Note: Descriptions are shown in the official language in which they were submitted.
li 1094098
¦ DETAILED DESCRIPTION OF THE INVE~TION:
This invention relates to a process for producing
methacrylic acid and a methacrylate or acrylic acid and an
acryla`te at the same time.
- More particularly, this invention relates to a
process for simultaneously producing methacrylic acid and a
methacrylate or acrylic acid and an acrylate by reacting
methacrolein or acrolein with an aliphatic alcohol and molecular
oxygen in the vapor phase by using a catalyst comprising (1)
palladium, (2) phasphorus, ~3~ antimony, t4) X and (5) oxygen
wherein X denotes at least one element selected from the group
consisting of potassium, sodium, lithium, rubidium, cerium,
beryllium, lead, magnesium, calcium, strontium, zinc, barium,
l thorium, bismuth, chromium, iron, nickel, cobalt, vanadium,
15 ~ manganese, tin, uranium and rhenium.
The process of the invention may further comprise
supplying into the reaction system a phosphoric acid or a
phosphorus compound capable of forming a phosphoric acid
through a chemical change during the reaction.
For the synthesis of methacrylic acid by oxidizing
methacrolein in a vapor phase a number of catalysts have
hitherio been proposed.
Almost all of these catalysts, however, have low
l activities. Further, if the reaction is carried out at an
elevated temperature in order to increase the conversion,
., I
09409~ j
large amounts of undesirable by-products such as carbon
monoxide, carbon dioxide, acetic acid etc. are produced so
that the per-pass yield of methacrylic acid is very low.
~ The catalysts as disclosed in the Japanese Patent
¦ Laid-Open Publication Nos. 67216/1973 and 61416/1973, which
are improved in their catalytic activity and selectivity,
I comprise phosphomolybdic acid or its salts as the main
ingredient,
Phosphomolybdic acid-based catalysts have a dis-
advantage that the catalyst lifetime is short. Once they lose
activity, it cannot be restored by means of a simple treatment
such as re-calcination, for example. When the temperature of
reaction or calcination exceeds 450C, they are abruptly
degraded in catalytic activity. Thus, they are thermally
unstable and they are not always available for commercial use.
Further, conventional phosphomolybdic acid-based
catalysts offer a notably short catalytic lifetime when the
reaction is carried out at a particularly high space velocity.
Japanese Patent Laid-Open Publication No. 30,826/1975
2Q discloses a process for producing methyl methacrylate which
!¦ comprises subjecting a gas mixture of methacrolein, methanol,
¦¦ oxy~en, steam and nitrogen to the reaction in the vapor phase
¦¦ in the presence of a molybdenum-vanadium-tungsten series catalyst.
¦ The process is far from commercially satisfactory because the
yield of methyl methacrylate is very low.
,
`` 1094098
Another disclosure relating to a catalyst containing
palladium, phosphorus and oxygen is described in Japanese
Patent Laid-Open Publication No. 37,719/1975. Methacrylic
acid is prepared by oxidizing methacrolein with molecular
oxygen in the presence of the above catalyst. The destined
product, methacrylic acid is produced in higher yield and
selectivity, while a comparatively large amount of steam is
required. The larger the feed, the larger the equipment,
which is undesirable on an industrial scale and economically
disadvantageous. Since the process of the above application
is only directed to the preparation of methacrylic acid,
it is, of course, impossible to prepare an ester at the same
time.
The present invention is directed at overcoming the
aforementioned disadvantages and according to the process of
the present invention, methacrolein or acrolein is oxidised
at low temperature such as 160 to 350C and methacrylic acid
and a methacrylate or acrylic acid and an acrylate are produced
in high yields at the same time. Further the formation of
by-products such as acetic acid, carbon monoxide and carbon
dioxide owing to the degradation is well suppressed. The
amount of steam to be fed during the reaction may be very small,
which is one of the important characteristics of the invention.
In addition the catalyst according to the present invention is
I ~094098
I
thermally stable and therefore has a substantially longer
service life, particularly even when the reaction is carried
out at high space velocities.
~ The process of the invention is not only economically
advantageous, but also industrially epoch-making.
The catalyst to be used in the present invention
comprises (1) palladium, (2) phosphorus, (3) antimony, (4)
X and (5) oxygen wherein X denotes at least one element selected
from the group consisting of potassium, sodium, lithium,
rubidium, cerium, beryllium, lead, magnesium, calcium,
strontium, zinc, ~arium, thorium, bismuth, chromium, iron,
nickel, cobalt, vanadium, manganese, tin, uranium, and rhenium
and has a long service life which is significantly superior to
those of the prior phosphomolybdic acid-based catalysts.
It has surprisingly been found that the catalyst is
stable at elevated temperatures, for example, at 600C.
However, this catalyst as such is not completely
satisfactory, because a part of phosphorus which is one of
the essential components of the catalyst, though in a very small
amount, leaves the catalyst system during the reaction.
Consequently, the semipermanent life required for commercial
catalysts can not be attained.
The inventors have found that when the reaction is
l carried out in the presence of the catalyst, the catalyst
can be st~bilized and its servi~e life can iurther be prol~nged
l - 5 -
i! ~
1094098
by continuously or intermittently supplementing phosphorus
in an appropriate amount corresponding to that of the phos-
phorus which leaves the catalyst system.
¦ The process of the present invention is epoch-
¦ making and of great value for commercial use since methacrylic
acid and a methacrylate or acrylic acid and an acrylate can be
selectively produced in high yields for long periods of time.
The term "a phosphoric acid or a phosphorus compound
capable of forming a phosphoric acid through a chemical change
during the reaction "(hereinafter to be referred to as a
phosphorus-containing compound~ which is to be supplied to the
reaction system in accordance with the present invention
means any of phosphoric acids and phosphorus compounds capable
of forming a phosphoric acld through a chemical reaction such
as hydrolysis, oxidation, etc., including orthophosphoric acid,
pyrophosphoric acid, metaphosphoric acid, phosphorous acid,
hypophosphorous acid, phosphine, organic phosphoric acids,
solid phosphoric acids, etc.
To the reaction system the phosphorus-containing
20 I compound may be supplied in any suitable manner.
For example, if the phosphorus-containing compound
is water-soluble, it may uniformly be dissolved in water to
be used for the reaction so that it is carried to the reaction
system along with water.
If the phosphorus-containing compound is solid, for
, l
li l
, . ,
' 6
1094098
1 i
1.
¦ example, a solid phosphoric acid, this solid material may be
charged in front of the catalyst layer. As steam is fed and
made contact with the charged material, the latter generates
~ a phosphoric acid, which is carried to the catalyst layer
, along with steam.
~urtheremore, if the phosphorus-containing compound
is gaseous, a gaseous mixture of the same and air may be
fed to the catalyst layer.
The amount of the phosphorus~containing compound
to be supplied may vary over a wide range. In general, the
phosphorus-containing compound is supplied so that the amount
of phosphorus contained in the compound is preferably 5 to
1 x 10 4 wt%, more particularly 0.5 to 1 x 10 3 wt% on the
l basis of a total amount of water and an aliphatic alcohol fed
1 during the reaction.
!l A preferred catalyst according to the present
invention has the following composition: ¦
PdaPbSbCXdOe
l wherein X denotes at least one element selected from the group
I consisting of potassium, sodium, lithium, rubidium, cerium,
!l beryllium, lead, magnesium, calcium, strontium, zinc, barium,
¦ thorium, bismuth, chromium, iron, nickel, cobalt, vanadium,
manganese, tin, uranium, and rhenium, the subscripts a, b, c,
! d and e denote the number of the Pd, P, Sb, X and O atoms,
" and wherein a is 1, b is 1 to 42, c is 0.1 to 15, d is 0.1 to 15
. ,
l 10~4098
i
¦ and e is a number determined by the valences of other elements
¦ and usually from 3.75 to 150.5.
Ii A more preferred catalyst is a composition represented
¦j the ab~ve formula in which the ratio among a, b, _, d and e
~' lies in the following range: a:b:c:d:e = 1:(1-28~:(0.2-10):
l ~0.1-10~:C6.4-101~.
! The catalyst according to the present invention can
be prepared in a conventional manner well known in the art,
I - for example, by the following procedures.
1 In one casej compounds of respective constituent
elements and the carrier, if a carrier is used, are mixed.
The resultant mixture is evaporated to dryness and then the
dried product is calcined.
ll In another case, a solid carrier is impregnated with
¦ compounds of each constituent element. This impregnated
Il carrier is evaporated to dryness and then calcined.
I In still another case, a solid carrier is impregnated
with compounds of some constituent elements and then subjected
to a heat treatment, preferably at a temperature of 200- 700C.
¦ The partly impregnated carrier is further impregnated with
compounds of the other constituent elements. This twice
impregnated carrier is evaporated to dryness and then calcined.
In any of the aboYe-described procedures the calcina-
~ tion temperature lies preferably in a range of 300-700C,
2S more preferably in a range of 400~ - 550C.
.,
1094098
ll I
li .
~i ,
¦ If necessary, the calcination or the heat treatment
may be carried out in an atmosphere of reducing agent such
as hydrogen, hydrocarbon etc.
, Examples of the compound of each constituent element
i are listed below.
! Examples of palladium compound include palladium
I chloride, palladium nitrate, pallad~um sulfate, palladium
black and the l~ke.
I Examples of phosphorus compound include orthophos-
1 phoric acid, phosphorous acid, hypophosphorous acid, pyro-
phosphoric acid, metaphosphoric acid, polyphosphoric acids,
their salts, and the like.
Examples of antimony compound include oxides,
hydroxides and chlorides of antimony, such as antimony
1 dichloride, antimony pentachloride, antimony trioxide, and
the like.
Examples of compound of the X constituent include
nitrates, hydrochlorides, phosphates, sulfates, oxides,
1~ hydroxides of the X constituent, and the like.
I More concrete procedures for the preparation of
the catalyst of this invention are explained as follows:
To an ammonia solution of any suita~le palladium
, salt, for example palladium chloride, is added ortho-
~ phosphoric acid (as 85% aqueous solution~,phosphorous acid,
2~ hypophosphorous acid or any other phosphoric acid or salt
_ g _
.
Il lO9A098
Il I
! thereof, yielding a clear solution. To this clear solution
I are further added a metal salt or oxide of antimony (such! as antimony trioxide) and a metal salt or oxide of the X
constituent, yielding an aqueous solution. Any suitable carrier
¦ is i~mpregnated with such aqueous solution, evaporated to
dryness and then calcined in air at 300- 700C, preferably
400 - 550C for five or more hours.
The carrier which has been impregnated first with a
palladium salt and thermally treated at a temperature
of preferably 200- 700C may ~e impregnated with phosphoric
acid, antimony trioxide and X compound and then calcined.
Or, the carrier which has been impregnated with
antimony trioxide and X compound and thermally treated m~y be
~ impregnated with palladium chloride dissolved in ammonia water
I and then calcined in air and thermally treated in an atmosphere
¦ of reducing agent such as hydrogen. The resultant substance
¦¦ is impregnated with phosphorus compound and then calcined.
¦ In either case the activity of the catalyst is not
I¦ adversely affected.
'l The catalyst can include a carrier to lower the catalyst
concentration, increase the catalyst strength or to enhance
1~ the economy of the catalyst. A suitable amount of a carrier
l! may be impregnated with a small amount of the catalyst. Even
I¦ a large amount of a carrier may be used.
1, As the carrier, may be employed inert substances such
,
., ,
1~ ,
1094098
l
as silica sol, silica gel, silicon carbide, a-alumina,
Alundum, celite, boiling bubble stone, aluminum powder,
silicahydro gel and the like.
l ` The catalyst may be used in the form of spherical
~ granules, pellets, particles crushed to suitable size, tablets
etc.
The aliphatic alcohol used herein is, for example,
methanol, ethanol, propanol and the like.
l The molecular oxygen used herein is usually air.
lQ ¦ The oxygen may be diluted with an inert gas which does not
adversely affect the reaction, such as nitrogen, carbon
dioxide and the like.
To the reaction system methacrolein or acrolein and
oxy~en are fed as a gaseous feed mixture in such proportions
! that the molar ratio of methacrolein or acrolein to oxygen
is preferably 1:(0.5-30), more preferably 1:(1-8).
When methacroiein or acrolein is oxidized by oxygen
in the presence of the catalyst of the invention and in the
~ absence of an aliphatic alcohol to produce methacrylic acid
1 or acrylic acid, the presence of steam is indispensable. If
steam is absent, the oxidation of methacrolein or acrolein to
1i¦ methacrylic acid or acrylic acid takes place almost to the
il least extent. Since an aliphatic alcohol is present according
I¦ to the process of the inventionr the destined products,
1, methacrylic acid and methacrylate or acrylic acid and acrylate,
!
1094098
I
can be obtained in high yields even in the absence of steam.
The selectivity of methacrylic acid and methacrylate or
acrylic acid and acrylate is very high. However, by introducing ¦
a smali amount of steam the conversion of methacrolein or
acrolein is further accelerated and the yield of methacrylic
acid and methacrylate or acrylic acid and acrylate is further
increased.
The steam is added in the gaseous feed mixture in such
proportions that the amount of steam is preferably 0.1 to 28
moles, more preferably 0.5 to 10 moles per mole of methacrolein
or acrolein.
The aliphat~c alcohol is preferably fed in an amount
from 0.1 to 25 moles, especially 0.3 to 10 moles per mole
of methacrolein or acrolein.
The temperature for carrying out the reaction is
not so critical. The reaction may preferably be carried
out at a temperature of 180 to 370C, especially 200to 330C.
The reaction can be carried out at atmospheric
pressure or at lower or higher pressures. In general it is
¦ convenient to carry out the reaction at atmospheric pressure.
¦ ~ preferable range of pressure is 0.3 to 15 atm.
ll The gaseous feed mixture can be introduced at
¦¦ any desirable space velocity, preferably at a space velocity
~ of 300 to 15,000 Q-gas/Q-cat.hr, especially 700 to 8,000
' Q-gas/Q~cat.hr.
!
,,
I, .
, 1 ~
1094098 1.
'.
1, ' ,
¦¦ According to the present invention satisfactory results
¦¦ are obtained even when the reaction is carried out at space
velocities as high as 2,000 to 8,000 Q-gas/~-cat.hr. Further
the service life of the catalyst is maintained for a long period
¦ of time under such conditions.
i The catalyst of the present in~ention may be applied
in any form selected from a fixed bed, a fluidized bed and a
moving bed.
The following examples are illustrative of the catalyst ¦
and the process of the present invention. In the examples, the
terms "conversion of methacrolein or acrolein", "selectivity
of methacrylic or acrylic acid", "selectivity of a methacrylate
! or acrylate", "yield of methacrylic or acrylic acid", "yield
l of a methacrylate or acrylate", and "space velocity" are
¦ defined as follows:
Conversion of methacrolein or acrolein
Moles of methacrolein or acrolein reacted 100
Moles of methacrolein or acrolein fed x
Selectivity of methacrylic or acrylic acid
l = Moles of methacrylic or acrylic acid produced x 100 % ¦
j Moles of methacrolein or acrolein reacted
, Selectivity of a methacrylate or acrylate
_ Moles of methacrylate or acrylate produced x 100 %
l Moles of methacroleln or acrolein reacted
`' Yield of methacrylic or acrylic acid
Moles of methacrylic or acrylic acid produced
I Moles of methacrolein or acrolein fed x 100
! `~
, . ,
l - 13 -
I094098
1, ~
¦I Yleld of a methacrylate or acrylate
¦ _ Moles of methacrylate or acrylate produced x 100
Moles of methacrolein or acrolein fed
l Space Velocity (SV)
The flow rate* of a geseous feed mixture (Q-gas/hr.)
The volume of a charged catalyst ~Q-cat.~
*calculated on a basis at the normal temperature
and pressure
Example 1:
While 16.0 g of Aerosil (SiO2) was heated and agitated,
0.4 g of antimony trioxide and 0.17 g of magnesium phosphate
(III) were added. The mixture was concentrated by heating, then
evaporated to dryness and thereafter, dried at 100C for eight
hours. The dried mixture was impregnated with an aqueous
15 1 ammonia solution containing 0.44 g of palladium chloride,
evaporated to dryness, thereafter repeatedly washed with 10
liters of distilled water and dried. The dried product was
subjected to a heat treatment in the air at 450C for five
hours and then thermally treated in an atmosphere of hydrogen
20 ¦ at 450C for five hours. The product was impregnated with
6.5 g of hypophosphorous acid ~30 %), evaporated to dryness.
Thereafter, the dried product was calcined in the air at 450~C
for five hours. The thus obtained product is named Catalyst A,
I¦ the composition of which is represented by the formula:
25Pdl,OPl2,3sbl.OMgO-5o33-75 1'
* trade mark
- 14 - ;
.,
10~4098
1~ s
l! '
A reaction tube of stainless steel having an inner
¦¦ diameter of 20 mm was filled with 10 mQ of the Catalyst A
Il and dipped in a bath of molten nitrate. With the use of this
¦¦ reaction tube filled with Catalyst A the oxidation of methacrolei~
was carried out for 120 days.
As the phosphorus-containing compound was used
trimethyl phosphate in the form of a 0.1 % solution (i.e.
methanol-water solution). This solution was fed in an amount
l of 5 cc per hour.
A gaseous feed mixture contained methacrolein, methanol,j
oxygen, steam, nitrogen and phosphorus in a relative molar
ratio of 1:1:2:5.5:18.1:1.8xlO 3.
The gaseous feed mixture was supplied at a SV of 1565
Q-gas/Q-cat.hr.
,¦ The thus obtained products were determined by gas
chromatography. The results are shown in Table 1.
Table
Reaction Tempera- Conversion Selectivity Yield of Yield of
time ture of of meth- of meth- meth- methyl
~day) the ni- acrolein acrylic acid acrylic meth-
trate (%~ + methyl acid acrylate
ll bath (~C) methacrylate (~
I I (% )
1'Initial 285 74.5 89.3 40.0 26.5
! 40 285 74.7 8g.2 40.3 26.3
120 285 74.7 8g.2 40.1 26.5
~' i
., .
i 1094098
On the production of methacrylic acid and methyl
methacrylate from methacrolein and methanol small amounts
of by-products were derived, including 1.0 %
l of acrylic acid, 0.5 % of acetic acid, 2.5 % of carbon dioxide
5 i and 4.0 % of carbon monoxide.
Exam~le 2:
Example 1 was repeated except that metaphosphoric
acid in the form of a 0.1 % solution (i.e. methanol-water
solutionl was used as the phosphorus-containing compound in
place of trimethyl phosphate.
Other reaction conditions were the same as those of
. Example 1. The results are shown in Table 2.
Table 2
Reaction Tempera- Con~ersion Selectivity Yield of Yield of
time ture of of meth- of meth- methacry- methyl
(day) the ni- acrolein acrylic lic acid meth-
trate ~%) acid + meth- (%) acrylate
bath (C~ yl methacry- (%)
late (%)
2Q stage 285 74.3 88.6 39.826.0
285 74.4 88.6 39.826.1
120 285 74.5 88.5 39.926.0
I . _ .
! On the production of methacrylic acid and methyl
~I methacrylate from methacrolein and methanol small amounts of
1¦ by-products were deri~ed, including 1.5 ~ of
,~l acrylic acid, 0.7 % of acetic acid, 2.0 % of carbon dioxide
'i
l - 16 -
., ,
" :
1094098
il
¦1 and 4.3 % of carbon monoxide.
,¦ Example 3:
I
A catalyst having the same composition with that of
¦ Example 1 was prepared in a similar way to that of Example 1,
5 l¦ except that hypophosphorous acid was replaced by phosphorous
acid.
With the use of the catalyst the reaction was carried
out in a similar manner as described in Example 1. The results
l are shown in Table 3.
¦ Table 3
Reaction Tempera- Converslon Selectivity Yield of Yield of
I time ture of of meth- of meth- meth- methyl
l (day) the ni- acrolein acrylic acrylic methacry- !
i trate (%) acid + meth- acid late
1 bath (C) yl meth- (%) (%)
, acrylate (%)
¦¦Initial 281 75.1 - 88.5 40.2 26.3
~¦stage
281 75.0 88.8 40.5 26.1
120 281 75.1 88.3 40.3 26.0
¦ On the production of methacrylic acid and methyl
¦¦ methacrylate from methacrolein and methanol small amounts
of by-products were derived, including 1.6 % of
¦¦ acrylic acid, 0.4 % of acetic acid, 2.3 % of carbon dioxide
and 4.3 % of carbon monoxide.
~5 ' Example 4:
1 l
,, The reaction described in Example 1 was repeated ~,
. ~ .
; 17 -
Il 1094098
¦l except that acrolein was used in place of methacrolein.
The results are shown in Table 4.
Table 4
l Reaction Tempera- Conv~rsion Selectivity Yield of Yield of
¦ time ture of of acro- of acrylic acrylic methyl
(day) the ni- lein acid + acid acrylate
trate (%~ methyl acry- (%~
bath ~C) latè (%)
stage 280 98.2 95.7 66.5 27.5
280 98.3 95.7 66.8 27.3
120 280 98.1 95.6 66.3 27.
On the production of acrylic acid and methyl acrylate
l from acrolein and methanol small amounts of by-products were
I derived, including 1.0 % of acetic acid, 1.5 % of carbon
¦~ monoxide, I.2 ~ of carbon dioxide and 0.5 ~ of acetone.
¦¦ Example 5:
The reaction was carried out under the same conditions
as those of Example 1, except that the phosphorus-containing
1 compound was not fed at all. The results are shown in Table 5.
l Example 6:
I The reaction was carried out under the same conditions
¦¦ as those of Example 4, except that the phosphorus-containing
compound was not fed at all. The results are shown in Table 5.
Il !
l i l
!
, ~
~i
"
' - 18 -
1094098
i
I
l Table 5
I .
Exam- Reaction Tempera- Conversion Selectivity Yield of Yield of
ple time ture of of meth- of meth- meth- methyl
No. (dayl the ni- acrolein acrylic acrylic methacry~
trate (%) acid + me- acid late
! bath (C) thyl meth- (%) (~)
l acrylate
. .... ~_
5 stage 287 74.7 88.8 40.0 26.3
287 70.1 90.2 39.1 24.1
Exam- Reaction Tempera- Conversion Selectivity Yield of Yield of
ple time ture of of acro- of acrylic acrylic methyl
No. (~ay) the ni- lein acid + acid acrylate
trate (~) methyl (%) (%)
bath (C) acrylate
6 stage 281 98.0 94.5 66.2 26.4
l 10 281 92.0 93.7 63.1 23.1
Examples 7 - 80:
The catalysts having the compositions shown in Table
6 were prepared in a manner similar to that described in Example
1, if necessary, using salts of the X constituent, ammonium
Il metavanadate and rhenium chloride etc. With use of these
! catalysts the reactions were carried out under the same condi-
I, tions as those of Example 1, except that the phosphorus-contain-
¦~ ing compound was not fed at all. The results are shown in
Table 6.
~1 1
.,
i~ 1,
, .
.
1094098
.~ a) i
~I s ,1 ~ ~ ~ u~ o o o~ ,!
dP . . . . . . . . . ~ . I'
~ ~ n ~ ~ ~ o ~o ~ ~ I~ ~ ~ ~ ~ ,
a~ ~ c) s~ ~ ~D ~D 0~ CO 0~ t~ CO 1` CO 1` C~ CO r` I~ I
Q~ !
~ o ~ ,
. 4~ ~ 1,
o ~ .,
~1 ~ co o ~ 00 ~ ~~ ~1
.............. ll
S S ~ ~ ~ ~ o o In ~r ~ ~ o ~ o ,1 oo i
O J,J J,~ ~ _r-l rl ~ ~ N~1 ~ ~ I
V
~1 I
O
~1 ~ t ~
. ~ 1~ ~ . . . . . . . . . . . . . . I
--I S ~ U~ Ul O O00 U~ D ~ O
. ~ O ~ ~ et'
.
~ I
S~O a) '
~ ~ ~ O d~ U~ O O U~ , I
S~ O ~ ~-- 1~-) Il') Il~ O ~i er N 11~ N ~ ~r ~ In N
O-rl ~ O 1~ t~ I` 1~ r~
a) c,) U~ E3 11~
_l
~ 1 ~1 1
E-l S.l O-r~ _
IU 5~ ~U ~_) 0~7 ~D C~ D N U~ ~ C~
a) ~ .~ O t~ I`I` t` a~ I` I` t~ co ~ 1` ~o t~ ~ .
. N N N N ~I Nn N N N N N N N i
. O ~r
.,1 U~
U~ U) ~ N U7 Ir)
u~ cs~ 0
O u~ ~D O~ ,~
n o. ~ o u ~D
r~i _I NO ~ O C~ N O O O O f O
o R O O 1` R R R ~i ~ ~i ~i R 1`
U u~ i R ~i u~ i R R R R U~ R
~) Q Q u~ o ~i u~ i
u~ n fi ~ fi ~ ~ ~D
{i ~i ~ t~l O ~i O ~ Ci O ll~i
~ ~ ~ ~ ~: ~ ~ m ~ m ~
--I ~, ~, ~ ~ , N ~i ~ ~ N ~i
NIn N ~
Pt ~ P~ ~ ~ ~ i
fi ~i fi r-ti f f f f ~ f f ~i ~i l
~i ~ ~i ~ ~ ~i ~ ~ ~ ~i ~ ~ ~ i
P~ i
a~ !
~ ll
E~ O ~` 00 cn O ~i N ~ ~r L~ ~ t~ a> ~ O l
~1 --- f i ~1 ~ i --- ~i r-i f --I N i
i
i!
- 20 -
1094098
~+~ .
,~ c) a)
~ n ~ ~ ~ r- I~ ~ Cl~ ~ ~ r~ O O ,'
.~ ~ .............
O ~1 ~ O~o ~ ~ ~ ~ ~ In o~ u~ ~ o I
C) a) ~ a) ~ ~ ~ ~ oo ~ ~ co 1~ co co 1
aJ~ ~ ~
C~ ~ .
rl Q) O
U~ o ~ ~ ~
~ ~ ,.
O ~ In u~
~,~_ ............. .
.~ .C >1 0\ ~J O C~ ~ ~ o
fV~ -- ~ ~ ~1 ~1 ~ ~ ~1 ~N ~ ~ 1
~ l
~ l
Ot~ ~I L~ 1.
............. ll
.~ O CO m t'~ CO O U~ o ~ ~D !.
o o ~ ~ ~ ~ ~ er ~ er ~ ~ d' ~ ~ ~1
_ ~
o ~ ,1
~ I q~ ~ ~1
_ s~ o aJi u~ In i'
a)I~_
~4 ~ O ~ ~ ~J O '.D '~ r) ~ ~ ~ N ~
~D S O ~ l-- I` I` I` I~ I` I` 1-- 1~ 1` ~- 1`1` r- 1;
o-~l a) o "
C~ li
Q CU,~ I !'`
E~ s~ 0
~ C) ~ O O O CO ~ ~D o ~ o ~ !
k ~ ~ o I` I` co r~ r` co ~o 1` co 1` t` ci~ 1` i:
O ~ _ ~ ~ ~ ~ ~ ~ t~
E~
~ ~ l
.~ ' ~ CO 11
-~ . U~
u~ ~ n . o ~. ~r I`
O . . O ~ o U~ ~ L'l O ~ ~ j,
~ r~ . rt Lt O l~
i~ r~7 ~ ~ O O N OO O Q O ~r 1:
O O OO O ,~ ~ O _l ~ ~ U~ ~ ~ i,
C~ ~ ~~ R Q Q 1` R Q u~ u~
,Q QQ u~ ~Q U~ ri ~ !.
U~ 7 . oC~ .
u~ ~ ~ ~ n~ ¢i Ul ~ ,~ o s~ o
:~ ~; ~CK O Z Z ~ itr; P; Q u~ I
.~ ~ ~~) K ~ ~ Z ~ o L ~ ~ u~ I
~1 ~1 ~ r~ ~1 ~ ~ ~ ~ ~D ~ C`l ~ i
P~ P~ ~ P. P~ ~ P~ P~ ~ ~ ~ P~ ~ !,
,1 ~ ~ ~ ~ ~ ~ ~ ~ ~i ~ ~ ~ i i
~i ~; ~ ~5 ~ ~ ~ ~ ~-i ~ ~ ~ ~~
~ ,
~ .`
~. ,.
~ O ~ ~ ~ ~ U~ n o ~ ~ ~ I i
X Z ~
,
1094098
1. :
. .
,
~+a~) I
a) I` ~ ~ ~ ~ O ~ O r~ o .
,,.~.,, ~_ . . . . . . . . . . . . . . i
U ~1 ~ d~ ~ ~ ~ o ~ ~ c~ ~ ~ o ~ o
u a) nS :~, ~1 ~ x co 1-- c~ co 1` t` 1- ~ ~ 0 ~` 00 CO ! I
~ ~ U ~:: ~ I!
a~ u 1!
u~ 0~ il
1l
o ~ l
~1 ~ ~1 1~ ~ Il') t~ ('~) 11~ 11~) C~ 1~ IJ-) t~ 11-) ~r) !
. ~ ~1 ~1~ . ~ . . . . .
,~ O ~ 1~ O ~ I~ CO O ~ G~ ~ ~1
~ 1~ ~ ~ ~ I ~1
-,~ a) a) u
00
I ~ ~ ~ o t~
00 Il~ r o ~ ~r o o~
a~ ~ ~ ~ ~ ~ ~ ~r
~ ~ ~U d
~5 1~ .~ I
~ S~ O Q) ~ u~ ~D In ~ ~ U~ ~ C5~ U~ U~ In 00 n
~ ~ 1~1~ .
O ~ ~ S O dP ~ ~ Ul ~ ~ ~9 er ~ D ~ ~ ~ ~r
~ ~ O ~ ~ ~ r~ ~ r~ ~ r~ ~ ~ I` r~ ~-- I` I` I` I~
_ V'~
~1
I
0 ~ _~ ~ co ~ ~ ~ t~ ~ .
~1 ~ a) ~ s O r~ 0 ~ ~ 00 ~ t`
t~ f~ ~ ~ `J N ~ !
E~ a) ~ s ~ ~d !
E~
.,1 u~ ~ ~ In . u~ u~ U~
c~ o u O
O ~o ~ ~ ~
~ ~ ~ ~) ~ O ~ `D O ~ ~D
~ O O O O O ~ O O - O O --I O O !
o ~ N Q ~ ~ o ~ ~ Q ~1 ~ R r~3
V R Qu~ Q r(2 Cl~ Q R u~ R Q u~ R Q
u~ cn ~ u~ t/~. Q u~
~ ~ U~ ~1 ~. ~1 ~.
u~ ~ ~o ~ o ~ o ~ ~1
~ ~ ~ ~ V ~ m m
,1 ~ ~ ~ ~ ~ C.) ~ ~ E~ ~ ~ u~
~ ~1 ~ ~ ~1 ~ ~) ~t ~ ~ ~ N ~ ~i
p~ I
(d ~ r l I
C~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ .
P~
Q~
~- ~
~ O ~ ~ D 1~ o ~1 ~ f'? ~ Ir) ~ t-- I !
X Z
r~ .
- 2 2 - ' i
1094098
~s~+~
,, C) ~ .
O 1` ~ ~ In ~ ~ o 1` oo u~ ;:
,~ .............. ,.
U ~ ~ ~ O G~ ~ o ~~3 o ~~rt~ ~ ~
V ~I~ 1-- ~ ~a) ~1` co co~DCO 1` ~ CO
u~
~ ~ a) u !
U~ 0 ~ d ,,
~ a~ 1.
o ~ ~ o~~ ~ ~ ~ ,i u~ I~ ~ o ~ ~ ~ !~
~1 ,1_~ . . . . . . . . . . . . . . 1'
.C ,~ ~1 ~ ~ D ~J O 1` ~ ~ ~ ~ 00 1~ CO
a~ , _ ~ ~ ~ ~1 ~ ~ ~ ~ ~ ~ ~ _1 ~ ~ li
,1 ~ ~ U ~l
O u o a~ o t~ ~ ~ O 1` ~1 l
~I~,_ .............. ,
~~ P u~ o co ~ ~ r~~r ~ o ~ ~ 1
~ ~7 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~r ~ ~ er , 1
,~ v ; I
O ~ ll
V ;~
~ ~ ~'
S~ O ~ U~ 1`
~D ~ I -1~ . . . . . . . . . . i'
o ~P n u~ er ~D er ~ n ~ ~ ~ ~ u~ ~ Lr~ 1`
~ O ~ ~~ r~ I
G) 0~1 0 0 ;
.4 C~ 1,
E~ ~q~ l .
~ 0 ~ _ ~ O ~ l
Q. O ~ ,C 1~ r- oo ~1~co o t~ co ~ D ~ I
~~ ~ ~ l
Id
E~.4 1.
~ 1,
~0 a~ 1'
~CO ~ D I !
~.
U~ U~ O ~ ~
O~ ~ ~ ~ O o ~ ~ ~ l
O ~ U~ 9 ~ ~ ~ o ~ ~ o ~ ;
~3 ~ O O O ~ O O O O ~ O ~1 I'
O R ~ ~ Q o ~ oo ~ ~ R ~ ~ !:
O u~ Q R u~ ,Q ~ ~1 ~ ~ u~ Q ~ u2 Q !
i~ j !
.~ I ~ I
o ~ ,1 o a) a) O O O o h h o 1: ; i
~I Zi Z ~ 4 V V O V V h :~: i
m ~ ~ z ~ o ~ r V ~ ,~D ~t ~ ~ ~1 ~ ~ ~ ~ ~ ~ ; I
P~ ~ P. ..
~ ~ ~ ~ ~ ~1 ~ ~ ~ ~ ~ ~ ~ ~ ~ i.
V ~ ~ ~ ~i ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ,
P~ .:
a)
.
O c~ ~ o ~ ~ ~ ~ n ~ 1` co ~ o ~ .
. X Z ~ 9
- 2 3 -
109~098
, .
il
s ,.,
.~ ~ + ~ oo ~ 1 ~ O ~ I~ o r~ '.
~ .............. ~'
'~I S ~rl ~ dP ~r ~ ~ OD ~ n er 1` ~ a~ ~1 ~ ~ ~ 1'
t~ 1'
li
a) ~ .1
~ q~ aJ o . !!
U~O~
I .
O ~ ~ ~ ~ cn In
,~ ............. ~ I'
~, ~ O CO ~D ~ ~ GO ~ ~1~` ~ ~ 0
_1 ~S S ~ _I ~I N _I _I ~ N ~1~`1 N ~ i
. ~ .) ll
~0 0
.,.1 O Ln 1~Il')C~ U~I` O 1~ 0 ~ OU')
I ~ . . . . , . . . . . . . . ~
--I S ~i dP O C~ D O 0~ r~ I,
a~ ~ ~ r ~ ~ ~.
~ ~ ' i
~i ~ 1 i
~ O ~U ~1 IJ') ~Il'~Il~I~ ~OD11')1~ ~ ~1
O ~, I ~1~ . ~ . . . . . . . . . .
~ ~ ~i S O dP
_ o ~ ~ h 'J ~` t~r` ~ t~ r_1~r` t`r` l` ~ l` 1
~ U~ !
Q~ ~ I il
~ ~ o.
R a~ ~ ~ ~ ~ ~ o
~ ~ ~ ~ S o ~ u~ ~ a~ ~ ~ ~D u~ t~ ~ ~ r~ co t~ I
E-~ ~ ~ S S-l ~ ~ ~ ~ ~`J ~ ~ N ~ ~
~ ~9 1.
rl 11l ~ l
In U~ ~ ~ ~ U~ In u~ ~ I
. .~ O U~ O i
u~ ~ 1 0 a~ l i
OIn O t~ ~ ~1 ~ ~ O ~ U~ i
QlO --I ~ ~ O O OIn Q o o oo o l
~ ~ Q o o ~D ~t <~ . u~ ~ o ~1 ~ Q I
O R u~ _I c~ Q Q Q o u~ Q ~ Q Q u~ i
V V~ u~ Q Q u~ Q u~ ~ :
. u~ o ~ a~ ~ ~ .
~:: o ~ ~. G) ~ ~ Q Qo
t~ ~ ~ ~ ~o t~ Q
m ~ l
U~ I ~~ i
P~ ~ ~ ~ P~ ~ ~ ~ .
_l l
~i ~ ~ ~ ~ ~ ~ I'
~ ~ ~1
!
~ i~
~ o C~l ~ ~ U~ ~ I~ ooC~ o ~ ~ ~ ~ ~ ; i
~c æ ~ 'I
~ li
,
- 24 -
1094098
'.
.,
,.
ll ll
~ ~
li
r~ S ~1 ~_ . ~ . . . j!
dP ~ O ~r ~r ~ ~l
Q~ CO OD 1~ ..
a, ~0 ~ ~ ~
4, a~ !1
O ~ ~ u~ ~ ~1 ~ ll
~ ~_. . . . . . I
~ ~ ~r) ~11~ ~ ~1 !
~ ~ l
, ~q I
O ~ ll
.,1 O r~ ~ o
_ ~ a~ D O
~5 a~ 1 ~ ~ ~ ~er ~
~ ~ d ,
UO I ~ '~ I
_ ~-1 0 ~U ~ u), I
~ 1~1_ . . . . . I
P~0P, ~ ~ ~ ~ ~ i
O ~~ 1~ l
a) ~ !
R I !
` ,~ ¢ ~ I - : !
E~ ~, 0 ~ ~ 7 o l
o ~ OD a~
.C ,~ i i ~ ~ c~l N
~ er . I
~, o I
~Fi ~D o~ ~D l
O ~ CD ~
o
ti O O O O
. U ~ ~ iJl ~i N
~) ~1
tll N 151 N
r~i ~ i
i~ -~i l
~ ~ ~ I
c~ ~ I!
Q), ll
~0 ~ i Q ~1
iX~Z ~ co ~ 1
t 1l
ll 1094098
!
1: .
Ii .
¦¦ Examples 81 - 102:
Reactions using the catalysts of the said Examples
were carried out under the same conditions as those of Example
1. ~he result- re b~wn in Table 7
~_ !
', `
l i
~ - 26 - ~
;, .
1094098
cn~ ,~c~oo u~ ~ oocoo ~ r r~
~h- ..- .. -. .- ... -. ...
~NN ~ NNN
~ oo a~ oo ot~ co oo co co co co co co o~ oo OD CO 00 C~ CO CO CO l
i
0~ lll
.~ ~ ~ ~ ~N ~ ~ ~ ~N
~1 _1_ . . . . . . . . . . . . . . . . . . . . .
N~N ~ ~ ~ ~ ~
~_ ~NN NNN NNN NNN NNN NNN NNN
~0~
.~ ~ ~0~ ~ON ~ ~0 ~ ~
~t_l _ .. . ... .. ... ... ...
. ~ o~ CD OO a~ o o o co co co ,~ o ,~ o o o a~
a~ , ~ ~ ~ ~ ~ ~r ~r er ~ ~ ~ er er ~ er ~r ~r
~ ~
~0 ~ ~ ~ ~ ~ ~NN ~ ~
a) 1~ .. -. .. ... ... ... ...
~0~ NN~ ~ ~ ~ ~ ~ ~
g O~ t~ 1` 1` 1` 1` 1` 1` 1~ 1` 1` r~ t~ I` l` r`
ul C~ m
.4 ~ o ,
5~ ~
~NN O O O
~ a~~ ~ 1~ ~ ~ 1~ ~ 1~ 1~ 1~ ~ 1~ 1~ t~ 1`1` r-- 1~ 1~ t-- ~ ~ 1~
~ N NN NN~ NN N N~N NNN NNN NNN
~
I
O _
I
a ooo ooo ooo ooo ooo ooo ooo I
V0~ ~N ~N ~N ~N ~N ~N ~N l
,~_ ~ _l ~ ,_1 ~_1 ~1 _~
~0 ~ ~ r` ~ In CO ~ ~ l
l ~ ~ ~ N N ~ ~ ~ l
~ l
xzta~ I
a) l
P~- i
~0 ~ N ~ ~ ~ ~ ~ 1~
XZ 00 CO CO ~ CO CO CO ll
Il
5 ~,
- 2 7
~094098
.,
~ ~ ~0 ~00 ~ ~N~ ~ _~ .
.~_ ... ... ... ... .-- . ... !
~-~ N~ ~0~ NNN ~ ~ NNN NNN ,1
C) ~ OD CO CO t` CO CO ~0 CO 0~ ~ CO 0 1~ CO O~ CO 0~ CO CO ~, ~
a~ 'i
U~ O ~ ~ ~ .,
~ O ., ill
O ~ ~ ~ ~ ~NN ~0 ~ ~N .
~ _ . . . . . . . . . . . . i
f ~ ~ ~00 000 ~ ~0 ~ NNN i
N N N N ~ . ~I N N _l _l N N ~ ~I ~ I l
. ~ 1
qo' c) - 1,
~ ~ t` CO Ct) O 1~ 1~ 11~ N ~ 1` 1~ 1~ C~ O O O 5~ O ~D 0 00 i
_. ~ ~ ~ o~ ~ cn o ~ ~ o o o o~ ol o o o a~ o ~) o o~ i
a)~ rl~, ~ ~ ~ ~ ~ er~ ~ l
1:~ `
U S: i
_ s-~ o a~ _~; ~ ~ ~r ~ D CD ~ I` U~ D ~ ~ N _l ~ ll
er ~r ~r ~ ~ er ~U) Il'~ U~ r er ~ In In u~ !
~i O ~ ~-1 ' ~ r~ 1` 1` 1` 1~ r~ 1~ t~ 1` 1` r- 1- r~ 1~ l
~ ~a''~u,
~ 0~ i
a) ~ a) ~ ~ ~ ~ ~ ~ _I _I r~ ~ ~ ~ ~ ~ ~ ~1
~ a) ~ ~c I` t` l` r~ ~ r~ r~ ~ t~
N~N NNN N~N NNN ~NN NNN NN~
~ I
,,01 ~ I
000 000 000 000 000 000 000 I
V~ ~ ~N ~N ~N ~N ~N ~N
~_ ~1 ~1 _~ _1 ~ ~1 ~
~ !
~ 1
~ o ~ r- o ~ ~ ~ ~ u~ I
~ S ~ ~r ~r ~ ~r Il. u~ !
~c z ~ ~ 1!
a) ll
l ~0 ~ ~ O ~ N ~ ~ 1~`
X Z C~ CO C5~ ~ CS~ C~
i 1i3
, .
2 8 - '
lo~A098
~ o~ ~ ~ ~o~ ~ ~ ~ l
~ . . . . . . . . . . . . . . . . . . . . . ~i
rl ~ r,~ d. ~ ~ d' ~ ~1 ~ N t~ l~l 111 ~ ~ ~ ~ ~ ~r ~ ~1 ~ ~ Ij
O ~ CO CO C~ 00 ~ CO 0~ CO OD 0~ C~ Cl~ CO CO CO CO CO l l
a) ~ .,C'; I'
U~O~+~'. i,l
!
O ~ O ~ ~ t~ OD 00 U~ I~ Lr) U~ r ~ o ~ ~ u~ e
o ~ CO~ ooo ~ ~ ~ ~ I
~I S~ ~ ~ ~J ~ r~ ~1 ~ ~ ~ ~ N ~ ~ ~ N ~ t`~
Q)~ ~1 l
;~aa5 . ~ .
~ 1 _ ~ ~ ~ ~1 0 0t~ l~ co ~ U~ 0 ~ 0 0 ~ ~1
. ~ a O\o ~ _i ~i~ ~ ~~ a~ ~ ~ _~ ~1 co c~ co O O O a~
a) ~ S~ ~r ~r ~ ~ r ~ ~ ~ ~ ~ er ~ ~ ~ er e
:~1 a) u u
1 u~ ~ 1~ r~~1 o ~1 ~ ~ ~r ~ ,1 o ~n ~1 o o
~ ~o ~ . . . . . . ~ ~ ~ ~ ~ . . . . . . . . . . l
~ ~ O ~ h t` r` ~` u~ (~ ~ ~ ~ ~ ~r ~r et' ~ r ~ D l I
I` ~ U
. I
a) Iq~l o~ I
R 5~1 o ~ 1~ ~ ~~ C~ a~ ~ ~ ~ ~ t~ 1 u~ r) t`~
1~1 ~ I)t~ I~ I~U~ 9 t` 1` ~ ~ ~ r~ ~` ~ I`
, E~l ~`t O ~ .C~ ~ ~ ~ ~I NN ~I ~ ~ ~ ~ ~ ~I ~ ~ ~ ~ ~1
O O O O Q
~'~t~ ~1 ~1 ~1 _1 ~1 _1 ~1 ~ '
~ o ~1 o~ ~1 ~r i~ o ~ ~ I
~ in ~D ~9 ~D t` I~ t~ l
IX53u I ~
~i O It~ ~ I~ co ~ O ~1 l
X:Z ~ ~ a~ ~ ~ ~o ~1 l
t
l I
~og4098
~ u~ -- ~
O ~ S~ ^ . . `I
U d~ ~r ~ ~ I
u ~ cl~ co oo ll
a) ~ u ~3 ~ '.
~no~+~ ill
O ~ ~I N N
1 ~1 ol~ N N N
U
O~U 00~1
~ OOO
~ ~
i
_ ~1 ~ I` 15~ !
~ ~ ~r ~r ~ ~
O ~-rl~U I~ i
r- Il.
~ ~01 ~
~ ~ ~ ~ ~ ll
E-~ ~ ~ ~ ~ ~ c~ N ll
E~ ,Q ll
~ 1~'
O ~ 000
~:40:~ ~
~ ~ ~ I~ i,
X~
~Z
,,
` 1094098
li
Examples 103 - 104:
The catalysts having the compositions shown in Table
8 were prepared in a manner similar as in Examples 7 - 80.
With use of these catalysts the reactions were carried out
, under the same conditions as those of Example 1. The
result are shown in Ta~le 8.
I
il ~
- 31 -
~ ~094098
,~ ~ ~
O O O U~ ~ ~9
o~O . . . . . .
,, .~ ~,~ ~ U~ U~
U ~ ~ ~ ~ c~ o~ co ~ 1--1`
_, F ~ F ~
u~ O n~ + ~ ,'
~ Q~ i'.
_l ~ ~ ~g ~ o C~
. . . . . . 1
cn~a~ ,loO !,
a~
. ~ F F
o C) . I,
.,, _1 o o o ,1 _1 ,1
i ~ . . . . . . jl
O O O cr o~ o~ ll
.~ ~ ~ ~ ~ ~ i
,~ l
~F ~ ~ l
. I
: ~ I
5~ 0 ~ ~ U~
. ~ t,1~ . . . . . .
dP 0 0 0 U~
. ~ O ~ h '-- t` I` r` 1`1--
O'rl ~ ~
. . U ~ : .
. l I
. Id ~ ~J
S-l O ~ --un u~ u~ ~ ~ ~ ! I
a~ ~ u r~ ~ I~ t~
~ ~ ~ J l
oo . E-~ q ~ i
~ i
_~:
. _~ ~~ O O O O O O j !
R ~~ ~ ~ i'
E~ ~ ~ ~ ,~ ~ ll
0~
Q~ o :~ il
~ ~:1 R ll
~ ,, u~
o ~ P.~ 1,
V ~ ~ I
I
ll ~Z ~ ~
,i
I .
I
- 32 ',
. 1094098
i, ,
,i Examples 105 - 126:
Reactions described in Example 4 were repeated
Il except that catalysts having the compositions shown in Table
,i 9 prepared in the same manner as in Examples 7 - 80 were used
.1 and the phosphorus-containing compound was not fed at all.
The results are shown in Ta~le 9.
;
" .
~ 33
1094098
~ .c ',,
.~ U~ lll
+ ~ ~ ~
"_ ~ ~ ~n ~ ~ ~ ~ ~ ~ ~
~ ~ o~ I
h ¦;
a) ~ !,
U~ O ~ ~
i
.
o ~ ,!
,~ ~ ~1 ~ ~_1 ~ ~ ~ ~ 1` ~_I ~ _I
~,
P ~D Lr~ ~ ~ ~ ~ U~ ~ U~ ~u~ ~r
. ~ ~ N ~~ ~ ~ ~ ~ ~ ~ N
q~ :
.
~1 ^ . ~ ~ `
~ ~ ~ I
. '~ ~ ~ ~ O l
o qJ , t~ ~ ~ ~ ~ O
~ ~ O ~ I` ~D ~ ~ GO ~ n ~ oo
0 ~ cn ~ I
O Q
:
~ ~ ~,
~ ~ol ~, I
~ ~ ~ ~ ~1 ~ ~D ~D ~ ~ O ~ U~ I .
E~ ~ ~ ~ ,S 0 t~ co 1~ o~ r~ oo co oo ~ oo 1~ ~ !
E'~ J,) ~ ~ ~ ~ ~ ~ ~ N t~ t~ l
S:: ' I
O ' 11~ In 11~ 11? In u~ Lr) I
. ~ ~ ~ Il O ~ ~ I` ~ a~ ~ o
~ ~ ~ 1-7 ~ ~ ~1 ~7 ~ '1 ~D ~ ~ I~
O O O 'r O O R O O O O O O
U ~ O ~ ~1 U~ ~ ~ ~ ~ o
R R~ R R ~r) R Q R R R R R
u~ n
U~ ,1 ~ U~ ~ ~ o ~1 ~ ~1 ~ ~ _I
r~ R
m ~ m æ
~D ~ ~ ~ ~ ~ ~ ~ ~ ~ ~7
~1 ~ ~ ~ ~ ~ ~ ~ ~1
~ P~
C) ~ ~ ~, ~ ~ ~ _, ~ ~ ~ ~ ~ _
~i ~ ~ ~i ~ ~ ~ ~ ~ ~ ~ ~i ~ l
P~ I j
~ ll
O ~ ~ I~ ~ ~ o ~ ~ ~ ~ i
~c Z o o o o o
~:~ ~ ~,1
,; I '.
- 3 4 - , `
10~4098
,
_, ..
. . . . . . . . .
,
+ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ,'
~~1 i l
a~ ~ ~
a~ !!
U~ O ~ ~ 1
i,
q~ ~ Ij
O ~ I~ 1 0 ~ ~ ~ O .
_1~ . . . . . . . . . !
r ~ ~ ~ I
_~,c ~_ ~ ~ ~ ~ ~ ~ ~ ~ ~ l
,
~ l
o C) I
"~1 r~ ~ ,
~s _l ~ . . . . . . . . . 'i
~1 ~1~ dP ~ _I N O 1~ ~ U~ u ) ~1
a~ "--
~ ~
O ~ ~ T~ o _1
s~ o al--; .
~ In ~i U~ ~ 00 In ~D r~ ~ ,
a~ ~i O h ~ ~i ~ ~ oi a~ ~
41 c~
~d ~ q~ I o
h o-,~i ~ ~ oo ~ I~ N a~ ~ !
O ~ G~i cor~ ~ 1
N ~; ~ ~i~ri ~ ' ~i i
~ ~ l
a) ~ )
E-'~ .. ,i
~ ii
O r
I
.,1 ~ u~ In ~ U~
~q . ~
O ~ ~ I` ~ O ~ O
~ ~ ~ ~1 ~ IS)
E3 O O O ~ \ Q O ~ I
O --I ~ ~ O ~ ~ o o I
U Q RQ ~I QIn Q ~I R Ij
u~ Q u~ Q u~ l I
~ ~ ~~ U~ ~10 ~ ~q
U~ 0 ~ ~ ~ a) tD Q ~ ~--1
C) ~ m P~ ~ ~ ~1
,
_1 ~ ~ ~ ~ ~ ~ ~1
P~ .
~ ~1 ~ ~ ~ ~ ~ ~ ~ ~i ,~
C)
~:4 Pl P. P. P. P~ P. ~ P~ i`
O, I`
j~ O 0~ ~ O r-r ~,`i ~ ~ Lr) ~D i
~i Z ~ ~ ~,ti ~i ~i ~ ~i
X r-i ~i r~'i ~r~ r ~i
i`
, ~ .
-- 35 - ~`
~ .
1094098
li ,
! Example 127:
il The reactions described in Example 4 were carried
l~ out for 120 days using the same catalysts as in Examples
! 105 - 126. The results obtained after 120 days were nearly
1 the same as those obtained at the initial stage. The yields
of acrylic acid and methyl acrylate were not decreased for
12Q days.
Example 128:
l Examples 1 and 4 were repeated except that solid
l phosphoric acid (celite/phosphorus = 50/50~ heat treated at
550C was used as the phosphorus-containing compound in place
i of trimethyl phosphate.
On the upper side of the catalyst layer consisting
l of 10 m~ of Catalyst A was placed 5 ml of the solid phosphoric
¦ acid.
The results were nearly the same as those of Examples
1 and 4.
Example 129;
l Examples 81 - 104 and 127 were repeated except that
1 orthophosphoric acid, metaphosphoric acid, pyrophosphoric
acid and solid phosphoric acid were used as the phosphorus-
containing compound in place of trimethyl phosphate, respectively,
¦ in each case. It has been found that the results are nearly
,~ the same as those of Examples 81 - 104 and 127.
,! !
- 36 -
i 1094098
,,
Example 130: 1
Examples 1 and 4 were repeated except that the amount
of the phosphorus-containing compound supplied was changed.
l The amount of phosphorus contained in the compound was changed
1 in the range of 0.5 wt% to 1 x 10`3 wt% based on total amount
of water and methanol fed. The results were nearly the same
as those of Examples 1 and 4.
Example 131:
A catalyst was prepared by following the procedure
noted in Example 1, except that the impregnation order of
palladium and phosphorus was changed. Using this catalyst the
reactions were carried out in the same manner as in Examples
1 and 4. The results were nearly the same as those of Examples
1 and 4.
Example 132:
A catalyst was prepared by following the procedure
noted in Example 1, except that palladium and phosphorus were
impregnated at the same time. Using this catalyst the reactions
were carried out in the same manner as in Examples 1 and 4.
The results were nearly the same as those of Examples 1 and 4.
i Example 133:
16.0 g of Aerosil, 0.4 g of antimony trioxide, 0.17 g
'I of magnesium phosphate, 6.5 g of hypophosphorous acid and 10 cc
¦¦ of an aqueous ammonia solution containing 0.44 g of palladium
I chloride were mixed together. The mixture was evaporated
.
37 ~,
. .
1094098
i! .
!l i
¦ to dryness. The dried product was calcined in the air at 450C
for five hours. The catalyst thus obtained had a composition ~,
represented by the formula: ¦
I PdlP12 3SblMgo~sO33~75
¦¦ Using this catalyst the reactions were carried out
in the same manner as Examples 1 and 4. The results were
nearly the same as those of Examples 1 and 4.
Example 134:
Example 1 was repeated except that the gaseous feed
mixture was supplied at a SV of 4000 Q-gas~Q-cat. hr. The
¦ results are shown in Table 10.
Table 10
i Reaction Tempera- Conversion Selectivity Yield of Yield of
l time ture of of meth- of meth- meth- methyl
l (day~ the ni- acrolein acrylic acrylic meth-
I trate (%) acid ~ acidacrylate
bath ~C~ methyl (%) (%)
methacry-
I
iInitial 296 67.7 89.5 37.223.4
stage
296 67.6 89.3 37.423.0
120 296 67.6 ag.4 37.423.0
.
. .
ll 1094098
¦ Example 135:
¦ Example 4 was repeated except that the gaseous feed
mixture was supplied at a SV of 4000 Q-gas/Q-cat. hr.
The results are shown in Table 11.
~ Table 11
Reac- Tempera- Conversion Selectivity Yield of Yield of
tion ture of of meth- of meth- methacry- methyl
time the ni- acrolein acrylic acid lic acid methacry-
(day) trate (~) ~ methyl (~) late
bath (C) methacrylate (~)
Initial 287 91.6 93.6 62.1 23.6
stage
287 91.4 93.7 62.3 23.3
120 287 91.3 93.9 62.4 23.3
Example 136-139:
The reaction described in Example 1 was repeated in
the presence of Catalyst A with a varying molar ratio between
reagents in a gaseous feed mixture. The results are shown in
Table 12.
¦ _ 39 _
,,
1, ,
"
1094098
¦l In Table 12, gaseous feed mixtures B - E have the
¦¦ following relative molar ratio:
feed acertOhlein : methanol : oxygen : stea~ : nitrogen : phhOrus
il B 1 1 2 0 18.1 1.8xlO
C 1 2 4 5.5 13.6 1.8xlO-~
D 1 1 3 8.0 15.9 3.6xlO I
E 1 4 8 13.0 25.0 1.8xlO 1
Table 12
i Exam- Gaseous Tempera- Conversion Selectivity Yield of Yield of
ple feed ture of of meth- of meth- meth- methyl
No. mixture the ni- acrolein acrylic acrylic methacry-
trate (%) acid ~ acid late
bath (C) methyl (%) (%)
methacry-
late 1%)
136 B 300 66.5 88.7 37.5 21.5
137 C 276 76.5 83.1 35.2 28.4
138 D 277 77.6 80.2 40.0 22.2
139 E 273 63.5 87.8 39.6 16.2
_
Example 140 - 143:
i The reaction described in Example 4 was repeated in
l~~ the presence of Catalyst A with a ~arying molar ratio be.ween
Il' reagents in the gaseous feed mixture. The results are shown in
li Table 13.
Il In Table 13, gaseous feed mixtures F - I have the
1. 1
"
- 40 -
~094098
¦ following relative molar ratio:
feed acrolein : amnOhl : oxygen : steam : genr : phhOorus
1 F 1 1.5 2 0 18.1 1.8x10-3
G 1 2 4 7.5 13.6 3.6xlO 3
H 1 1 8 12.5 21.6 1.8xlO 3
I 1 4 5 3 12.3 5.4xlO
Table 13
Exam- Gaseous Tempera- Conversion Selectivity Yield of Yield of
ple feed ture of of acro- of acrylic acrylic methyl
No. mixture the ni- lein acid + acid acrylate
trate (%) methyl (%) (~)
bath (C) acrylate
140 F 287 94.8 91.7 58.1 28.8
141 G 272 98.8 93.0 64.9 27.0
142 H 270 98.7 90.2 67.3 21.7
143 I 282 95.1 92.7 60.1 28.1
.
I
!
.
~ ' I
- 41 - !
