USOO5300703A
Knifton
[45]
Date of Patent:
5,300,703
Apr. 5, 1994
[75] Inventor:
OTHER PUBLICATIONS
K. Nowinska et al, J. Chem. Soc. Faraday Trans; vol.
I .
[73] Asslgneei
Hams NY~
[57]
ABSTRACT
[22] Filed;
[51]
[52]
[58]
AP]; 5, 1993
H8n[xMl2O40l
[56]
References Cited
where x=P or Si, M=Mo or wv and n is an integer
2/1986
4.912.264
5,059.727 10/1991
1171.896
12/1992
5,175.375 12/1992
568/794
Ito ............. ..
Knifton et
.. 568/794
.
568/794
7 Claims, No Drawings
5,300,703
catalyst.
'
'
35
alkylphenols.
Although heteropoly acids (EPA) and their salts
have been known and studied for over 160 years, the
catalyst is also employed in U.S. Pat. No. 3,876,710 to 50 about 20 years ago.
In an article titled Heterogeneous Catalysis by Het
Hitachi to produce PTBP from phenol and isobutylene.
eropoly
Compounds of Molybdenum and Tungsten",
A BF3 catalyst is used for of phenol and isobutene in
by
M.
Misono,
Catal. Rev. Sci. Eng, 29. 269 (1987)
British Patent 1,294,781 to Hoechst where the product
1,249,571 is related.
In German Offen. 3,443,736 to l-Iuels the catalyst is a
(Eq. 1)
(Eq. 2)
5,300,703
(Eq. 3)
The acid strength tends to decrease upon reduction 45 821, ibid, it is stated massive HPAs exhibit purely
Bronsted acidity. In terms of strength, they are superior
or partial substitution of M0 or W6+ by V5+ owing
to aluminosilicates and, at least in the dehydration of
to an increased negative charge. The thermal stability of
propanol,
are much more active than zeolite I-IY.
the elements constituting a polyanion vary and gener
origins of acidity.
Though there has been a long history of studies on 55
5,300,703
ignored.
(Eq. 5)
on > C,,H h.
phenol products.
SUMMARY OF THE INVENTION
In accordance with the foregoing, the novel method
of the instant invention for preparing alkylphenols com
'
5,300,703
TABLE I
Tvpical heteromlvmolvbdate anions
CONDENSATION RATIOS
CHEMICAL FORMULAS
20
n is an integer which is 4 or 5.
trons.
would
likely
have
the
Keggin
structure,
.v
__
LHS '
'
| '
in
or '-
our
The support should preferably comprise an inert 35 Conversion of ole?ns (wt %) is estimated in the fol
lowing examples using the equation:
compound. Compounds which may be employed are
those containing elements of Group III and IV of the
Periodic Table. Suitable compounds include the oxides
loo-t
)x too
10o
X
120, LHSV l.
1-30 wt %.
reaches 15.7 at 80 C.
55
of Ex. 2, where:
Preparation of alkylphenols is conducted in a ?xed
a) P'Nonylphenol to o-nonylphenol weight ratio is
bed, continuous flow reactor.
13.2 at 120 C.
The reaction is conducted under adiabatic conditions.
b) Nonylphenol to dinonylphenol ratio climbs to 16.3
The hot spot or maximum temperature of the reactor
at 100 C., LHSV 3.
can be in the range of 60-250 C. and preferably 80 C. 65
3) In general, this class of heteropoly acid catalyst can
to 140 C. The preferred temperature depends on the
choice of reactants, however, in the case of nonene and
provide:
5,300,703
.
'
10
Acidity=0.40 meq/g
EXAMPLE 3
5
(Ex. 4).
e) Good performance at high LHSVs (Ex. 3).
4) The generation of nonylphenol from phenol/nonene
regulating devices.
1200 g
25
W = 16.7%
Acidity=0.25 meq/g
TABLE 2
EX.
3
PhOH/Co"
MOLAR
CONTROL
TEMP
CATALYST
RATlO
(Cl
Ex]
1.34
NONYLPHENOL SYNTHESES
FEED
PRODUCT COMPOSITION (721"
RATE
~g/cv
~-lc-
(Cc/hr)
80
100
120
100
100
SAMPLE
Cq'"
PhOH
FS-l
50.1
49.9
1
2
3
4
5
10.6
3.8
4.3
8.2
10.4
24.9
20.8
21.4
26.0
28.8
400
400
400
800
1200
NP
DNP
54.7
64.0
63.3
55.3
51.4
9.6
11.2
10.2
10.3
9.3
HOT SPOT
TEMP
4.8
4.9
6.5
5.3
6.0
75.4
75.2
73.0
74.4
73.1
("C1
95
111
130
108
110
"Designations: Nonene. Cq
TABLE 3
EX.
SAMPLE
l
3
5
1
1
3
EXAMPLE 2
55
63
51
15.7
11.2
12.2
5.7
6.2
5.5
'
EXAMPLE 4
79
91
79
55
65
H3O=0.9%
5.
5,300,703
11
12
TABLE4
NONYLPHENOL SYNTHESES
FEED
PRODUCTCOMPOSITIONW?)
PhoH/c6-
CONTROL
MOLAR
TEMP
RATE
cc.)
(cc/hr)
Ex.
CATALYST
RATIO
Ex. 2
1.34
30
100
120
100
100
400
400
400
300
1200
ag/c~
SAMPLE
cq-
PhOH
FS-l
50.11
49.29
1
2
3
4
s
39.6
31.3
26.0
36.1
34.0
33.4
36.7
33.5
39.4
311.2
'
NP
25.2
29.6
36.9
22.9
26.1
HOT sPoT
._1~
TEMP
7.1
7.8
9.2
6.8
6.4
7.5
6.7
6.0
6.4
6.6
78.1
711.3
79.2
79.6
31.0
("c1
86
103
120
103
132
TABLE 5
NONYLPHENOL PRODUCT ANALYSES DATA
CONTROL
NONENE
NP
WEIGHT RATIO
Ex.
SAMPLE
TEMP (C.)
LHSV
CONV. 1%)
CONCW?)
1
3
s
30
120
100
1
1
3
21
48
32
25
37
26
p-NP/o-NP NP/DNP
10.4
13.2
12.3
EXAMPLES
13.3
10.3
16.3
from phenol plus mixed nonenes using a solubilized 25 supported on an inert oxide selected from the group
consisting of titanium dioxide, alumina and silica. as
heteropoly acid catalyst.
well as mixtures thereof, at a temperature of from 60 C.
A mix of phenol (85.0 g, 0.90 mole). nonene (85.0 g.
500 psi.
55
65
It
I.
it
It