Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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1 BACKGROUND OF THE INVENTIO~
2 1. Field of ~he Invention
3 This invention relates to a process for the pro-
4 duction of an unsaturated glycol diester ~rom a conjugated
diene compound and, more particularly, it is concerned ~Jith
6 a process for the production of an unsaturated glycol diester
7 comprising reacting a conjugated diene compound, carboxylic
8 acid and molecular oxygen in the presence of a solid
9 ca~alyst.
2. Description of the Prior Art
11 The above reaction is k~own. In particular,
12 when the carboxylic acid is acetic acid, the reactior. may
13 be depicted illustratively as follows:
14 Rl R6
\ C~C ~-C \ + 2CH3COOH + 1/2 2
16 R2 R3 4 R5
17 ll l3 l4 ~5
18 R2~ C===C--C n6 + H~O
19 CH3COO OOCCH3
2~
21 wherein Rl to R6 are individually a hydrogen a~om or a
22 hydrocarbon group9 preferably an alkyl group having 1 to
23 carbon atoms.
24 Unsaturated glycol diesters are very useful as
raw materials for various chemical processes. Above all,
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l 1,4-glycol diesters are particularly important as raw
2 materials for preparing organic solvents such as tetrahydro-
3 furan or synthetic resins such as polyurethane resins and
4 polybutylene terephthalate and various proposals have
hitherto ~een made for the production of the same.
6 In ~he process for the production of 1~4-glycol
7 diesters, it has been considered desirable to use a palladium
8 type catalyst. For example, in U.S. Patent 3,755,423,
9 1,4-diacetoxy-2-butene is obtained with high conversion as
well as high selectivity by reacting 1,3-butadiene with
,ll acetic acid using a solid catalyst containing palladium, at
12 least one of antimony and bismuth and at least one of
13 tellurium and selenium.
14 Even in the case of using this catalyst, however,
the catalyst efficiency, in particular, the palladium
16 efficiency (Mols of diacetoxybutene formed/Catalyst palladîum
17 atnm,hour) is quite low and unsatisfactory in comparison
18 with t'ne catalyst for the synthesis of vinyl acetate by
19 ethylene process which has already bPen practiced on a
commercial scale as a reaction of this type
21 A representative patent of Mitsubishi ~hemical
22 Company, Japanese Patent Public Disclosure No. 11812/74,
23 reported that the addition of a small amount of tellurium
24 to the Pd/C catalyst results in a dramatic increase in
activity for ace~oxylation with high selectivity to 1,4-
26 diacetoxy-2-butene (92%).
27 On thP other hand, BASF's patent, Japanese
28 Pa~ent Public Disclosure No. 63119/76, repor~ed that carbon-
29 suppor~ed~palladium telluride (Pd4Te/C) catalyst, which is
prepared with a controlled ratio of Pd to Te and gave no
31 diffraction line of metallic palladium in X-ray analysis,
32 shows good activity for acetoxylation.
33 Both palla~ium efficiency for diacetoxy~utenes
34 (DAB) formation over Pd-Te/C (8.4 mol-DAB/g-atom Pd/Hr~ and
Pd4Te/C catalyst (6.4), however, remained at an insufficient
36 level as a commercial catalyst.
~3~
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1 . Other patents in this area include U.S. Patents
2 3,671,577; 3,922,300; 4,075,413; 4~121,.039 and the
3 followin~ Japanese Patent Public Disclosures:
4 No. 47-39003
47-39004
6 47-39006
7 47-31919
8 49-101322
9 49-11813
50-51094
11 50-51095
12 51-149220
13 52-28495
14 Thus the prior art has taught that in the
preparation of solvents such as 1,4-butanediol from
16 butadiene, the key to the process is the initial acetoxyla-
17 tion step wherein a carbon supported Pd-Te catalyst system
18 is used~ -
19 SUMMARY OF 1~ INVENTION
Applicants have made studies on a catalyst
21 system capable of producing unsaturated esters, for example,
22 1,4-diacetoxy-2-butene9 with a higher catalytic efficiency
23 suitable for co~mercial scale operation for the purpose of
24 solving the above described problems and ha~e found that
unsaturated esters can be obtained with a high catalytic
26 efficiency and a higher selectivity by ~he use of a solid
27 catalyst cont~ining (a) palladium, (b~ tellurium and (c)
28 at least one of ~in~ germanium and lead. The present in-
29 vention is based on this finding.
That is to szy9 the present invention provides
31 a process for the production of an unsaturated glycol
32 diester, which comprises reactin~ a conjugated diene compoun~
33 a carboxy~ic acid and molecular oxygen in the presence of
34 a solid catalyst containing (a) palladium, ~) tellurium
35 and (c) at least one of Group IV elements of the Periodic
36 Table selected from the group consisting of tin, germanium
37 and lead. These are the heavy metals of Group IVA.
38 3E~AI~J7 D~sc~ lo~
39 The metallic components used for the preparation
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1 o the catalyst used in the process of the present invention
2 come from the following compounds:
3 For palladium, there may be used palladium
4 chloride, palladium nitrate, palladium sulfate, palladium
hydroxide, palladium oxide and the like.
6 For tellurium, there may be used tellurium
7 dio~ide, tellurium trioxide, telluri~m dichloride,
8 tellurium tetrachloride, tellurium tetraoxide, telluric
g acid and the like.
For the third components, i.e., tin, germanium
ll and lead, there may be used their oxides, chlorides,
12 nitrates, carboxylates and the like, for example, stannous
13 chloride, tin nitrates, tin oxides, germanium tetrachloride,
14 germanium oxides, germanium hydroxides, lead nitrate, lead
chloride, lead acetate, etc.
16 The support for the catalytic components is
17 not particularly limited, but, for example, active carbon,
18 silica gel, silica-alumina, alumina~ pumice, kieselguhr
l9 and silicon carbide may be used. In particular, active
carbon is preferred. The support may be used as it is
21 commercially sold or after it is subjected to a heat treat-
22 ment or an acid treatment with nitric acid or hydrochloric
23 acid.
24 The method of suppor~ing the catalytic components
may suitably be chosen from the ordinary methods of pre-
26 paring supported catalysts. In the case of supporting by
27 impregnation, for example, catalytic components are dis-
28 solved in a suitable solvent such as water7 aqueous acidic
29 solution of hydrochloric acid or nitric acid, aqueous
alkaline solution or organic solvent, in which a support
31 is immersed. Catalytic components may simuLtaneously or
32 successively be dissolved in a solvent followed by
33 impregnation.
34 In the present invention, the amounts of the
catalytic components supported are preferably adjusted as
36 follows. The amount of palladium supported is preferably
-- 4 --
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l 0.1 to 10.0 % by weight and even if less than 0.1 % by
2 weight or more than 10.0 % by weight, the reaction can
3 proceed. The amount of tellurium is preferably 0.01 to
4 5.0 % by weight, more preferably 0.1 to 3.0 % by weight.
S The amount of at least one of tin, germanium and lead is
6 preferably 0.01 to 10.0 % by weight, more preferably 0.1
7 to 3.0 % by weight of the total catalyst.
8 The atomic ratio of tellurium and at least
9 ona of tin, germ~nium and lead to palladium in the catalyst
is preferably 0.05 to 10 gram atoms to 1 gram atom of
11 palladium, more preferably 0.1 to 5 gram atoms of teLlurium
12 and 0.1 to 2 gram atoms of at least one of tin, germanium
13 and lead to 1 gram atom of palladium.
14 The support having the catalytic components is
then subjected to removal of the solvent and to reduction
16 in a hydrogen stream or in a gaseous stream containing an
17 organic compound capable of reducing, in general, at a re-
18 ducing temperature of 150 to 500C., preferably 200 ~o
l9 400C., for 2 to 10 hours, thus producing a catalyst.
2~ Examples of the conju~ated diene compound usPd
21 as a raw material in the process of the present invention
22 are 1,3-bu~adiene and hydrocarbon substituted derivatives
23 thereof such as isoprene, 1,3-pentadiene, 2,3-dimethyl-
24 1,3-butadiene, 1,3-hexadiene, ~,4-hexadiene~ 1,3-oc~adiene
and 4-phenyl-~butadiene, and cyclic conjugated diene
26 compounds such as cyclopentadiene, 1,3-cyclohexadiene and
27 1,3~cyclooctadiene. Above all~ 1,3-butadiene is preferred.
28 It is not always required that the con~ugated diene compound
29 be pure, but nitrogen, carbon dioxide or a lower saturated
hydrocarbon such as methane, ethane, propane or butane
31 may be admixed therewith.
32 The carbo~ylic acid as another raw material
33 in the process of the present invention may be selected from
34 saturated or unsaturated aliphatic carboxylic acids and
aromatic carbaxylic acids having 2 to 20 carbon atoms.
Lower aliphatic mono carboxylic acids containing 2 to 4
-- 5 --
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-- 6 --
1 carbon atoms such as acetic acid, propionic acid and
2 butyric acid are preferably used and, in particular, acetic
3 acid is more preferable.
4 The molecular oxygen used in the process of the
present invention does not have to be pure but may be diluted
6 wi~h an inert gas such as nitrogen or carbon dioxide, and
7 of course may be air.
8 The reaction conditions employed in the process
9 of the present invention are as follows: The reaction
10 may be carried out batch-wise or continuously in liquid
11 phase using a fixed bed or fluidized bed. The reaction
12 temperature, pressure and feed quantities of a conjugated
13 diene compound, carboxylic acid and molecular oxygen are
14 not particularly limited but preferably the reaction
15 temperature ranges from 40C to L80C.~ the pressure
16 ranges from atmospheric to 100 Kg/cm2 and the molar ratio
17 of conjugated diene compound/carboxylic acid/molecuLar
18 oxygen is in the range of 1/0.5-10.0/0.1-5Ø
19 The following examples are provided in order to
illustrate the present invention in detail without limit-
21 ing the same.
22 Example_ 1
23 0.1750 g of palladium chloride and 0.0250 g of
24 tellurium dioxide were dissolved in 40 ml of 6N hydrochloric
25 acid, to which a methanol solution of 0.2214 g of stannous
26 chloride (SnC12 2H20~ was added, and 10 g of active carbon
27 of 24 to 42 mesh, previously heated and refluxed with 15
28 % by weight nitric acid for 6 hours, was immersed in the
29 resulting solution at room tempera~ure for 24 hours. After
30 the immersion, the mixture was then evaporated gradually
31 to dryness on a warm water bath, dried at 150C for 3
32 hours in a nitrogen stream ln a tube and reduced with
33 nitrogen saturated with methanol at room temperature at
34 200C ror 3 hours and at 400C for 2 hours, thus obtaining
35 a catalyst containing 1.05 % by weight of palladium,
36 0.20 % by weight of tellurium and 1.16 % by weight of tin
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1 and having a palladium/~ellurium/tin atomic ratio of
2 1.0/0.16/l.o
3 4 g of the catalyst prepared in this way was
4 charged to a reaction tube of stainless steel with an
inner diameter of 18 mm, through which glacial acetic
6 acid, butadiene and oxygen were passed at a rate of 12.5
7 ml/hr, 60 mmol/hr and 40 mmol/hr respectiveLy, and
8 the reaction was carried out continuously at a reaction
9 temperature of 80C.
Analysis of the product after passage of 5 hours
11 from the start of the reaction gave the space time yield
12 (glcatalyst 1 hr), palladium efficiency (mollpalladium atom-hr)
13 and 1,4-isomer selectivity (%) shown in Table 1.
14 ExamPles 2 and 3
The preparation of a catalyst and the reaction
16 using the same were carried out in a manner analogous to
17 Example 1 except that 0.2124 g of germanium tetrachloride
18 or 0.3271 g of lead nitrate was added in place of the
19 stannous chloride of Example 1, thus obtaining the results
shown in Table 1. In Example 2 7 a solu~ion of germanium
21 tetrachloride in absolute alcohol was added and in Example
22 3, a svlution of lead nitrate in hydrochloric acid was added.
23 ~om~arative Exam~les 1 and 2
24 The preparation of a catalyst and the reaction
using the same were carried out in a manner analogous to
26 Example l except that a combination of palladium chloride
27 with tellurium dioxide or palladium chloride with stannous
28 chlori~e was used to obtain the results shown in:Table 1.
29 Comparative Example 3
The preparation of a catalyst and ~he react;on
- 31 using the same were carried out in a manner analogous to
32 Example 1 except that a combination Oc 0.0250 g of tellurium
33 dioxide and 0.2214 g of stannous chloride only was used
34 to obtain the results shown in Table 1
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1 Comparative Examples 4 to 10
2 The preparation o a catalyst and the reaction
3 using the same were carried out in a manner analogous to
4 Example 1 except that each of the following metal salts was
added in such a manner that the atomic ratio of the sup-
6 ported metal to palladium was 1.0 in place o the stannous
7 chloride of Example 1, thus obtaining the results shown
8 in Table 2.
9 Each of cuprous chloride, nickel nitrate, ferric
nitrate, ammonium molybdenate, potassium acetate, antimony
11 trichloride and bismuth nitrate was dissolved in 6N hydro-
12 chloriG acid with palladium chloride and tellurium dioxide.
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1 Example 4
2 The catalyst of palladium-tellurium-tin/active
3 carbon prepared in Example l was charged to a pressure-
4 resisting reaction tube of stainless steel with an inner
S diameter of 14mm, through which 6~7 ml/hr of glacial
6 acetic acid, 4.0 ml/hr of liquid 1,3-butadiene and 470 N
7 ml/min of nitrogen gas containing 3 mol % of oxygen were
8 passed, and the reaction was continuously carried out in
9 liquid phase at a reaction temperature of 100C under a
pressure of 40 Kg/cm2 to obtain the results shown in
11 Table 3.
12 Comparative Example 11
13 The reaction was carried out in a manner analogous
14 to Example 4 except that the catalyst of palladium-tellurium/
active carbon prepared in Comparative Example 1 was used
16 to obtain the results shown in Table 3.
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1 Ex2m~1es 5 to 8
2 The reaction was carried out in a manner analogous
3 to Exam~le 1 and eack of the Pd-Te-Sn catalysts was pre-
4 pared similarly except that stannous chloride was added to
give an Sn/Pd atomic ratio ranging from 0.1 to 2.0, thus
6 obtaining the results shown in Table 4.
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l Exam~les 9-10 and Com~arative Examples 12-14
2 Comparison with BASF and Mitsubishi Chemical Co.
3 processes in catalyst performance is summarized in Table 5.
4 The catalysts of Examples 9 and 10 were prepared in a manner
analogous to Example 1.
6 Both Examples 9 and 10 gave a Pd efficiency superior
7 to Comparative Examples 12-14. The Pd-Te-Sn/C catalyst in
8 Example 10 gave excellent palladium efficiency (32.7 mol-
9 DAB/g-atom Pd/hr) which is substantially equivalent to the
commercial one of vinyl acetate synthesis from ethylene over
11 a Pd catalyst. Pd efficiency for commercial vinyl acetate
12 synthesis is estimated to be about 50. This value corres-
13 ponds to about 25 Pd efficiency for diacetoxylation.
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