example of the diol used in the method for preparing
lactone of the present invention includes for instance,
1,3-propylene glycol, 2-methyl-1,3-propylene glycol, 1,3-butylene
glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,4-petanediol,
1,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol,
1,9-nonanediol, 1,10-decanediol, etc.
[0014] In the dehydrocyclization reaction of the method for
preparing lactone such as .gamma.-butyrolactone used in the present
invention, the reaction temperature usually ranges from 160 to
280.degree. C., preferably 180 to 250.degree. C.. If the reaction
temperature is too low, the conversion of 1,4-butylene glycol may
be decreased. Although the higher temperature may increase the
conversion of 1,4-butylene glycol, the selectivity of
.gamma.-butyrolactone may be substantially decreased.
[0015] In the dehydrocyclization reaction of the method for
preparing lactone such as .gamma.-butyrolactone used in the present
invention, the reaction pressure usually ranges from 0 to 10 atm.,
preferably from 1 to 5 atm. However, the higher reaction pressure
may easily carry out an undesired reaction, decreasing the
yield.
[0016] In the dehydrocyclization reaction of the method for
preparing lactone such as .gamma.-butyrolactone used in the present
invention, the hydrogen gas is needed as a carrier gas. If the
hydrogen gas do not exist in the reaction system, the lifetime of
catalyst may be shortened. The amount of hydrogen gas must at least
maintain the reaction system in gas phase. In generally, the molar
ratio of hydrogen gas to 1,4-butylene glycol used in the present
invention ranges from (12 to 1): 1, preferably from (8 to
1.5):1.
[0017] In the dehydrocyclization reaction of the method for
preparing lactone such as .gamma.-butyrolactone used in the present
invention, if the gas hourly space velocity of 1,4-butylene glycol
is too low, the retention time of gas in the catalyst bed is also
too long so that the product may be decomposed, resulting in the
decreasing selectivity of .gamma.-butyrolactone. If the gas hourly
space velocity of 1,4-butylene glycol is too high, the retention
time of gas in the catalyst bed is also too short so that the
conversion of 1,4-butylene glycol decreases. In general, the gas
hourly space velocity of 1,4-butylene glycol ranges from 10 to
20,000 hr.sup.-1, preferably 30 to 9,000 hr.sup.-1.
[0018] In the dehydrocyclization reaction of the method for
preparing lactone such as .gamma.-butyrolactone used in the present
invention, the catalyst bed may be a fixed bed or a fluid bed.
[0019] The present invention will be further described in the
following Examples and Comparative Examples. However, the scope of
the present invention is not restricted by such Examples.
EXAMPLE
[0020] In a given time after the dehydrocyclization reaction, the
product was collected by condensation. The component of the efflux
from the outlet was analyzed by HP-6890 gas chromatograph. The
conversion of diol and the selectivity of lactone were calculated
according to the following equation (1) and (2), and the yield of
lactone is also obtained: 1 The Conversion of Diol ( % ) = The Mole
of Feed - in Diol - The Mole of Feed - out Diol The Mole of Feed -
in Diol .times. 100 % ( 1 ) The Selectivity of Lactone ( % ) = The
Mole of Lactone Product The Mole of Feed - in Diol - The Mole of
Feed - out Diol .times. 100 % ( 2 )
Reference Example 1
[0021] A commercially available copper-chromium catalyst (30 ml)
(wherein copper oxide was 42 wt %, chromium oxide was 28 wt %, and
a diameter was 5 mm) was packed in the stainless steel reactor
having an inside diameter of 23.5 mm. After the temperature was
elevated to 150.degree. C. with nitrogen gas, the mixed gas of 10
vol % hydrogen gas was passed into the reactor, then the catalytic
reduction reaction was initiated. The temperature and the
concentration of hydrogen gas were gradually elevated until the
reduction temperature of catalyst was 200.degree. C. and the
concentration of hydrogen gas was 100 vol %. When the temperature
of catalyst bed was confirmed to be the same as that of the heating
equipment, the reduction reaction was terminated.
[0022] Subsequently, the temperature of the reactor was elevated to
210.degree. C. 1,4-butylene glycol was pumped into the reactor
using a quantitative pump, and the gas hourly space velocity of
1,4-butylene glycol was maintained at 4500 hr.sup.-1. After the
dehydrogenation reaction was carried out at a hydrogen
gas/1,4-butylene glycol ratio of 5 mole:1 mole, the product was
collected and analyzed. The results are shown in Table 1.
Reference Example 2
[0023] The same steps as in Reference Example 1 were repeated, but
a commercially available copper-zinc catalyst (G-66) was used,
wherein the component was 60 wt % of copper oxide and 30 wt % of
zinc oxide. The results are shown in Table 1.
Reference Example 3
[0024] The same steps as in Reference Example 1 were repeated, but
a copper/chromium/zinc catalyst which was prepared by the method of
Japanese Patent Unexamined Publication No. Hei-61-246173 was used,
wherein the component was 35 wt % of copper oxide, 4.5 wt % of zinc
oxide and 60 wt % of chromium oxide. The results are shown in Table
1.
Reference Example 4
[0025] The same steps as in Reference Example 1 were repeated, but
a commercially available copper-zinc catalyst (G-66) which was
immersed in 0.5 wt % of aqueous sodium hydroxide solution and then
dried was used, wherein the component was 60 wt % of copper oxide,
30 wt % of zinc oxide and 0.12 wt % of sodium hydroxide. The
results are shown in Table 1.
1TABLE 1 Reference Example 1 2 3 4 Reaction Temperature (.degree.
C.) 210 210 210 210 Reaction Pressure (atm) 1 1 1 1 Gas Hourly
Space Velocity of 4500 4500 4500 4500 1,4-Butylene Glycol
(h.sup.-1) Molar Ratio of Hydrogen Gas to 5/1 5/1 5/1 5/1
1,4-Butylene Glycol Conversion of 1,4-Butylene Glycol 72.50 91.50
81.30 97.20 (mol %) Selectivity of .gamma.-Butyrolactone 88.30
92.50 90.50 95.30 (mol %) Yield of .gamma.-Butyrolactone (mol %)
64.02 84.64 73.82 92.63
Example 1
[0026] 60 wt % of aqueous copper nitrate solution (350 g) was
slowly poured into 40 wt % of aqueous zinc nitrate solution (220 g)
and the powder of silica (10 g) wherein the BET surface area was
185 m.sup.2/g (said surface area was measured according to the
Brunner-Emmett-Teller Method), and the mixture was stirred
vigorously. Subsequently, 25 wt % of ammonia water was added to
maintain the pH value of the mixed aqueous solution at 10 while the
mixture was still stirred. The precipitate was filtered and
separated, washed with water, and placed into a oven to dry at
100.degree. C. for 12 hours, after which time a catalyst precursor
was obtained. This catalyst precursor was moved to a tubular
high-temperature furnace ,heated to 450.degree. C., and calcined
for 4 hours. The component of this catalyst was at a copper
oxide/zinc oxide ratio of 3:1.
[0027] 1.0 wt % of graphite was added to the above catalyst, then
that catalyst was extruded to a roundly-granular catalyst having a
diameter of 5 mm. The same steps as in Reference Example 1 were
repeated with this catalyst (30 ml). The results are shown in Table
2.
Example 2 to 7
[0028] The same steps as in Example 1 were repeated, but the ratio
by weight of copper oxide to zinc oxide, the temperature of
dehydrogenation, and the molar ratio of hydrogen gas to
1,4-butylene glycol are all shown in Table 2. The results of Table
2 are as follows.
2TABLE 2 Example 1 2 3 4 5 6 7 Ratio by Weight of Cupric Oxide to
3/1 5/1 1/2 5/1 3/1 5/1 3/1 Zinc Oxide Reaction Temperature
(.degree. C.) 210 210 210 210 210 230 230 Reaction Pressure (atm) 1
1 1 1 1 1 1 Gas Hourly Space Velocity of BOD (hr.sup.-1) 4500 4500
4500 4500 4500 4500 4500 Molar Ratio of Hydrogen Gas to BOD 5/1 5/1
5/1 2/1 2/1 5/1 5/1 Conversion of BOD (mol %) 97.30 98.50 92.10
95.30 93.50 98.10 97.20 Selectivity of .gamma.-Butyrolactone (mol
%) 96.10 97.40 90.50 97.10 96.50 91.50 90.30 Yield of
.gamma.-Butyrolactone (mol %) 93.50 95.94 83.35 92.53 90.22 89.76
87.77
Example 8
[0029] The catalyst precursor prepared by Example 1 was immersed in
1.5 wt % of aqueous barium hydroxide solution. Then, this catalyst
was moved to a tubular high-temperature furnace, heated to
450.degree. C., and calcined for 4 hours. The component of this
catalyst was 55 wt % of copper oxide, 22 wt % of zinc oxide and 1.2
wt % of barium oxide.
[0030] The same steps as in Reference Example 1 were carried out
with this catalyst. The results are shown in Table 3.
Example 9
[0031] The catalyst precursor prepared by Example 1 was immersed in
1.0 wt % of aqueous calcium hydroxide solution. Then, this catalyst
was moved to a tubular high-temperature furnace, heated to
450.degree. C., and calcined for 4 hours. The component of this
catalyst was 53 wt % of copper oxide, 24 wt % of zinc oxide and
0.81 wt % of calcium oxide.
[0032] The same steps as in Reference Example 1 were carried out
with this catalyst. The results are shown in Table 3.
Example 10
[0033] The catalyst precursor prepared by Example 1 was immersed in
1.0 wt % of aqueous magnesium hydroxide solution. Then, this
catalyst was moved to a tubular high-temperature furnace heated to
450.degree. C., and calcined for 4 hours. The component of this
catalyst was 49 wt % of copper oxide, 26 wt % of zinc oxide and
0.52 wt % of magnesium oxide.
[0034] The same steps as in Reference Example 1 were carried out
with this catalyst. The results are shown in Table 3.
Example 11
[0035] The catalyst precursor prepared by Example 1 was immersed in
1.5 wt % of aqueous barium hydroxide solution and 0.3 wt % of
aqueous calcium hydroxide solution. Then, this catalyst was moved
to a tubular high-temperature furnace, heated to 450.degree. C.,
and calcined for 4 hours. The component of this catalyst was 55 wt
% of copper oxide, 22 wt % of zinc oxide, 1.2 wt % of barium oxide
and 0.14 wt % of calcium oxide.
[0036] The same steps as in Reference Example 1 were carried out
with this catalyst. The results are shown in Table 3.
Example 12
[0037] The catalyst precursor prepared by Example I was immersed in
1.0 wt % of aqueous calcium hydroxide solution and 0.4 wt % of
aqueous magnesium hydroxide solution. Then, this catalyst was moved
to a tubular high-temperature furnace, heated to 450.degree. C.,
and calcined for 4 hours. The component of this catalyst was 53 wt
% of copper oxide, 24 wt % of zinc oxide, 0.81 wt % of calcium
oxide and 0.16 wt % of magnesium oxide.
[0038] The same steps as in Reference Example 1 were carried out
with this catalyst. The results are shown in Table 3.
Example 13
[0039] The catalyst precursor prepared by Example 1 was immersed in
1.0 wt % of aqueous magnesium hydroxide solution and 0.2 wt % of
aqueous barium hydroxide solution. Then, this catalyst was moved to
a tubular high-temperature furnace, heated to 450.degree. C., and
calcined for 4 hours. The component of this catalyst was 49 wt % of
copper oxide, 26 wt % of zinc oxide, 0.52 wt % of magnesium oxide
and 0.1 wt % of barium oxide.
[0040] The same steps as in Reference Example 1 were carried out
with this catalyst. The results are shown in Table 3.
3TABLE 3 Example 8 9 10 11 12 13 Reaction Temperature (.degree. C.)
210 210 210 210 210 210 Reaction Pressure (atm) 1 1 1 1 1 1 Gas
Hourly Space Velocity of BOD (hr.sup.-1) 4500 4500 4500 4500 4500
4500 Molar Ratio of Hydrogen Gas to BOD 5/1 5/1 5/1 5/1 5/1 5/1
Conversion of BOD (mol %) 99.50 99.20 99.60 99.90 99.50 99.80
Selectivity of .gamma.-Butyrolactone (mol %) 99.10 98.60 98.10
99.80 99.10 99.30 Yield of .gamma.-Butyrolactone (mol %) 98.60
97.81 97.70 99.70 98.60 99.10
* * * * *