United States Patent (19) 11, 3,935,282

Kudo et al. (45) Jan. 27, 1976

54 PROCESS FOR PREPARATION OF 3.354.23 l l if 1967 Maloy et al..................... 26()1621 H

Oy-NAPHTHOL 3,378,59 | 4/1968 Freure ............................ 26()/62 H
(75). Inventors: Ken-ichi Kudo, Niihama; Tadayuki
Ohmae, Kobe; Akihiko Uno, Primary Examiner-James O. Thomas, Jr.
Toyonaka, all of Japan Assistant Examiner-W. B. Lone
Attorney, Agent, or Firm-Sughrue. Rothwell, Mion,
(73) Assignee: Sumitomo Chemical Company, Ltd., Zinn & Macpeak
Osaka, Japan
22 Filed: May 6, 1974 57 ABSTRACT
(21) Appl. No.: 467,541 -
a-Naphthol is prepared by dehydrogenating o-Tetra
lone in the presence of a catalyst comprising (1) plati
52 U.S. C. P. P. so a s so a a n a so a v s a s a s 260/621 H num or a platinum compound, (2) an alkali metal salt,
51 Int, Cl........................................... C07C 39/14 and (3) a manganese compound and/or a chromium
58 Field of Search............ 260/621, 62 H, 621 R; compound supported O gamma-type alumina car
252/47 ricr. By using such catalyst, the conversion of o-Tetra
- lone is markedly increased, and the catalyst life is very
56 References Cited much prolonged.
UNITED STATES PATENTS
2,848.5l () 8/1958 Myers et al......................... 252/471 3 Claims, 2 Drawing Figures
U.S. Patent Jan. 27, 1976 3,935,282

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3,935,282 2
Examples of alkali metal salts which can be used as
PROCESS FOR PREPARATION OF a-NAPHTHOL the second active component of the catalyst are sodium
BACKGROUND OF THE INVENTION sulfate, sodium carbonate, sodium acetate, sodium
chloride, and sodium chloroplatinate.
1. Field of the Invention Examples of manganese compounds which can be
This invention relates to a process for preparing a used as the third active component of the catalyst are
naphthol by dehydrogenating ketotetrahydronaphtha manganous sulfate, manganous chloride, manganous
lene (to be referred to herein for brevity as “o-Tetra nitrate, manganous acetate, manganic sulfate, and so
lone," a well-known registered trademark), and more dium permanganate. Examples of chromium com
specifically, to a process for preparing a-naphthol 10 pounds which can be used as the third active compo
which comprises dehydrogenating o-Tetralone using a nent of the catalyst include chromous sulfate, chro
catalyst comprising (1) platinum or a platinum com mous acetate, chromic chloride, chromium trioxide,
pound, (2) an alkali metal salt and (3) a manganese and sodium bichromate.
compound and/or a chromium compound supported It is apparent that the carrier should be one capable
on a gamma-type alumina carrier. 15 of maintaining the activity of the catalyst at a high
2. Description of the Prior Art level. In the preparation of the catalyst composition
a-Naphthol is a very important industrial material used in this invention, y-alumina is used as a carrier.
useful, for example, as dye intermediates or raw materi Based on the information that the pore diameter of a
als for agricultural chemicals. carrier exerts influences on the catalytic activity, con
A number of studies have previously been made on 20 version, selectivity and catalyst life in a catalytic reac
methods for preparing a-naphthol. Typical prior art tion, extensive studies have been made on the dehydro
techniques are methods such as the alkali fusion of genation reaction in accordance with this invention of
o-chloronaphthalene and the hydrolysis of o-naphtha a-Tetralone in the presence of the specific catalyst
lenesulfonic acid. These methods, however, are not composition described above to prepare a-naphthol.
free from the formation of 6-naphthol as a by-product, 25 Although, it is well known that micropores (pores hav
and therefore, the resulting product is contaminated ing a pore diameter of not more than 100 A) are impor
with a certain amount of such by-products. Further tant factors for the activity and selectability of the
more, these known methods are disadvantageous for catalyst composition it has been found that macropores
commercial mass-production because an undesirable (pores having a pore diameter of more than 100 A)
procedure such as alkali fusion is employed. The pro 30 significantly influence the conversion of o-Tetralone,
duction of a-naphthol by the dehydrogenation reaction the selectivity to ov-naphthol, and the catalyst life. Spe
of o-Tetralone is described, for example, in U.S. Pat. cifically, we have found that by selecting alumina using
No. 3,378,591, but the catalyst used in the method as a carrier on the basis of the distribution of macro
disclosed therein has a short lifetime and is disadvanta 35 pores and the ratio of the macropore volume to the
geous as a commercial method. total pore volume of the carrier, the yield of o-naphthol
Lengthy studies on methods for producing a-naph is increased, and the catalyst life is remarkably length
thol by the dehydrogenation reaction of ov-Tetralone as ened.
a starting material in the presence of a catalyst com Thus, it is more preferable to use y-alumina as a
prising various kinds of metals or compounds thereof carrier material containing micropores and, at the same
supported on alumina have been made to arrive at the 40 time, having a pore diameter distribution from 100 A to
present invention. 75,000 A, that is, having a macropore volume of at
SUMMARY OF THE INVENTION least 0.2 cm/g, preferably at least 0.3 cm/g.
The pore size distribution of the alumina carrier is
According to this invention, therefore, there is pro measured by means of a porosimeter (Aminco 60,000
vided a process for preparing ov-naphthol, which com 45 psi). The typical pore diameter distribution of an ordi
prises dehydrogenating a-Tetralone in the presence of nary alumina carrier as used in this invention is shown
a catalyst comprising (1) platinum or a platinum com in FIG. 1 of the accompanying drawings, and that of a
pound, (2) an alkali metal salt, and (3) a manganese preferred alumina carrier as used in this invention
compound and/or a chromium compound supported which has macropores is shown in FIG. 2.
on a y-alumina carrier. 50 There is no particular restriction on the method of

BRIEF DESCRIPTION OF THE ACCOMPANYING supporting the active catalyst components on the alu
DRAWINGS
FIGS. 1 and 2 show the typical pore size distribution
of an ordinary aluminum carrier and a preferred alumi
num carrier, respectively.
DETAILED DESCRIPTION OF THE INVENTION
According to the process of this invention, the con
version of o-Tetralone is remarkably improved and the
activity of the catalyst is extremely lengthened, as com
pared with the method disclosed in the above-cited
U.S. Pat. Thus, the process of this invention is a very
advantageous commercial process for producing o
naphthol. - --
The platinum compound used as one active compo
nent of the catalyst can, for example, be chloroplatinic
acid, or its salts such as sodium chloroplatinate.
mina carrier, and any of those methods generally em
ployed can be used. For example, the y-alumina car
rier, preferably one having a macropore distribution as
55
defined above, can be immersed in an aqueous solution
having the catalyst components employed in this inven
tion dissolved therein, and the volatile substances are
removed at atmospheric or reduced pressure at room
60
temperature or at an elevated temperature, thereby to
support these catalyst components on the y-alumina
carrier. Alternatively, the first, second and third cata
lyst components can be supported sequentially on the
y-alumina carrier. In addition, the y-alumina carrier
can be immersed in an aqueous solution of the first
65 component for a certain period of time, and the first
component is then reduced using a conventional reduc
ing agent such as hydrazine, formaldehyde or hydro
gen, after which the second and third components are
 3,935,282
3 4
supported. ralone and hydrogen were continuously fed into the
The amount of the catalyst supported is not particu reaction tube at a flow rate of 20 ml/hour and 180
larly limited, and usually, it is 0.1 to 5.0% by weight, ml/hour, respectively, and they were contacted with
preferably 0.1 to 1.0% by weight as platinum, 0.1 to the catalyst at a reaction temperature of 360°C under
4.0% by weight, preferably 0.1 to 2.0% by weight, as 5 atmospheric pressure. With the lapse of time, the con
the alkali metal, and 0.1 to 5.0% by weight as manga version of o-Tetralone and the selectivity to a-naphthol
nese and/or chromium. changed as shown in Table 1 below.
The O-Tetralone used as a starting material is usually Table 1
of pure quality. At times, however, starting materials
containing more than 20% o-Tetralone, or starting 10 Lapse of Time Conversion of
or-Tetralone
Selectivity for
or-naphthol
materials containing naphthalene can also be used, and
there is no particular limitation on the content of the (hours) (mol%) (mol%)
impurities except that catalyst poisoning impurities 10 90 94
should not be present. 100 89 95
In practice, the supported catalyst prepared by the 15 200
300
87
86
98
98
method described above is charged into a reaction zone 400 85 98
such as a tubular reactor having a suitable length and a 500 85 98
suitable diameter and activated by heating at 200° to
400°C for 10 to 30 hours under a stream of hydrogen.
Then, the starting material o-Tetralone is continuously 20 COMPARATIVE EXAMPLE
fed together with hydrogen into the reaction tube and
the dehydrogenation reaction is carried out by contact A catalyst containing 1.0% by weight of platinum,
ing the reactant with the catalyst at an elevated temper 1.32% by weight of sodium ion and 0.54% by weight of
ature under atmospheric or pressurized conditions. sulfate supported on y-alumina was prepared in the
The reaction temperature is 200 to 450°C, prefera 25 same way as described in Example 1 except that chro
bly 330” to 410°C. The reaction pressure is normal mium trioxide was not used.
atmospheric pressure or higher. Usually, it is advanta a-Tetralone was dehydrogenated in the same way as
geous to operate at about normal atmospheric pres in Example 1 using a catalyst obtained as described in
SeS. Example 1 above except that the activation of the cata
The amount of the starting o-Tetralone to be fed is 30 lyst was performed for 150 hours, and the flow rate of
not particularly limited, but usually, it is 0.3 to 5.0 hydrogen was changed to 150 ml/min. The results ob
liters/liter of catalyst/hour, preferably 0.4 to 2.0 liters/- tained are shown in Table 2.
liter of catalyst/hour. Table 2
Hydrogen is preferably used as a carrier gas. The
molar ratio of Hafo-Tetralone ranges from 0.5 to 15, 35 Lapse of Time Conversion of Selectivity for
a-Tetratone a-naphthol
preferably 2.0 to 6.0.
According to the process of this invention, since the (hours) (mol%) (mol%)
catalyst life is extremely prolonged as compared with 10
00
88
86
96
97
the known conventional catalysts, the number of regen 200 8 98
erations and rechargings of the catalyst can be mini- 40 300 77 98
mized, and the process of this invention is very advan 400
500
73
67
98
98
tageous commercially.
The following Examples are illustrative of preferred
embodiments of the present invention with Compara
tive Examples shown at the same time. It will be under- 45 EXAMPLE 2
stood that these examples are given for the purposes of Manganese acetate tetrahydrate (0.80 g) and 1.40 g
illustration and the present invention is not to be inter of sodium acetate trihydrate were dissolved in 31 g of
preted as limited to those examples. Unless otherwise water, and 1.5 ml of an aqueous solution of chloropla
indicated, all parts, ratios and percents are by weight.
o tinic acid (platinum content 12.1 g/100 ml) was further
EXAMPLE added. 18 g of the same spherical y-alumina as used in
Anhydrous sodium sulfate (0.14 g), 0.44 g of anhy Example 1 was immersed in the resulting aqueous solu
drous sodium carbonate and 0.35 g of chromium triox tion for 24 hours. Then, by the same procedure as used
ide were dissolved in 31 g of water, and 1.5 ml of an in Example 1, a catalyst containing 1.0% by weight of
aqueous solution of chloroplatinic acid (platinum con 55 platinum, 1.32% by weight of sodium ion and 1.0% by
tent 12.1 g/100 ml) was further added. 18 g of spherical weight of manganese supported on the y-alumina was
y-alumina (average diameter 3 mm, bulk density 0.55 obtained.
Using 30 ml of the catalyst obtained above, dehydro
g/cm, specific surface area 150 m/g) was immersed in genation of o-Tetralone was performed under the same
the resulting aqueous solution for 24 hours. Then,
water was removed while rotating the mixture under 60 results
reaction conditions as in Comparative Example 1. The
obtained are shown in Table 3 below.
heat at reduced pressure, thereby to form a dry carrier
supported catalyst containing 1.0% by weight of plati Table 3
num, 1.32% by weight of sodium ion, 0.54% by weight Lapse of Time Conversion of Selectivity for
of sulfate, and 1.0% by weight of chromium. or-Tetralone a-naphthol
30 ml of the catalyst thus obtained was packed in a 65 (hours) (mol%) (mol%)
stainless steel reaction tube with an inside diameter of
O 9 83
18 mm and a length of 400 mm, and activated in a 00 90 88
stream of hydrogen at 370°C for 15 hours. Then, a-Tet 200 89 92
 3,935,282
5 6
Table 3-continued was obtained. Using 30 ml of this catalyst, dehydrogen
Lapse of Time Conversion of Selectivity for ation of a-Tetralone was performed under the same
a-Tetralone o-naphthol conditions as described in Example 1. The results ob
tained are shown in Table 5.
(hours) (mol%) (mol%) 5
300 87 93
Table 5
400 86 93 Lapse of Time Conversion of Selectivity for
500 85 96 or-Tetralone or-naphthol
(hours) (mol%) (mol%)
O
O 9. 88
EXAMPLE 3 100 90 92
200 88 95
Manganese acetate tetrahydrate (0.40 g) and 1.40 g 300 86 96
400 85 96
of sodium acetate trihydrate were dissolved in 31 g of 500 84 97
water, and 1.5 ml of an aqueous solution of chloropla 15
tinic acid (platinum content 12.1 g/100 ml) was further
added. 18 g of the same spherical y-alumina as used in While the invention has been described in detail and
Example 1 was immersed in the resulting aqueous solu with reference to specific embodiments thereof, it will
tion for 24 hours, and then using the same procedure as be apparent to one skilled in the art that various
used in Example 1, a catalyst containing 1.32% by 20 changes and modifications can be made therein with
weight of sodium ion, 1.0% by weight of platinum and out departing from the spirit and scope thereof.
0.5% by weight of manganese supported on y-alumina What is claimed is:
was obtained. Using 30 ml of this catalyst, dehydrogen 1. A process for preparing ov-naphthol, which consists
ation of o-Tetralone was performed under the same essentially of dehydrogenating ketotetrahydronaphtha
conditions as used in Example 1. The results obtained 25 lene at a temperature of from 200 to 450°C at from
are shown in Table 4.
atmospheric pressure to a slightly elevated pressure, in
Table 4 the presence of a catalyst comprising (1) platinum or a
Lapse of Time Conversion of Selectivity for platinum compound selected from the group consisting
or-Tetralone or-naphthol of chloroplatinic acid and the salts thereof; (2) an al
30 kali metal salt selected from the group consisting of
(hours) (mol%) (mol%)
10 91 84 sodium sulfate, sodium carbonate, sodium acetate,
100 90 92 sodium chloride and sodium chloroplatinate; and (3) a
200
300
88
87
94
95
maganese compound selected from the group consist
400 85 95
35
ing of maganous sulfate, manganous chloride, manga
500 85 96 nous nitrate, manganous acetate, manganic sulfate and
sodium permanganate and/or a chromium compound
selected from the group consisting of chromous sulfate,
EXAMPLE 4 chromous acetate, chromic chloride, chromium triox
ide and sodium bichromate; supported on a y-alumina
40 carrier.
Chromium trioxide (0.17 g), 0.40 g of manganese
acetate tetrahydrate and 1.40 g of sodium acetate trihy 2. The process of claim 1, wherein said y-alumina
drate were dissolved in 31 g of water, and 1.5 ml of an carrier has a macropore volume of at least 0.2 cm/g.
aqueous solution of chloroplatinic acid (platinum con 3. The process of claim 1, wherein said catalyst con
tent 12.1 g/100 ml) was further added. 18 g of the same 45
tains 0.1 to 5.0% by weight as platinum of said platinum
y-alumina as used in Example 1 was immersed in the or said platinum compound, 0.1 to 4.0% by weight as
resulting aqueous solution for 24 hours, and then using alkali metal of said alkali metal salt and 0.1 to 5.0% by
the same procedure as described in Example 1, a cata weight as manganese and/or as chromium of said man
lyst containing 1.0% by weight of platinum, 1.32% by ganese compound and/or said chromium compound
weight of sodium ion, 0.5% by weight of chromium and 50 supported on said y-alumina carrier.
0.5% by weight of manganese supported on y-alumina ck >k cc clic ck

55

60

65